Sample records for catalyzing ester bond

  1. A free-standing condensation enzyme catalyzing ester bond formation in C-1027 biosynthesis. (United States)

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


    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

  2. Copper-catalyzed oxidative C-O bond formation of 2-acyl phenols and 1,3-dicarbonyl compounds with ethers: direct access to phenol esters and enol esters. (United States)

    Park, Jihye; Han, Sang Hoon; Sharma, Satyasheel; Han, Sangil; Shin, Youngmi; Mishra, Neeraj Kumar; Kwak, Jong Hwan; Lee, Cheong Hoon; Lee, Jeongmi; Kim, In Su


    A copper-catalyzed oxidative coupling of 2-carbonyl-substituted phenols and 1,3-dicarbonyl compounds with a wide range of dibenzyl or dialkyl ethers is described. This protocol provides an efficient preparation of phenol esters and enol esters in good yields with high chemoselectivity. This method represents an alternative protocol for classical esterification reactions.

  3. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

    Munk, Line; Sitarz, Anna Katarzyna; Kalyani, Dayanand;


    illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin...

  4. Lipase-catalyzed (trans)esterification of 5-hydroxy- methylfurfural and separation from HMF esters using deep-eutectic solvents. (United States)

    Krystof, Monika; Pérez-Sánchez, María; Domínguez de María, Pablo


    5-Hydroxymethylfurfural (HMF) is a valuable biomass-derived building block. Among possible HMF valorization products, a broad range of HMF esters can be synthesized. These HMF esters have found some promising applications, such as monomers, fuels, additives, surfactants, and fungicides, and thus several catalytic approaches for HMF (trans)esterifications have been reported. The intrinsic reactivity of HMF is challenging, forcing the use of mild reaction conditions to avoid by-product formation. This paper explores the lipase-catalyzed (trans)esterification of HMF with different acyl donors (carboxylic acids and methyl- and ethyl esters) mostly in solvent-free conditions. The results demonstrate that lipases may be promising alternatives for the synthesis of HMF esters-with high productivities and reactions at high substrate loadings-provided that robust systems for lipase immobilization are applied to assure an adequate reusability of the enzymes. Once (trans)esterifications have been conducted, the separation of unreacted HMF and HMF esters is performed by using deep-eutectic solvents (DES) as separation agents. DES are able to dissolve hydrogen-bond donors (e.g., HMF), whereas non-hydrogen-bond donors (in this case HMF esters) form a second phase. By using this approach, high ester purities (>99 %) and efficiencies (up to >90 % HMF ester recovery) in separations were obtained by using choline chloride-based DES. PMID:23456887

  5. Solvent effects on hydrogen bonding between primary alcohols and esters

    Institute of Scientific and Technical Information of China (English)



    The interaction by hydrogen bond formation of some primary alcohols (1-heptanol, 1-octanol and 1-decanol) with esters (methyl methacrylate, ethyl methacrylate and butyl methacrylate) was investigated in non-polar solvents viz., n-heptane,CCh and benzene by means of FTIR spectroscopy. Formation constants and free energy changes of complex formation were determined. The dependence of the equilibrium constants and free energy changes of complex formation on the alkyl chain length of both the alcohols and esters are discussed. The solvent effect on the hydrogen bond formation is discussed in terms of specific interaction between the solute and solvent.

  6. Choline Chloride Catalyzed Amidation of Fatty Acid Ester to Monoethanolamide: A Green Approach. (United States)

    Patil, Pramod; Pratap, Amit


    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

  7. Synthesis of Fluoroalkoxy Substituted Arylboronic Esters by Iridium-Catalyzed Aromatic C–H Borylation

    KAUST Repository

    Batool, Farhat


    The preparation of fluoroalkoxy arylboronic esters by iridium-catalyzed aromatic C–H borylation is described. The fluoroalkoxy groups employed include trifluoromethoxy, difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, and 2,2-difluoro-1,3-benzodioxole. The borylation reactions were carried out neat without the use of a glovebox or Schlenk line. The regioselectivities available through the iridium-catalyzed C–H borylation are complementary to those obtained by the electrophilic aromatic substitution reactions of fluoroalkoxy arenes. Fluoroalkoxy arylboronic esters can serve as versatile building blocks.

  8. Lipase catalyzed synthesis of aromatic esters of sugar alcohols

    NARCIS (Netherlands)

    Croitoru, R.; Broek, van den L.A.M.; Frissen, A.E.; Davidescu, C.M.; Peter, F.; Boeriu, C.G.


    Commercially available lipases (Candida antarctica lipase B, Novozyme 435, Thermomyces lanuginosus lipase, and Lipozyme TL IM), as well as sol-gel immobilized lipases, have been screened for their ability to acylate regioselectively xylitol, sorbitol, and mannitol with a phenolic ester in a binary m

  9. Enantioselective Rh-catalyzed hydrogenation of N-formyl dehydroamino esters with monodentate phosphoramidite ligands

    NARCIS (Netherlands)

    Panella, L; Aleixandre, AM; Kruidhof, GJ; Robertus, J; Feringa, BL; de Vries, JG; Minnaard, AJ; Aleixandre, Alicia Marco; Kruidhof, Gerlof J.; Feringa, Bernard


    Enantioselectivities up to > 99% ee were achieved in the rhodium-catalyzed asymmetric hydrogenation of N-formyl dehydroamino esters using morrodentate phosphoramidites as chiral ligands. The substrates were synthesized by condensation of methyl isocyanoacetate with a range of aldehydes and with cycl

  10. Nickel-Catalyzed Cross-Coupling of Redox-Active Esters with Boronic Acids. (United States)

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


    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

  11. Ruthenium(II)-PNN pincer complex catalyzed dehydrogenation of benzyl alcohol to ester: A DFT study (United States)

    Tao, Jingcong; Wen, Li; Lv, Xiaobo; Qi, Yong; Yin, Hailiang


    The molecular mechanism of the dehydrogenation of primary alcohol to ester catalyzed by the ruthenium(II)-PNN pincer complex Ru(H)(η2-BH4)(PNN), [PNN: (2-(di-tert-butylphosphinomethyl)-6-(diethlaminomethyl)-pyridine)] has been investigated using density functional theory calculations. The catalytic cycle includes three stages: (stage I) alcohol dehydrogenation to form aldehyde, (stage II) coupling of aldehyde with alcohol to give hemiacetal or ester, and (stage III) hemiacetal dehydrogenation to form ester. Two dehydrogenation reactions occur via the β-H elimination mechanism rather than the bifunctional double hydrogen transfer mechanism, which could be rationalized as the fluxional behavior of the BH4- ligand. At the second stage, the coupling reaction requires alcohol or the ruthenium catalyst as mediator. The formation of hemiacetal through the alcohol-mediated pathway is kinetically favorable than the ruthenium catalyst-mediated one, which may be attributed to the smaller steric hindrance when the aldehyde approaches the alcohol moiety in the reaction system. Our results would be helpful for experimental chemists to design more effective transition metal catalysts for dehydrogenation of alcohols.

  12. Rhodium-Catalyzed Acyloxy Migration of Propargylic Esters in Cycloadditions, Inspiration from Recent “Gold Rush”


    Shu, Xing-Zhong; Shu, Dongxu; Schienebeck, Casi M.; TANG, WEIPING


    Transition metal-catalyzed acyloxy migration of propargylic esters offers versatile entries to allene and vinyl carbene intermediates for various fascinating subsequent transformations. Most π-acidic metals (e.g. gold and platinum) are capable of facilitating these acyloxy migration events. However, very few of these processes involve redox chemistry, which are well-known for most other transition metals such as rhodium. The coupling of acyloxy migration of propargylic esters with oxidative a...

  13. Chiral Borated Esters in Asymmetric Synthesis:1.The First Asymmetric Reaction Catalyzed by Chiral Spiroborated Esters with an O3BN Framework

    Institute of Scientific and Technical Information of China (English)

    LIU, De-Jun(刘德军); SHAN, Zi-Xing(单自兴); QIN, Jin-Gui(秦金贵)


    The first asymmetric reaction catalyzed by chiral spiroborated esters with an O3BN framework was reported. In the presence of 0.1 equivalent of (R,S)-1 or (S,S)-1, acetophenone was reduced by 0.6 equivalent of borane in THF at 0-5 ℃ for 2 h to give (R)-1-phenylethanol of up to 76% ee and 73% isolated yield. Influence of reaction conditions on the stereoselectivity of the reduction was investigated and a possible catalytic mechanism of the chiral spiroborated esters toward the reduction was also suggested.

  14. Probing backbone hydrogen bonding in PDZ/ligand interactions by protein amide-to-ester mutations

    DEFF Research Database (Denmark)

    Pedersen, Søren W; Pedersen, Stine B; Anker, Louise;


    via backbone hydrogen bonds; however, little is known about the role of these hydrogen bonds due to experimental challenges with backbone mutations. Here we address this interaction by generating semisynthetic PDZ domains containing backbone amide-to-ester mutations and evaluating the importance...... of individual hydrogen bonds for ligand binding. We observe substantial and differential effects upon amide-to-ester mutation in PDZ2 of postsynaptic density protein 95 and other PDZ domains, suggesting that hydrogen bonding at the carboxylate-binding site contributes to both affinity and selectivity....... In particular, the hydrogen-bonding pattern is surprisingly different between the non-canonical and canonical interaction. Our data provide a detailed understanding of the role of hydrogen bonds in protein-protein interactions....

  15. Dehydrogenative Coupling of Primary Alcohols To Form Esters Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte; Madsen, Robert


    The ruthenium complex [RuCl2(IiPr)(p-cymene)] catalyzes the direct condensation of primary alcohols into esters and lactones with the release of hydrogen gas. The reaction is most effective with linear aliphatic alcohols and 1,4-diols and is believed to proceed with a ruthenium dihydride as the c...

  16. Rhodium(III)-Catalyzed C-H Activation/Annulation with Vinyl Esters as an Acetylene Equivalent


    Webb, NJ; Marsden, SP; Raw, SA


    The behavior of electron-rich alkenes in rhodium-catalyzed C–H activation/annulation reactions is investigated. Vinyl acetate emerges as a convenient acetylene equivalent, facilitating the synthesis of sixteen 3,4-unsubstituted isoquinolones, as well as select heteroaryl-fused pyridones. The complementary regiochemical preferences of enol ethers versus enol esters/enamides is discussed

  17. Production of sunflower oil methyl esters by optimized alkali-catalyzed methanolysis

    Energy Technology Data Exchange (ETDEWEB)

    Rashid, Umer; Anwar, Farooq; Ashraf, Samia [Department of Chemistry, University of Agriculture, Faisalabad 38040 (Pakistan); Moser, Bryan R. [United States Department of Agriculture, National Center for Agricultural Utilization Research, Peoria, IL 61604 (United States); Agricultural Research Service, National Center for Agricultural Utilization Research, Peoria, IL 61604 (United States)


    We report the optimization of sunflower oil methyl esters (SOME/biodiesel) production via alkaline catalyzed transesterification of crude sunflower oil and subsequent physical and chemical characterization. The optimum conditions elucidated for the methanolysis of sunflower oil were found to be: methanol/sunflower oil molar ratio, 6:1; reaction temperature, 60 C; and NaOH catalyst concentration, 1.00% (w/w). An optimum SOME yield of 97.1% was achieved. SOME were analyzed by gas-liquid chromatography (GLC). A number of fuel properties of SOME as measured according to accepted methods were found to satisfy nearly all prescribed ASTM D 6751 specifications, where applicable. The results of the present study indicated that SOME could be a potential alternative to other common biodiesels and petrodiesel. (author)

  18. Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene. (United States)

    Xu, Songchen; Boschen, Jeffery S; Biswas, Abhranil; Kobayashi, Takeshi; Pruski, Marek; Windus, Theresa L; Sadow, Aaron D


    An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ(3)-N,Si,C-PhB(Ox(Me2))(Ox(Me2)SiHPh)Im(Mes)}Rh(H)CO][HB(C6F5)3] (, Ox(Me2) = 4,4-dimethyl-2-oxazoline; Im(Mes) = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(Ox(Me2))2Im(Mes)}RhH(SiH2Ph)CO () and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(Ox(Me2))2Im(Mes)}RhH(SiHPh)CO][HB(C6F5)3] generated by H abstraction. Complex catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C6F5)3 catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH3 as the reducing agent. PMID:26278517

  19. Copper-catalyzed Suzuki-Miyaura coupling of arylboronate esters: transmetalation with (PN)CuF and identification of intermediates. (United States)

    Gurung, Santosh K; Thapa, Surendra; Kafle, Arjun; Dickie, Diane A; Giri, Ramesh


    An efficient Cu(I)-catalyzed Suzuki-Miyaura reaction was developed for the coupling of aryl- and heteroarylboronate esters with aryl and heteroaryl iodides at low catalyst loadings (2 mol %). The reaction proceeds under ligand-free conditions for aryl-heteroaryl and heteroaryl-heteroaryl couplings. We also conducted the first detailed mechanistic studies by synthesizing [(PN-2)CuI]2, [(PN-2)CuF]2, and (PN-2)CuPh (PN-2 = o-(di-tert-butylphosphino)-N,N-dimethylaniline) and demonstrated that [(PN-2)CuF]2 is the species that undergoes transmetalation with arylboronate esters.

  20. Influence of fatty acid on lipase-catalyzed synthesis of ascorbyl esters and their free radical scavenging capacity. (United States)

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


    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

  1. Rh-Catalyzed Asymmetric Hydrogenation of a-Enol Ester Phosphonates with 1-Phenylethylamine-Derived Phosphine- Phosphoramidite Ligands

    Institute of Scientific and Technical Information of China (English)


    HU Juan, WANG Dao-yong, ZHENG Zhuo, HU Xiang-ping J. Mol. Catal. (China) 2012, 26(6), 487 ~492 Chiral phosphine-phosphoramidite ligand, ( So, S,, )-2b, was found to be highly efficient in the Rh-catalyzed asymmetric hydrogenation of various α-enol ester phosphonates, in which excellent enantioselectivities (up to 〉99% ee) and high catalyticactivity ( S/C up to 5000) were achieved.

  2. Photoresponsive Liquid Crystalline Epoxy Networks with Shape Memory Behavior and Dynamic Ester Bonds. (United States)

    Li, Yuzhan; Rios, Orlando; Keum, Jong K; Chen, Jihua; Kessler, Michael R


    Functional polymers are intelligent materials that can respond to a variety of external stimuli. However, these materials have not yet found widespread real world applications because of the difficulties in fabrication and the limited number of functional building blocks that can be incorporated into a material. Here, we demonstrate a simple route to incorporate three functional building blocks (azobenzene chromophores, liquid crystals, and dynamic covalent bonds) into an epoxy-based liquid crystalline network (LCN), in which an azobenzene-based epoxy monomer is polymerized with an aliphatic dicarboxylic acid to create exchangeable ester bonds that can be thermally activated. All three functional building blocks exhibited good compatibility, and the resulting materials exhibits various photomechanical, shape memory, and self-healing properties because of the azobenzene molecules, liquid crystals, and dynamic ester bonds, respectively.

  3. Synthesis of sulfonamides via copper-catalyzed oxidative C-N bond cleavage of tertiary amines. (United States)

    Ji, Jing; Liu, Zhengyi; Liu, Ping; Sun, Peipei


    A copper-catalyzed coupling reaction of sulfonyl chlorides with tertiary amines via the oxidative C-N bond cleavage of tertiary amines was developed. Sulfonamides were synthesized using this strategy in moderate to good yields. The reaction was applicable to various tertiary amines, as well as sulfonyl chlorides. PMID:27356858

  4. Characterization of Wax Esters by Electrospray Ionization Tandem Mass Spectrometry: Double Bond Effect and Unusual Product Ions. (United States)

    Chen, Jianzhong; Green, Kari B; Nichols, Kelly K


    A series of different types of wax esters (represented by RCOOR') were systematically studied by using electrospray ionization (ESI) collision-induced dissociation tandem mass spectrometry (MS/MS) along with pseudo MS(3) (in-source dissociation combined with MS/MS) on a quadrupole time-of-flight (Q-TOF) mass spectrometer. The tandem mass spectra patterns resulting from dissociation of ammonium/proton adducts of these wax esters were influenced by the wax ester type and the collision energy applied. The product ions [RCOOH2](+), [RCO](+) and [RCO-H2O](+) that have been reported previously were detected; however, different primary product ions were demonstrated for the three wax ester types including: (1) [RCOOH2](+) for saturated wax esters, (2) [RCOOH2](+), [RCO](+) and [RCO-H2O](+) for unsaturated wax esters containing only one double bond in the fatty acid moiety or with one additional double bond in the fatty alcohol moiety, and (3) [RCOOH2](+) and [RCO](+) for unsaturated wax esters containing a double bond in the fatty alcohol moiety alone. Other fragments included [R'](+) and several series of product ions for all types of wax esters. Interestingly, unusual product ions were detected, such as neutral molecule (including water, methanol and ammonia) adducts of [RCOOH2](+) ions for all types of wax esters and [R'-2H](+) ions for unsaturated fatty acyl-containing wax esters. The patterns of tandem mass spectra for different types of wax esters will inform future identification and quantification approaches of wax esters in biological samples as supported by a preliminary study of quantification of isomeric wax esters in human meibomian gland secretions.

  5. Novel hot-melting hyperbranched poly(ester-amine) bearing self-complementary quadruple hydrogen bonding units

    Institute of Scientific and Technical Information of China (English)

    Yi Peng Qiu; Li Ming Tang; Yu Wang; Shi You Guan


    Hyperbranched poly(amine-ester)s bearing serf-complementary quadruple hydrogen bonding units display excellent mechanical and temperature-dependent melt rheological properties,which make them suitable as novel hot-melting materials.

  6. Lipase-catalyzed Synthesis of Caffeic Acid Phenethyl Ester in Ionic Liquids:Effect of Specific Ions and Reaction Parameters

    Institute of Scientific and Technical Information of China (English)

    王俊; 李晶; 张磊霞; 顾双双; 吴福安


    Caffeic acid phenethyl ester (CAPE) is a rare, naturally occurring phenolic food additive. This work systematically reported fundamental data on conversion of caffeic acid (CA), yield of CAPE, and reactive selectiv-ity during the lipase-catalyzed esterification process of CA and phenylethanol (PE) in ionic liquids (ILs). Sixteen ILs were selected as the reaction media, and the relative lipase-catalyzed synthesis properties of CAPE were meas-ured in an effort to enhance the yield of CAPE with high selectivity. The results indicated that ILs containing weakly coordinating anions and cations with adequate alkyl chain length improved the synthesis of CAPE. [Emim][Tf2N] was selected as the optimal reaction media. The optimal parameters were as follows by response surface methodology (RSM):reaction temperature, 84.0 °C;mass ratio of Novozym 435 to CA, 14︰1;and molar ratio of PE to CA, 16︰1. The highest reactive selectivity of CAPE catalyzed by Novozym 435 in [Emim][Tf2N] reached 64.55%(CA conversion 98.76%and CAPE yield 63.75%, respectively). Thus, lipase-catalyzed esterifica-tion in ILs is a promising method suitable for CAPE production.

  7. Thermodynamically leveraged Tandem catalysis for ester RC(O)O-R' bond hydrogenolysis. scope and mechanism.

    Energy Technology Data Exchange (ETDEWEB)

    Lohr, Tracy L.; Li, Zhi; Assary, Rajeev S.; Curtiss, Larry A.; Marks, Tobin J.


    Rapid and selective formal hydrogenolysis of aliphatic ester RC(O)O-R' linkages is achieved by a tandem homogeneous metal triflate + supported palladium catalytic system. The triflate catalyzes the mildly exothermic, turnover-limiting O-R' cleavage process, whereas the exothermic hydrogenation of the intermediate alkene further drives the overall reaction to completion.

  8. Palladium-Catalyzed C–C Bond Formations via Activation of Carboxylic Acids and Their Derivatives


    Song, Bingrui


    Applications of carboxylic acids and their derivatives in transition metal-catalyzed cross-coupling reactions regio-selectively forming Csp3-Csp2, and Csp2-Csp2 bonds were explored in this thesis. Several important organic building blocks such as aryl acetates, diaryl acetates, imines, ketones, biaryls, styrenes and polysubstituted alkenes were successfully accessed from carboxylic acids and their derivatives by the means of C–H activation and decarboxylative cross-couplings. An efficient ...

  9. Unsaturated Fatty Acid Esters Metathesis Catalyzed by Silica Supported WMe5

    KAUST Repository

    Riache, Nassima


    Metathesis of unsaturated fatty acid esters (FAEs) by silica supported multifunctional W-based catalyst is disclosed. This transformation represents a novel route towards unsaturated di-esters. Especially, the self-metathesis of ethyl undecylenate results almost exclusively on the homo-coupling product whereas with such catalyst, 1-decene gives ISOMET (isomerization and metathesis olefin) products. The olefin metathesis in the presence of esters is very selective without any secondary cross-metathesis products demonstrating that a high selective olefin metathesis could operate at 150 °C. Additionally, a cross-metathesis of unsaturated FAEs and α-olefins allowed the synthesis of the corresponding ester with longer hydrocarbon skeleton without isomerisation.

  10. Electrolysis of trichloromethylated organic compounds under aerobic conditions catalyzed by the B12 model complex for ester and amide formation. (United States)

    Shimakoshi, Hisashi; Luo, Zhongli; Inaba, Takuya; Hisaeda, Yoshio


    The electrolysis of benzotrichloride at -0.9 V vs. Ag/AgCl in the presence of the B12 model complex, heptamethyl cobyrinate perchlorate, in ethanol under aerobic conditions using an undivided cell equipped with a platinum mesh cathode and a zinc plate anode produced ethylbenzoate in 56% yield with 92% selectivity. The corresponding esters were obtained when the electrolysis was carried out in various alcohols such as methanol, n-propanol, and i-propanol. Benzoyl chloride was detected by GC-MS during the electrolysis as an intermediate for the ester formation. When the electrolysis was carried out under anaerobic conditions, partially dechlorinated products, 1,1,2,2-tetrachloro-1,2-diphenylethane and 1,2-dichlorostilibenes (E and Z forms), were obtained instead of an ester. ESR spin-trapping experiments using 5,5,-dimethylpyrroline N-oxide (DMPO) revealed that the corresponding oxygen-centered radical and carbon-centered radical were steadily generated during the electrolyses under aerobic and anaerobic conditions, respectively. Applications of the aerobic electrolysis to various organic halides, such as substituted benzotrichlorides, are described. Furthermore, the formation of amides with moderate yields by the aerobic electrolysis of benzotrichloride catalyzed by the B12 model complex in the presence of amines in acetonitrile is reported. PMID:27071703

  11. The ability of fruit and vegetable enzyme system to hydrolyse ester bonds

    Directory of Open Access Journals (Sweden)

    Agnieszka Mironowicz


    Full Text Available The pulp of potato tubers (Solanum tuberosum, topinambur (Helianthus tuberosus and apples (Malus silvestris can hydrolyse totally, or almost totally, ester bonds in phenyl, α- and β-naphthyl, benzyl and cinnamyl acetates. In methyl 4-acetoxy-3-metoxybenzoate and methyl 2,5-diacetoxybenzoate as well as testosterone propionate and 16,17-acetonide of 21-acetoxy-6-fluoro-16α,17β,21-trihydroxy-4-pregnen-3,20-dione, the hydrolysis is selective towards the substrate and the bioreagent. In contrast, ethyl benzoate and cinnamate are resistant to hydrolysis.

  12. Synthesis of 1,2,4-triazolines: base-catalyzed hydrazination/cyclization cascade of α-isocyano esters and amides. (United States)

    Monge, David; Jensen, Kim L; Marín, Irene; Jørgensen, Karl Anker


    A convenient, efficient synthesis of 1,2,4-triazolines from α-isocyano esters/amides and azodicarboxylates is presented. The developed reaction cascade is based on a base-catalyzed hydrazination-type reaction followed by a subsequent cyclization providing the triazolines in good to excellent yields (75-99%). Phosphine-catalyzed and preliminary asymmetric phase-transfer catalysis approaches have also been investigated. PMID:21166428

  13. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan


    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach

  14. Papain-Catalyzed Chemoenzymatic Synthesis of Telechelic Polypeptides Using Bis(Leucine Ethyl Ester) Initiator. (United States)

    Tsuchiya, Kousuke; Numata, Keiji


    In order to construct unique polypeptide architectures, a novel telechelic-type initiator with two leucine ethyl ester units is designed for chemoenzymatic polymerization. Glycine or alanine ethyl ester is chemoenzymatically polymerized using papain in the presence of the initiator, and the propagation occurs at each leucine ethyl ester unit to produce the telechelic polypeptide. The formation of the telechelic polypeptides is confirmed by (1) H NMR and MALDI-TOF mass spectroscopies. It is revealed by AFM observation that long nanofibrils are formed from the telechelic polyalanine, whereas a conventional linear polyalanine with a similar degree of polymerization shows granule-like structures. The telechelic polyglycine and polyalanine show the crystalline structures of Polyglycine II and antiparallel β-sheet, respectively. It is demonstrated that this method to synthesize telechelic-type polypeptides potentially opens up a pathway to construct novel hierarchical structures by self-assembly. PMID:26947148

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

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


    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

  16. Enantioselective epoxidation and carbon-carbon bond cleavage catalyzed by Coprinus cinereus peroxidase and myeloperoxidase. (United States)

    Tuynman, A; Spelberg, J L; Kooter, I M; Schoemaker, H E; Wever, R


    We demonstrate that myeloperoxidase (MPO) and Coprinus cinereus peroxidase (CiP) catalyze the enantioselective epoxidation of styrene and a number of substituted derivatives with a reasonable enantiomeric excess (up to 80%) and in a moderate yield. Three major differences with respect to the chloroperoxidase from Caldariomyces fumago (CPO) are observed in the reactivity of MPO and CiP toward styrene derivatives. First, in contrast to CPO, MPO and CiP produced the (S)-isomers of the epoxides in enantiomeric excess. Second, for MPO and CiP the H(2)O(2) had to be added very slowly (10 eq in 16 h) to prevent accumulation of catalytically inactive enzyme intermediates. Under these conditions, CPO hardly showed any epoxidizing activity; only with a high influx of H(2)O(2) (300 eq in 1.6 h) was epoxidation observed. Third, both MPO and CiP formed significant amounts of (substituted) benzaldehydes as side products as a consequence of C-alpha-C-beta bond cleavage of the styrene derivatives, whereas for CPO and cytochrome c peroxidase this activity is not observed. C-alpha-C-beta cleavage was the most prominent reaction catalyzed by CiP, whereas with MPO the relative amount of epoxide formed was higher. This is the first report of peroxidases catalyzing both epoxidation reactions and carbon-carbon bond cleavage. The results are discussed in terms of mechanisms involving ferryl oxygen transfer and electron transfer, respectively.

  17. Hydrogenation of esters catalyzed by ruthenium PN3-Pincer complexes containing an aminophosphine arm

    KAUST Repository

    Chen, Tao


    Hydrogenation of esters under mild conditions was achieved using air-stable ruthenium PN3-pincer complexes containing an aminophosphine arm. High efficiency was achieved even in the presence of water. DFT studies suggest a bimolecular proton shuttle mechanism which allows H2 to be activated by the relatively stable catalyst with a reasonably low transition state barrier. © 2014 American Chemical Society.

  18. Direct aerobic oxidation of primary alcohols to methyl esters catalyzed by a heterogeneous gold catalyst

    DEFF Research Database (Denmark)

    Nielsen, Inger Staunstrup; Taarning, Esben; Egeblad, Kresten;


    Methyl esters can be produced in high yield by oxidising methanolic solutions of primary alcohols with dioxygen over a heterogeneous gold catalyst. The versatility of this new methodology is demonstrated by the fact that alkylic, benzylic and allylic alcohols, as well as alcohols containing...

  19. Simultaneous clostridial fermentation, lipase-catalyzed esterification, and ester extraction to enrich diesel with butyl butyrate

    NARCIS (Netherlands)

    Berg, C. van den; Heeres, A.S.; Wielen, L.A.M. van der; Straathof, A.J.J.


    The recovery of 1-butanol from fermentation broth is energy-intensive since typical concentrations in fermentation broth are below 20gL -1. To prevent butanol inhibition and high downstream processing costs, we aimed at producing butyl esters instead of 1-butanol. It is shown that it is possible to

  20. Regioselective Synthesis of Polymerizable Vinyl Guaifenesin Esters Catalyzed by an Alkaline Protease of Bacillus subtilis

    Institute of Scientific and Technical Information of China (English)

    Na WANG; Qi WU; Jian Ming XU; Xiu Ming JIANG; Xian Fu LIN


    Three polymerizable vinyl guaifenesin esters with different acyl donor carbon chain lengths (C4,C6,C10) were regioselectivly synthesized by an alkaline protease from Bacillus subtilis in pyridine at 50°C for 1, 3, 5 days respectively.

  1. Probing the role of backbone hydrogen bonds in protein-peptide interactions by amide-to-ester mutations

    DEFF Research Database (Denmark)

    Eildal, Jonas N N; Hultqvist, Greta; Balle, Thomas;


    -protein interactions, those of the PDZ domain family involve formation of intermolecular hydrogen bonds: C-termini or internal linear motifs of proteins bind as β-strands to form an extended antiparallel β-sheet with the PDZ domain. Whereas extensive work has focused on the importance of the amino acid side chains...... of the protein ligand, the role of the backbone hydrogen bonds in the binding reaction is not known. Using amide-to-ester substitutions to perturb the backbone hydrogen-bonding pattern, we have systematically probed putative backbone hydrogen bonds between four different PDZ domains and peptides corresponding...... to natural protein ligands. Amide-to-ester mutations of the three C-terminal amides of the peptide ligand severely affected the affinity with the PDZ domain, demonstrating that hydrogen bonds contribute significantly to ligand binding (apparent changes in binding energy, ΔΔG = 1.3 to >3.8 kcal mol(-1...

  2. Enantioselective synthesis of 1,2,4-triazolines by chiral iron(II)-complex catalyzed cyclization of α-isocyano esters and azodicarboxylates. (United States)

    Wang, Min; Liu, Xiaohua; He, Peng; Lin, Lili; Feng, Xiaoming


    Enantioselective cyclization of α-isocyano esters with azodicarboxylates catalyzed by Fe(II)-N,N'-dioxide complexes has been developed. Under mild conditions, a variety of 1,2,4-triazoline derivatives was obtained in high yields and enantioselectivities. PMID:23423581

  3. Synthesis of Wax Esters by Lipase-catalyzed Esterification with Immobilized Lipase from Candida sp. 99-125

    Institute of Scientific and Technical Information of China (English)

    邓利; 王晓静; 聂开立; 王芳; 刘军峰; 王璞; 谭天伟


    Wax esters were synthesized in a solvent free system catalyzed by immobilized lipase from Candida sp. 99-125, with oleic acid and cetyl alcohol. The effects of substrate molar ratio, lipase dosage and water removal were investigated in a 50 ml flask incubated in a thermostatic cultivation cabinet. The optimized conditions were: temperature 40 ℃, shaking at 170 r·min-1, acid/alcohol molar ratio 1:0.9, lipase dosage in 10% (by mass) of oleic acid, and open reaction for water removal. As a result, the conversion rate reached 98% for reaction of 8 h. The volume of reactor was scaled up to 1 L three-neck flask. The optimized parameters were: 200 r·min-1 agitation speed, 2.5% (by mass) lipase dosage, others were the same as the parameters described above. The conversion rate reached 95% for reaction of 24 h. The lipase retained 46% conversion rate after reuse for 6, 7 batches. The products were purified by removing remained cetyl alcohol and fatty acids with ethanol and saturated sodium carbonate so-lution, respectively. The purity of the wax ester, cetyl oleate, was 96%. The physical and chemical properties of cetyl oleate were tested and compared with those of jojoba oil. The results show that the product cetyl oleate has great potential to use as the substitute of natural jojoba oil.

  4. Switching the Cleavage Sites in Palladium on Carbon-Catalyzed Carbon-Carbon Bond Disconnection. (United States)

    Hattori, Tomohiro; Takakura, Ryoya; Ichikawa, Tomohiro; Sawama, Yoshinari; Monguchi, Yasunari; Sajiki, Hironao


    We have demonstrated a palladium on carbon-catalyzed approach to regioselectively alter the cleavage sites of the C-C bonds of cinnamaldehyde derivatives by a slight change in the reaction conditions in isopropanol under an O2 atmosphere. Styrene derivatives could be selectively formed by the addition of Na2CO3 in association with the dissociation of carbon monoxide, while benzaldehyde derivatives were generated by the addition of CuCl and morpholine instead of Na2CO3. PMID:26944077

  5. Effect of Alcohol Structure on the Optimum Condition for Novozym 435-Catalyzed Synthesis of Adipate Esters

    Directory of Open Access Journals (Sweden)

    Mohd Basyaruddin Abdul Rahman


    Full Text Available Immobilized Candida antarctica lipase B, Novozym 435, was used as the biocatalyst in the esterification of adipic acid with four different isomers of butanol (n-butanol, sec-butanol, iso-butanol, and tert-butanol. Optimum conditions for the synthesis of adipate esters were obtained using response surface methodology approach with a four-factor-five-level central composite design concerning important reaction parameters which include time, temperature, substrate molar ratio, and amount of enzyme. Reactions under optimized conditions has yielded a high percentage of esterification (>96% for n-butanol, iso-butanol, and sec-butanol, indicating that extent of esterification is independent of the alcohol structure for primary and secondary alcohols at the optimum conditions. Minimum reaction time (135 min for achieving maximum ester yield was obtained for iso-butanol. The required time for attaining maximum yield and also the initial rates in the synthesis of di-n-butyl and di-sec-butyl adipate were nearly the same. Immobilized Candida antarctica lipase B was also capable of esterifying tert-butanol with a maximum yield of 39.1%. The enzyme is highly efficient biocatalyst for the synthesis of adipate esters by offering a simple production process and a high esterification yield.

  6. Rh(III)-Catalyzed C-H Bond Addition/Amine-Mediated Cyclization of Bis-Michael Acceptors. (United States)

    Potter, Tyler J; Ellman, Jonathan A


    A Rh(III)-catalyzed C-H bond addition/primary amine-promoted cyclization of bis-Michael acceptors is reported. The C-H bond addition step occurs with high chemoselectivity, and the subsequent intramolecular Michael addition, mediated by a primary amine catalyst, sets three contiguous stereocenters with high diastereoselectivity. A broad range of directing groups and both aromatic and alkenyl C-H bonds were shown to be effective in this transformation, affording functionalized piperidines, tetrahydropyrans, and cyclohexanes.

  7. Metal Nanoparticles Catalyzed Selective Carbon-Carbon Bond Activation in the Liquid Phase. (United States)

    Ye, Rong; Yuan, Bing; Zhao, Jie; Ralston, Walter T; Wu, Chung-Yeh; Unel Barin, Ebru; Toste, F Dean; Somorjai, Gabor A


    Understanding the C-C bond activation mechanism is essential for developing the selective production of hydrocarbons in the petroleum industry and for selective polymer decomposition. In this work, ring-opening reactions of cyclopropane derivatives under hydrogen catalyzed by metal nanoparticles (NPs) in the liquid phase were studied. 40-atom rhodium (Rh) NPs, encapsulated by dendrimer molecules and supported in mesoporous silica, catalyzed the ring opening of cyclopropylbenzene at room temperature under hydrogen in benzene, and the turnover frequency (TOF) was higher than other metals or the Rh homogeneous catalyst counterparts. Comparison of reactants with various substitution groups showed that electron donation on the three-membered ring boosted the TOF of ring opening. The linear products formed with 100% selectivity for ring opening of all reactants catalyzed by the Rh NP. Surface Rh(0) acted as the active site in the NP. The capping agent played an important role in the ring-opening reaction kinetics. Larger particle size tended to show higher TOF and smaller reaction activation energy for Rh NPs encapsulated in either dendrimer or poly(vinylpyrrolidone). The generation/size of dendrimer and surface group also affected the reaction rate and activation energy. PMID:27322570

  8. Practical Ni-Catalyzed Aryl-Alkyl Cross-Coupling of Secondary Redox-Active Esters. (United States)

    Cornella, Josep; Edwards, Jacob T; Qin, Tian; Kawamura, Shuhei; Wang, Jie; Pan, Chung-Mao; Gianatassio, Ryan; Schmidt, Michael; Eastgate, Martin D; Baran, Phil S


    A new transformation is presented that enables chemists to couple simple alkyl carboxylic acids with aryl zinc reagents under Ni-catalysis. The success of this reaction hinges on the unique use of redox-active esters that allow one to employ such derivatives as alkyl halides surrogates. The chemistry exhibits broad substrate scope and features a high degree of practicality. The simple procedure and extremely inexpensive nature of both the substrates and pre-catalyst (NiCl2·6H2O, ca. $9.5/mol) bode well for the immediate widespread adoption of this method. PMID:26835704

  9. Reaction Pathways and Energetics of Etheric C–O Bond Cleavage Catalyzed by Lanthanide Triflates

    Energy Technology Data Exchange (ETDEWEB)

    Assary, Rajeev S.; Atesin, Abdurrahman C.; Li, Zhi; Curtiss, Larry A.; Marks, Tobin J.


    Efficient and selective cleavage of etheric C-O bonds is crucial for converting biomass into platform chemicals and liquid transportation fuels. In this contribution, computational methods at the DFT B3LYP level of theory are employed to understand the efficacy of lanthanide triflate catalysts (Ln(OTf)3, Ln = La, Ce, Sm, Gd, Yb, and Lu) in cleaving etheric C-O bonds. In agreement with experiment, the calculations indicate that the reaction pathway for C-O cleavage occurs via a C-H → O-H proton transfer in concert with weakening of the C-O bond of the coordinated ether substrate to ultimately yield a coordinated alkenol. The activation energy for this process falls as the lanthanide ionic radius decreases, reflecting enhanced metal ion electrophilicity. Details of the reaction mechanism for Yb(OTf)3-catalyzed ring opening are explored in depth, and for 1-methyl-d3-butyl phenyl ether, the computed primary kinetic isotope effect of 2.4 is in excellent agreement with experiment (2.7), confirming that etheric ring-opening pathway involves proton transfer from the methyl group alpha to the etheric oxygen atom, which is activated by the electrophilic lanthanide ion. Calculations of the catalytic pathway using eight different ether substrates indicate that the more rapid cleavage of acyclic versus cyclic ethers is largely due to entropic effects, with the former C-O bond scission processes increasing the degrees of freedom/particles as the transition state is approached.

  10. Hydrolysis of Surfactants Containing Ester Bonds: Modulation of Reaction Kinetics and Important Aspects of Surfactant Self-Assembly (United States)

    Lundberg, Dan; Stjerndahl, Maria


    The effects of self-assembly on the hydrolysis kinetics of surfactants that contain ester bonds are discussed. A number of examples on how reaction rates and apparent reaction orders can be modulated by changes in the conditions, including an instance of apparent zero-order kinetics, are presented. Furthermore, it is shown that the examples on…

  11. Hydrolysis of carboxylate ester catalyzed by a new artificial abzyme based on molecularly imprinted polymer

    Institute of Scientific and Technical Information of China (English)


    A new kind of artificial abzyme MIP-3, which contains N-phenyl benzonic amide group and “nanochannel” formed by embedded ZnO nano materials, and is imprinted by a transition-state analogue of p-nitrophenyl methyphosphonate in the hydrolysis of p-nitrophenyl acetate, was prepared by radical co-polymerization. Hydrolytic kinetics of p-nitrophenyl carboxylate catalyzed by MIP-3 was investigated. The results showed that the artificial abzyme exhibited notable substructure selectivity and strong catalytic ability in hydrolysis of p-nitrophenyl acetate

  12. Synthesis of Biaryls through Nickel-Catalyzed Suzuki-Miyaura Coupling of Amides by Carbon-Nitrogen Bond Cleavage. (United States)

    Shi, Shicheng; Meng, Guangrong; Szostak, Michal


    The first Ni-catalyzed Suzuki-Miyaura coupling of amides for the synthesis of widely occurring biaryl compounds through N-C amide bond activation is reported. The reaction tolerates a wide range of electron-withdrawing, electron-neutral, and electron-donating substituents on both coupling partners. The reaction constitutes the first example of the Ni-catalyzed generation of aryl electrophiles from bench-stable amides with potential applications for a broad range of organometallic reactions. PMID:27101428

  13. Carbon-Oxygen Bond Cleavage by Bis(imino)pyridine Iron Compounds : Catalyst Deactivation Pathways and Observation of Acyl C-O Bond Cleavage in Esters

    NARCIS (Netherlands)

    Trovitch, Ryan J.; Lobkovsky, Emil; Bouwkamp, Marco W.; Chirik, Paul J.


    Investigations into the substrate scope of bis(imino)pyridine iron-catalyzed hydrogenation and [2 pi + 2 pi]. diene cyclization reactions identified C-O bond cleavage as a principal deactivation pathway. Addition of diallyl or allyl ethyl ether to the bis(imino)pyridine iron dinitrogen complex, ((iP

  14. Astaxanthin preparation by lipase-catalyzed hydrolysis of its esters from Haematococcus pluvialis algal extracts. (United States)

    Zhao, Yingying; Guan, Feifei; Wang, Guili; Miao, Lili; Ding, Jing; Guan, Guohua; Li, Ying; Hui, Bodi


    Five of 8 fungal lipases screened were found to effectively hydrolyze astaxanthin esters from Haematococcus pluvialis algal cell extracts. Among these, an alkaline lipase from Penicillium cyclopium, expressed in Pichia pastoris, had the highest enzymolysis efficiency. Tween80 was shown to be an effective emulsifier in this lipase hydrolysis system for the 1st time. A series of experiments were performed to find optimal conditions for hydrolysis (pH, temperature, reaction time, lipase dosage). In the optimal reaction system, Tween80 and H. pluvialis extracts (mass ratio 1:1) were emulsified and added to the above lipase at a dosage of 4.6 U/μg (relative to total carotenoids), in phosphate buffer (0.1 M, pH 7.0), and incubated at 28 °C for 7 h, with agitation at 180 rpm. The free astaxanthin recovery ratio under these conditions was 63.2%. PMID:22417348

  15. Solvent-Free Lipase-Catalyzed Synthesis of Technical-Grade Sugar Esters and Evaluation of Their Physicochemical and Bioactive Properties

    Directory of Open Access Journals (Sweden)

    Ran Ye


    Full Text Available Technical-grade oleic acid esters of sucrose and fructose were prepared using solvent-free biocatalysis at 65 °C, without any downstream purification applied, and their physicochemical and bioactivity-related properties were evaluated and compared to a commercially available sucrose laurate emulsifier. To increase the conversion of sucrose and fructose oleate, prepared previously using solvent-free lipase-catalyzed esterification catalyzed by Rhizomucor miehei lipase (81% and 83% ester, respectively, the enzymatic reaction conditions was continued using CaSO4 to control the reactor’s air headspace and a lipase (from Candida antarctica B with a hydrophobic immobilization matrix to provide an ultralow water activity, and high-pressure homogenation, to form metastable suspensions of 2.0–3.3 micron sized saccharide particles in liquid-phase reaction media. These measures led to increased ester content of 89% and 96% for reactions involving sucrose and fructose, respectively. The monoester content among the esters decreased from 90% to <70% due to differences in regioselectivity between the lipases. The resultant technical-grade sucrose and fructose lowered the surface tension to <30 mN/m, and possessed excellent emulsification capability and stability over 36 h using hexadecane and dodecane as oils, comparable to that of sucrose laurate and Tween® 80. The technical-grade sugar esters, particularly fructose oleate, more effectively inhibited gram-positive foodborne pathogens (Lactobacillus plantarum, Pediococcus pentosaceus and Bacillus subtilis. Furthermore, all three sugar esters displayed antitumor activity, particularly the two sucrose esters. This study demonstrates the importance of controlling the biocatalysts’ water activity to achieve high conversion, the impact of a lipase’s regioselectivity in dictating product distribution, and the use of solvent-free biocatalysis to important biobased surfactants useful in foods, cosmetics

  16. Controllable Orientation of Ester-Group-Induced Intermolecular Halogen Bonding in a 2D Self-Assembly. (United States)

    Zha, Bao; Dong, Meiqiu; Miao, Xinrui; Miao, Kai; Hu, Yi; Wu, Yican; Xu, Li; Deng, Wenli


    Halogen bonding with high specificity and directionality in the geometry has proven to be an important type of noncovalent interaction to fabricate and control 2D molecular architectures on surfaces. Herein, we first report how the orientation of the ester substituent for thienophenanthrene derivatives (5,10-DBTD and 5,10-DITD) affects positive charge distribution of halogens by density functional theory, thus determining the formation of an intermolecular halogen bond and different self-assembled patterns by scanning tunneling microscopy. The system presented here mainly includes heterohalogen X···O═C and X···S halogen bonds, H···Br and H···O hydrogen bonds, and I···I interaction, where the directionality and strength of such weak bonds determine the molecular arrangement by varying the halogen substituent. This study provides a detailed understanding of the role of ester orientation, concentration, and solvent effects on the formation of halogen bonds and proves relevant for identification of multiple halogen bonding in supramolecular chemistry. PMID:27482936

  17. Simulated sunlight photodegradation of aqueous phthalate esters catalyzed by the polyoxotungstate/titania nanocomposite. (United States)

    Xu, Lei; Yang, Xia; Guo, Yihang; Ma, Fengyan; Guo, Yingna; Yuan, Xing; Huo, Mingxin


    A series of porous polyoxotungstate/titania nanocomposites (PW(12)/TiO(2)) with particle size lower than 10nm and BET surface area of ca. 200 m(2)g(-1) was prepared by sol-gel chemistry combined with solvothermal treatment. The composites were successfully applied to the degradation of aqueous phthalate esters (PAEs) including di-n-butyl phthalate (DBP), diethyl phthalate (DEP), and dimethyl phthalate (DMP) under the simulated sunlight irradiation (lambda=320-680 nm) for the first time, and the conversion of DBP, DEP, and DMP reached to 98%, 84%, and 80%, respectively, after the simulated sunlight irradiation the suspension including PAE (5 mg L(-1), 100 mL) and PW(12)/TiO(2)-19.8 (100 mg) for 90 min. In addition, nearly total mineralization of DBP and DEP was realized by further increasing light irradiation time to 12h. Based on the intermediates identified in the reaction system, the photocatalytic degradation pathway of PAEs was put forward. PMID:20236760

  18. Efficient Synthesis of Functionalized Benzimidazoles and Perimidines: Ytterbium Chloride Catalyzed CmC Bond Cleavage%Efficient Synthesis of Functionalized Benzimidazoles and Perimidines: Ytterbium Chloride Catalyzed CmC Bond Cleavage

    Institute of Scientific and Technical Information of China (English)

    Cai, Lijian; Ji, Xiaofeng; Yao, Zhigang; Xu, Fan; Shen, Qi


    An efficient method is developed for the synthesis of functionalized benzimidazoles and perimidines by the condensation of aryl diamines with β-carbonyl compounds catalyzed by ytterbium chloride. The reactions give good yields under mild conditions. A mechanism involving a lanthanide activated C--C bond cleavage is proposed.

  19. Two-step synthesis of fatty acid ethyl ester from soybean oil catalyzed by Yarrowia lipolytica lipase

    Directory of Open Access Journals (Sweden)

    Chen Jinnan


    Full Text Available Abstract Background Enzymatic biodiesel production by transesterification in solvent media has been investigated intensively, but glycerol, as a by-product, could block the immobilized enzyme and excess n-hexane, as a solution aid, would reduce the productivity of the enzyme. Esterification, a solvent-free and no-glycerol-release system for biodiesel production, has been developed, and two-step catalysis of soybean oil, hydrolysis followed by esterification, with Yarrowia lipolytica lipase is reported in this paper. Results First, soybean oil was hydrolyzed at 40°C by 100 U of lipase broth per 1 g of oil with approximately 30% to 60% (vol/vol water. The free fatty acid (FFA distilled from this hydrolysis mixture was used for the esterification of FFA to fatty acid ethyl ester by immobilized lipase. A mixture of 2.82 g of FFA and equimolar ethanol (addition in three steps were shaken at 30°C with 18 U of lipase per 1 gram of FFA. The degree of esterification reached 85% after 3 hours. The lipase membranes were taken out, dehydrated and subjected to fresh esterification so that over 82% of esterification was maintained, even though the esterification was repeated every 3 hours for 25 batches. Conclusion The two-step enzymatic process without glycerol released and solvent-free demonstrated higher efficiency and safety than enzymatic transesterification, which seems very promising for lipase-catalyzed, large-scale production of biodiesel, especially from high acid value waste oil.

  20. Enhancement of Lipase-catalyzed Synthesis of Caffeic Acid Phenethyl Ester in Ionic Liquid with DMSO Co-solvent☆

    Institute of Scientific and Technical Information of China (English)

    Shuangshuang Gu; Jun Wang; Xianbin Wei; Hongsheng Cui; Xiangyang Wu; Fuan Wu


    Caffeic acid phenethyl ester (CAPE) is a natural and rare ingredient with several biological activities, but its indus-trial production using lipase-catalyzed esterification of caffeic acid (CA) and 2-phenylethanol (PE) in ionic liquids (ILs) is hindered by low substrate concentrations and long reaction time. To set up a high-efficiency bioprocess for production of CAPE, a novel dimethyl sulfoxide (DMSO)–IL co-solvent system was established in this study. The 2%(by volume) DMSO–[Bmim][Tf2N] system was found to be the best medium with higher substrate solu-bility and conversion of CA. Under the optimum conditions, the substrate concentration of CA was raised 8-fold, the reaction time was reduced by half, and the conversion reached 96.23%. The kinetics follows a ping-pong bi-bi mechanism with inhibition by PE, with kinetic parameters as follows:Vmax=0.89 mmol · min−1 · g−1, Km,CA=42.9 mmol · L−1, Km,PE=165.7 mmol · L−1, and Ki,PE=146.2 mmol · L−1. The results suggest that the DMSO co-solvent effect has great potential to enhance the enzymatic synthesis efficiency of CAPE in ILs.

  1. Nickel-Catalyzed C sp2 –C sp3 Cross-Coupling via C–O Bond Activation

    KAUST Repository

    Guo, Lin


    A new and efficient nickel-catalyzed alkylation of CAr-O electrophiles with B-alkyl-9-BBNs is described. The transformation is characterized by its functional group tolerance and provides a practical and versatile access to various Csp2-Csp3 bonds through Csp2-O substitution, without the restriction of β-hydride elimination. Moreover, the advantage of the newly developed method was demonstrated in a selective and sequential C-O bond activation process. © 2016 American Chemical Society.

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

    Directory of Open Access Journals (Sweden)

    Ohgi Takahashi


    Full Text Available 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.

  3. Asymmetric Synthesis of (-)-Incarvillateine Employing an Intramolecular Alkylation via Rh-Catalyzed Olefinic C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, Andy; Bergman, Robert; Ellman, Jonathan


    An asymmetric total synthesis of (-)-incarvillateine, a natural product having potent analgesic properties, has been achieved in 11 steps and 15.4% overall yield. The key step is a rhodium-catalyzed intramolecular alkylation of an olefinic C-H bond to set two stereocenters. Additionally, this transformation produces an exocyclic, tetrasubstituted alkene through which the bicyclic piperidine moiety can readily be accessed.

  4. Palladium-catalyzed picolinamide-directed iodination of remote ortho-C−H bonds of arenes: Synthesis of tetrahydroquinolines (United States)

    Nack, William A; Wang, Xinmou; Wang, Bo


    Summary A new palladium-catalyzed picolinamide (PA)-directed ortho-iodination reaction of ε-C(sp2)−H bonds of γ-arylpropylamine substrates is reported. This reaction proceeds selectively with a variety of γ-arylpropylamines bearing strongly electron-donating or withdrawing substituents, complementing our previously reported PA-directed electrophilic aromatic substitution approach to this transformation. As demonstrated herein, a three step sequence of Pd-catalyzed γ-C(sp3)−H arylation, Pd-catalyzed ε-C(sp2)−H iodination, and Cu-catalyzed C−N cyclization enables a streamlined synthesis of tetrahydroquinolines bearing diverse substitution patterns. PMID:27559375

  5. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Bergman, Robert; Ellman, Jonathan


    Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of

  6. Diastereoselective Ni-catalyzed 1,4-hydroboration of chiral dienols#


    Ely, Robert J.; Yu, Zhiyong; Morken, James P.


    The Ni-catalyzed hydroboration of dienols occurs in a 1,4 fashion and delivers a syn-propionate motif in high diastereoselectivity and with a stereodefined trisubstituted crotylboronic ester. The boronic ester can be further manipulated to provide carbon-carbon or carbon-oxygen bonds.

  7. Synthesis of ethoxy dibenzooxaphosphorin oxides through palladium-catalyzed C(sp2–H activation/C–O formation

    Directory of Open Access Journals (Sweden)

    Seohyun Shin


    Full Text Available We report an efficient Pd-catalyzed C(sp2–H activation/C–O bond formation for the synthesis of ethoxy dibenzooxaphosphorin oxides from 2-(arylarylphosphonic acid monoethyl esters under aerobic conditions.

  8. Synthesis, Anti-HCV, Antioxidant and Reduction of Intracellular Reactive Oxygen Species Generation of a Chlorogenic Acid Analogue with an Amide Bond Replacing the Ester Bond

    Directory of Open Access Journals (Sweden)

    Ling-Na Wang


    Full Text Available Chlorogenic acid is a well known natural product with important bioactivities. It contains an ester bond formed between the COOH of caffeic acid and the 3-OH of quinic acid. We synthesized a chlorogenic acid analogue, 3α-caffeoylquinic acid amide, using caffeic and quinic acids as starting materials. The caffeoylquinc acid amide was found to be much more stable than chlorogenic acid and showed anti-Hepatitis C virus (anti-HCV activity with a potency similar to chlorogenic acid. The caffeoylquinc acid amide potently protected HepG2 cells against oxidative stress induced by tert-butyl hydroperoxide.

  9. C-H Bond Oxidation Catalyzed by an Imine-Based Iron Complex: A Mechanistic Insight. (United States)

    Olivo, Giorgio; Nardi, Martina; Vìdal, Diego; Barbieri, Alessia; Lapi, Andrea; Gómez, Laura; Lanzalunga, Osvaldo; Costas, Miquel; Di Stefano, Stefano


    A family of imine-based nonheme iron(II) complexes (LX)2Fe(OTf)2 has been prepared, characterized, and employed as C-H oxidation catalysts. Ligands LX (X = 1, 2, 3, and 4) stand for tridentate imine ligands resulting from spontaneous condensation of 2-pycolyl-amine and 4-substituted-2-picolyl aldehydes. Fast and quantitative formation of the complex occurs just upon mixing aldehyde, amine, and Fe(OTf)2 in a 2:2:1 ratio in acetonitrile solution. The solid-state structures of (L1)2Fe(OTf)(ClO4) and (L3)2Fe(OTf)2 are reported, showing a low-spin octahedral iron center, with the ligands arranged in a meridional fashion. (1)H NMR analyses indicate that the solid-state structure and spin state is retained in solution. These analyses also show the presence of an amine-imine tautomeric equilibrium. (LX)2Fe(OTf)2 efficiently catalyze the oxidation of alkyl C-H bonds employing H2O2 as a terminal oxidant. Manipulation of the electronic properties of the imine ligand has only a minor impact on efficiency and selectivity of the oxidative process. A mechanistic study is presented, providing evidence that C-H oxidations are metal-based. Reactions occur with stereoretention at the hydroxylated carbon and selectively at tertiary over secondary C-H bonds. Isotopic labeling analyses show that H2O2 is the dominant origin of the oxygen atoms inserted in the oxygenated product. Experimental evidence is provided that reactions involve initial oxidation of the complexes to the ferric state, and it is proposed that a ligand arm dissociates to enable hydrogen peroxide binding and activation. Selectivity patterns and isotopic labeling studies strongly suggest that activation of hydrogen peroxide occurs by heterolytic O-O cleavage, without the assistance of a cis-binding water or alkyl carboxylic acid. The sum of these observations provides sound evidence that controlled activation of H2O2 at (LX)2Fe(OTf)2 differs from that occurring in biomimetic iron catalysts described to date. PMID

  10. Immobilized Rhizopus oryzae lipase catalyzed synthesis of palm stearin and cetyl alcohol wax esters: Optimization by Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Gargouri Youssef


    Full Text Available Abstract Background Waxes are esters of long-chain fatty acids and long-chain alcohols. Their principal natural sources are animals (sperm whale oil and vegetables (jojoba which are expensive and not easily available. Wax esters synthesized by enzymatic transesterification, using palm stearin as raw material, can be considered as an alternative to natural ones. Results Palm stearin is a solid fraction obtained by fractionation of palm oil. Palm stearin was esterified with cetyl alcohol to produce a mixture of wax esters. A non-commercial immobilized lipase from Rhizopus oryzae was used as biocatalyst. Response surface methodology was employed to determine the effects of the temperature (30-50°C, the enzyme concentration (33.34-300 IU/mL, the alcohol/palm stearin molar ratio (3-7 mol/mol and the substrate concentration (0.06-0.34 g/mL on the conversion yield of palm stearin. Under optimal conditions (temperature, 30°C; enzyme concentration, 300 IU/mL; molar ratio 3 and substrate concentration 0.21 g/mL a high conversion yield of 98.52% was reached within a reaction time of 2 h. Conclusions Response surface methodology was successfully applied to determine the optimum operational conditions for synthesis of palm stearin based wax esters. This study may provide useful tools to develop economical and efficient processes for the synthesis of wax esters.

  11. Asymmetric transesterification of ibuprofen methyl ester catalyzed by Novozym 435%Novozym435催化布洛芬甲酯的不对称醇解反应

    Institute of Scientific and Technical Information of China (English)

    徐景侠; 李立标; 孙建华


    目的 制备S(+)-布洛芬.方法 以布洛芬甲酯为原料,利用酶催化的 不对称转酯反应,将R(-)-布洛芬甲酯转化为R(-)-布洛芬丁酯,反应条件:布洛芬甲酯,10 g(100 mmol);Novozym 435,10 g;正丁醇,5.9 g(80 mmol);温度,39℃;时间,8~10 h.结果 不对称转酯反应的收率为83%,将得到的S(+)-布洛芬甲酯进行水解得S(+)-布洛芬,其收率为90%,光学纯为93%ee.结论 该本反应体系下,酶可以被回收利用,绿色经济,该方法有工业放大的潜力.%Aim To prepare S( + )-ibuprofen. Methods R( - )-ibuprofen methyl ester was transferred to R( - )-ibuprofen butyl ester catalyzed by enzyme. The reaction was performed as follows : Ibuprofen methyl ester, 10 g , 100 mmol; Novozym 435 , 10 g; 1-butanol, 5. 9 g,80 mmol;Temperature , 39℃ ; Time.8 - 10 h. Results The yield of asymmetric transesterification was 83% . The S( + )-ibuprofen methyl ester was then hydrolyzed. The yield of S( + )-ibuprofen with 93% ee was 90℃ . Conclusion The enzyme can be used repeatedly in these methods. The procedure has potential to be applied in industrial scale which was economic and environmental friendly.

  12. Solvent-Free Selective Condensations Based on the Formation of the Olefinic (C=C Bond Catalyzed by Organocatalyst

    Directory of Open Access Journals (Sweden)

    Heyuan Song


    Full Text Available Pyrrolidine and its derivatives were used to catalyze aldol and Knoevenagel condensations for the formation of the olefinic (C=C bond under solvent-free conditions. The 3-pyrrolidinamine showed high activity and afforded excellent yields of α,β-unsaturated compounds. The aldol condensation of aromatic/heterocyclic aldehydes with ketones affords enones in high conversion (99.5% and selectivity (92.7%. Good to excellent yields of α,β-unsaturated compounds were obtained in the Knoevenagel condensation of aldehydes with methylene-activated substrates.

  13. Atmospheric Hydrogenation of Esters Catalyzed by PNP-Ruthenium Complexes with an N-Heterocyclic Carbene Ligand. (United States)

    Ogata, Osamu; Nakayama, Yuji; Nara, Hideki; Fujiwhara, Mitsuhiko; Kayaki, Yoshihito


    New pincer ruthenium complexes bearing a monodentate N-heterocyclic carbene ligand were synthesized and demonstrated as powerful hydrogenation catalysts. With an atmospheric pressure of hydrogen gas, aromatic, heteroaromatic, and aliphatic esters as well as lactones were converted into the corresponding alcohols at 50 °C. This reaction protocol offers reliable access to alcohols using an easy operational setup. PMID:27439106

  14. A Facile Construction of Eudesmanolide Denebutenolide via SmI2-catalyzed Rearrangement of an Enol Ester Epoxide

    Institute of Scientific and Technical Information of China (English)


    A very convenient construction procedure of the a, b-unsaturated lactone has been carried out in 98% yield. SmI2 (10%) was used as catalyst for rearrangement of an enol ester epoxide of eudesmanolide sesquiterpene. The possible mechanism was also discussed.

  15. A Facile Construction of Eudesmanolide Denebutenolide via SmI2—catalyzed Rearrangement of an Enol Ester Epoxide

    Institute of Scientific and Technical Information of China (English)

    WuJiongXIA; AoChengCAO; 等


    A very convenient construction procedure of the α,β-unsaturated lactone has been carried out in 98% yield. SmI2 (10%) was used as catalyst for rearrangement of an enol ester exoxide of eudesmanolide sesquiterpene. The possible mechanism was also discussed.

  16. Atmospheric Hydrogenation of Esters Catalyzed by PNP-Ruthenium Complexes with an N-Heterocyclic Carbene Ligand. (United States)

    Ogata, Osamu; Nakayama, Yuji; Nara, Hideki; Fujiwhara, Mitsuhiko; Kayaki, Yoshihito


    New pincer ruthenium complexes bearing a monodentate N-heterocyclic carbene ligand were synthesized and demonstrated as powerful hydrogenation catalysts. With an atmospheric pressure of hydrogen gas, aromatic, heteroaromatic, and aliphatic esters as well as lactones were converted into the corresponding alcohols at 50 °C. This reaction protocol offers reliable access to alcohols using an easy operational setup.

  17. Palladium(ii)-catalyzed C-C and C-O bond formation for the synthesis of C1-benzoyl isoquinolines from isoquinoline N-oxides and nitroalkenes. (United States)

    Li, Jiu-Ling; Li, Wei-Ze; Wang, Ying-Chun; Ren, Qiu; Wang, Heng-Shan; Pan, Ying-Ming


    C1-Benzoyl isoquinolines can be generated via a palladium(ii)-catalyzed C-C and C-O coupling of isoquinoline N-oxides with aromatic nitroalkenes. The reaction proceeds through remote C-H bond activation and subsequent intramolecular oxygen atom transfer (OAT). In this reaction, the N-O bond was designed as a directing group in the C-H bond activation as well as the source of an oxygen atom. PMID:27443150

  18. Homogeneous and heterogeneous photoredox-catalyzed hydroxymethylation of ketones and keto esters: catalyst screening, chemoselectivity and dilution effects

    Directory of Open Access Journals (Sweden)

    Axel G. Griesbeck


    Full Text Available The homogeneous titanium- and dye-catalyzed as well as the heterogeneous semiconductor particle-catalyzed photohydroxymethylation of ketones by methanol were investigated in order to evaluate the most active photocatalyst system. Dialkoxytitanium dichlorides are the most efficient species for chemoselective hydroxymethylation of acetophenone as well as other aromatic and aliphatic ketones. Pinacol coupling is the dominant process for semiconductor catalysis and ketone reduction dominates the Ti(OiPr4/methanol or isopropanol systems. Application of dilution effects on the TiO2 catalysis leads to an increase in hydroxymethylation at the expense of the pinacol coupling.

  19. Long-chain ethers as solvents can amplify the enantioselectivity of the Carica papaya lipase-catalyzed transesterification of 2-(substituted phenoxy)propanoic acid esters. (United States)

    Miyazawa, Toshifumi; Iguchi, Wakana


    The enantioselectivity of the transesterification of the 2,2,2-trifluoroethyl esters of 2-(substituted phenoxy)propanoic acids, as catalyzed by the lipase from Carica papaya, was greatly improved by using long-chain ethers, such as di-n-hexyl ether, as solvents instead of the conventional diisopropyl ether. Thus, for example, the E value was enhanced from 21 [in diisopropyl ether (0.8 ml)] to 57 [in di-n-hexyl ether (0.8 ml)] in the reaction of 2,2,2-trifluoroethyl(RS)-2-phenoxypropanoate (0.1 mmol) with methanol (0.4 mmol) in the presence of the plant lipase preparation (10 mg); it was also improved from 13 (in diisopropyl ether) to 44 (in di-n-hexyl ether) in the reaction of 2,2,2-trifluoroethyl(RS)-2-(2-chlorophenoxy)propanoate with methanol under the same reaction conditions.

  20. Ruthenium-catalyzed C-H/N-O bond functionalization: green isoquinolone syntheses in water.


    Ackermann, Lutz; Fenner, Sabine


    Ruthenium-catalyzed isoquinolone syntheses with ample scope were accomplished through carboxylate assistance in environmentally benign water as a reaction medium. The high chemoselectivity of the ruthenium(II) carboxylate complex also set the stage for the direct use of free hydroxamic acids for annulations of alkynes.

  1. Enantioselective epoxidation and carbon-carbon bond cleavage catalyzed by Coprinus cinereus peroxidase and myeloperoxidase

    NARCIS (Netherlands)

    Tuynman, A; Lutje Spelberg, Jeffrey; Kooter, IM; Schoemaker, HE; Wever, R


    We demonstrate that myeloperoxidase (MPO) and Coprinus cinereus peroxidase (CiP) catalyze the enantioselective epoxidation of styrene and a number of substituted derivatives with a reasonable enantiomeric excess (up to 80%) and in a moderate yield. Three major differences with respect to the chlorop

  2. Localization of double bonds in wax esters by high-performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry utilizing the fragmentation of acetonitrile-related adducts. (United States)

    Vrkoslav, Vladimír; Háková, Martina; Pecková, Karolina; Urbanová, Klára; Cvačka, Josef


    Unsaturated wax esters (WEs) provided molecular adducts with C(3)H(5)N ([M + 55](+•)) in APCI sources in the presence of acetonitrile. CID MS/MS of [M + 55](+•) yielded fragments allowing the localization of double bond(s) in the hydrocarbon chains of the WEs. These fragments were formed by a cleavage on each side of the double bond. In methylene-interrupted polyunsaturated WEs, diagnostic fragments related to each double bond were detected; the most abundant were those corresponding to the cleavage of the C-C bond next to the first and the last double bond. To differentiate between those fragments differing in their structure or origin, a simple nomenclature based on α and ω ions has been introduced. Fragmentation of the α-type ions (fragments containing an ester bond) provided information on the occurrence of a double bond in the acid or alcohol part of the WEs. While no significant differences between the spectra of the WEs differing by cis/trans isomerism were found, the isomers were separated chromatographically. A data-dependent HPLC/APCI-MS(2) method for the comprehensive characterization of WEs in their complex mixtures has been developed and applied to natural mixtures of WEs isolated from jojoba oil and beeswax. More than 50 WE molecular species were completely identified, including the information on the acid and alcohol chain length and the position of the double bonds.

  3. An Upstream By-product from Ester Activation via NHC-Catalysis Catalyzes Downstream Sulfonyl Migration Reaction. (United States)

    Han, Runfeng; He, Liwenze; Liu, Lin; Xie, Xingang; She, Xuegong


    A sequential reaction combining N-heterocyclic carbene (NHC) and N-hydroxyphthalimide (NHPI) catalysis allowed for the upstream by-product NHPI, which was generated in the NHC-catalyzed cycloaddition reaction, to act as the catalyst for a downstream nitrogen-to-carbon sulfonyl migration reaction. Enantiomeric excess of the major product in the cycloaddition reaction remained intact in the follow-up sulfonyl migration reaction. PMID:26522328

  4. Efficient synthesis of π-conjugated molecules incorporating fluorinated phenylene units through palladium-catalyzed iterative C(sp2–H bond arylations

    Directory of Open Access Journals (Sweden)

    Fatiha Abdelmalek


    Full Text Available We report herein a two or three step synthesis of fluorinated π-conjugated oligomers through iterative C–H bond arylations. Palladium-catalyzed desulfitative arylation of heteroarenes allowed in a first step the synthesis of fluoroaryl-heteroarene units in high yields. Then, the next steps involve direct arylation with aryl bromides catalyzed by PdCl(C3H5(dppb to afford triad or tetrad heteroaromatic compounds via regioselective activation of C(sp2–H bonds.

  5. Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV)


    Tenn, William J., III; Conley, Brian L.; Hovelmann, Claas H.; Ahlquist, Marten; Nielsen, Robert J.; Ess, Daniel H.; Oxgaard, Jonas; Bischof, Steven M.; Goddard, William A.; Periana, Roy A.


    We report that SeO_2 catalyzes the facile oxy-functionalization of (CO)_5Re(I)-Me^(δ−) with IO_4− to generate methanol. Mechanistic studies and DFT calculations reveal that catalysis involves methyl group transfer from Re to the electrophilic Se center followed by oxidation and subsequent reductive functionalization of the resulting CH_3Se(VI) species. Furthermore, (CO)_3Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO_2 to generate the primary alcohols. T...

  6. Silver-catalyzed silicon-hydrogen bond functionalization by carbene insertion. (United States)

    Iglesias, M José; Nicasio, M Carmen; Caballero, Ana; Pérez, Pedro J


    The catalytic functionalization of silicon-hydrogen bonds by means of the insertion of carbene units :CHCO(2)Et from ethyl diazoacetate (EDA) has been achieved using a silver-based catalyst, constituting the first example of this metal to promote this transformation. Competition experiments have revealed that the relative reactivity of substituted silanes depends on the bond dissociation energy of the Si-H bond (tertiary > secondary > primary for ethyl substituted). In the presence of bulky substituents such order reverts to secondary > primary ≈ tertiary (for phenyl substituted). Screening with other diazo compounds has shown that N(2)C(Ph)CO(2)Et displays similar reactivity to that of EDA, whereas other N(2)C(R)CO(2)Et (R = Me, CO(2)Et) gave lower conversions. PMID:23114570

  7. Borane-catalyzed cracking of C-C bonds in coal; Boran-katalysierte C-C-Bindungungsspaltung in Steinkohle

    Energy Technology Data Exchange (ETDEWEB)

    Narangerel, J.; Haenel, M.W. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)


    Coal, especially coking coal, was reacted with hydrogen at comparatively mild reaction conditions (150-280 degrees centigrade, 20 MPa hydrogen pressure) in the presence of catalysts consisting of borange reagents and certain transition metal halides to obtaine more than 80 percent of pyridine-soluble products. The influence of the degree of coalification, catalyst and temperature on the borane-catalyzed hydrogenolysis of C-C bonds in coal was investigated. (orig.) [Deutsch] Steinkohlen, insbesondere im Inkohlungsbereich der Fettkohlen (Kokskohlen), werden in Gegenwart von Katalysatoren aus Boran-Reagentien und bestimmten Uebergangsmetallhalogeniden mit Wasserstoff bei vergleichsweise milden Reaktionsbedingungen (250-280 C, 20 MPa Wasserstoffdruck) in zu ueber 80% pyridinloesliche Produkte umgewandelt. Der Einfluss von Inkohlungsgrad, Katalysator und Temperatur auf die Boran-katalysierte C-C-Bindungshydrogenolyse in Kohle wurde untersucht. (orig.)

  8. Copper-Catalyzed Redox-Triggered Remote C-H Functionalization: Highly Selective Formation of C-CF3 and C-O Bonds

    Institute of Scientific and Technical Information of China (English)

    Taotao Li; Peng Yu; Jin-Shun Lin; Yonggang Zhi; Xin-Yuan Liu


    A Cu-catalyzed remote sp3 C-H/unactivated alkenes functionalization reaction for the concomitant construction ofC-CF3 and C-O bonds was described.An 1,5-H radical transfer involving an sp3 C-H bond adjacent to a nitrogen atom and an α-CF3-alkyl radical intermediate derived from unactivated alkenes was observed and demonstrated to proceed via the radical process.

  9. Esterification and Chemoselective Synthesis of R-Tetrahydrothiazo-2- thione-4-carboxylic Esters Catalyzed by TiCl4

    Institute of Scientific and Technical Information of China (English)

    SHANG Yan-mei; LI Jing; SONG Zhi-guang; LI Ye-zhi; HUANG Hua-min


    A series of esters of R-tetrahydrothiazo-2-thione-4-carboxylic acid[ R-TTCA] was synthesized by direct esterification of R-TTCA with alcohols(CH3OH, C2H5OH, n-C3H7OH, i-C3H7OH, n-C4H9OH, sec-C4H9OH) in the presence of TiCl4 as the catalyst at room temperature without using any other solvent or dehydrant in high yields,91.6%-99.1% for primary alcohols and 55%- 80% for secondary alcohols. The catalyst has a strong chemoselecfive activity for the esterification of primary alcohols with R-TTCA in the presence of secondary alcohols. Owing to high yield, high chemoselectivity, and mild conditions used, this is an efficient method for the esterification of primary alcohols with R-TTCA.

  10. Lipase-Catalyzed Production of 6-O-cinnamoyl-sorbitol from D-sorbitol and Cinnamic Acid Esters. (United States)

    Kim, Jung-Ho; Bhatia, Shashi Kant; Yoo, Dongwon; Seo, Hyung Min; Yi, Da-Hye; Kim, Hyun Joong; Lee, Ju Hee; Choi, Kwon-Young; Kim, Kwang Jin; Lee, Yoo Kyung; Yang, Yung-Hun


    To overcome the poor properties of solubility and stability of cinnamic acid, cinnamate derivatives with sugar alcohols were produced using the immobilized Candida antarctica lipase with vinyl cinnamate and D-sorbitol as substrate at 45 °C. Immobilized C. antarctica lipase was found to synthesize 6-O-cinnamoyl-sorbitol and confirmed by HPLC and (1)H-NMR and had a preference for vinyl cinnamate over other esters such as allyl-, ethyl-, and isobutyl cinnamate as co-substrate with D-sorbitol. Contrary to D-sorbitol, vinyl cinnamate, and cinnamic acid, the final product 6-O-cinnamoyl-sorbitol was found to have radical scavenging activity. This would be the first report on the biosynthesis of 6-O-cinnamoyl-sorbitol with immobilized enzyme from C. antarctica.

  11. Hydrogen Bonding, (1)H NMR, and Molecular Electron Density Topographical Characteristics of Ionic Liquids Based on Amino Acid Cations and Their Ester Derivatives. (United States)

    Rao, Soniya S; Bejoy, Namitha Brijit; Gejji, Shridhar P


    Amino acid ionic liquids (AAILs) have attracted significant attention in the recent literature owing to their ubiquitous applications in diversifying areas of modern chemistry, materials science, and biosciences. The present work focuses on unraveling the molecular interactions underlying AAILs. Electronic structures of ion pairs consisting of amino acid cations ([AA(+)], AA = Gly, Ala, Val, Leu, Ile, Pro, Ser, Thr) and their ester substituted derivatives [AAE(+)] interacting with nitrate anion [NO3(-)] have been obtained from the dispersion corrected M06-2x density functional theory. The formation of ion pair is accompanied by the transfer of proton from quaternary nitrogen to anion facilitated via hydrogen bonding. The [Ile], [Pro], [Ser], and [Thr] and their esters reveal relatively strong inter- as well as intramolecular hydrogen-bonding interactions. Consequently, the hierarchy in binding energies of [AA][NO3] ion pairs and their ester analogues turns out to be [Gly] > [Ala] > [Ser] ∼ [Val] ∼ [Ile] > [Leu] ∼ [Thr] > [Pro]. The work underlines how the interplay of intra- as well as intermolecular hydrogen-bonding interactions in [AA]- and [AAE]-based ILs manifest in their infrared and (1)H NMR spectra. Substitution of -OCH3 functional group in [AA][NO3] ILs lowers the melting point attributed to weaker hydrogen-bonding interactions, making them suitable for room temperature applications. As opposed to gas phase structures, the presence of solvent (DMSO) does not bring about any proton transfer in the ion pairs or their ester analogues. Calculated (1)H NMR chemical shifts of the solvated structures agree well with those from experiment. Correlations of decomposition temperatures in [AA]- and [AAE]-based ILs with binding energies and electron densities at the bond critical point(s) in molecular electron density topography, have been established. PMID:26192454

  12. Nickel-catalyzed Csp2-Csp3 bond formation by carbon-fluorine activation. (United States)

    Sun, Alex D; Leung, Kaylyn; Restivo, Anita D; LaBerge, Nicole A; Takasaki, Harumi; Love, Jennifer A


    We report herein a general catalytic method for Csp(2)-Csp(3) bond formation through C-F activation. The process uses an inexpensive nickel complex with either diorganozinc or alkylzinc halide reagents, including those with β-hydrogen atoms. A variety of fluorine substitution patterns and functional groups can be readily incorporated. Sequential reactions involving different precatalysts and coupling partners permit the synthesis of densely functionalized fluorinated building blocks.

  13. Boron-Catalyzed Aromatic C-H Bond Silylation with Hydrosilanes. (United States)

    Ma, Yuanhong; Wang, Baoli; Zhang, Liang; Hou, Zhaomin


    Metal-free catalytic C-H silylation of a series of aromatic compounds such as N,N-disubstituted anilines with various hydrosilanes has been achieved for the first time using commercially available B(C6F5)3 as a catalyst. This protocol features simple and neutral reaction conditions, high regioselectivity, wide substrate scope (up to 40 examples), Si-Cl bond compatibility, and no requirement for a hydrogen acceptor. PMID:26959863

  14. DFT Studies on the Isomerization of Butene Double Bond Catalyzed by 1-Butyl-3-methyl-imidazolium in Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    LI Ying-Xia; PU Min; CHEN Biao-Hua; LI Hui-Ying; LIU Kun-Hui; WANG Wen-Xing


    The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels.The variations of the bond parameters in the course of reaction were analyzed.The zero point energy corrections were performed by vibrational analysis.The equilibrium states and the transition state were verified according to the number of virtue frequency of geometry.The intrinsic reaction coordinates (IRC) were calculated from the transition state.The calculated results show that the double bond rearrangement of butene catalyzed by 1-butyl-3-methyl-imidazolium cation is a one-step reaction.The forward energy barrier of isomerization from 1-butene to 2- butene is about 193 kJmol-1 and the reverse energy barrier about 209 kJmol-1 at the B3LYP/6- 31G(d,p) level, which means that the reaction is easy to proceed at or above room temperature.

  15. Ampicillin-Ester Bonded Branched Polymers: Characterization, Cyto-, Genotoxicity and Controlled Drug-Release Behaviour

    Directory of Open Access Journals (Sweden)

    Ewa Oledzka


    Full Text Available The development and characterization of novel macromolecular conjugates of ampicillin using branched biodegradable polymers has been described in this study. The conjugates have been prepared coupling the β-lactam antibiotic with branched polymer matrices based on the natural oligopeptide core. The cyto- and genotoxicity of the synthesized polymers were evaluated with a bacterial luminescence test, two protozoan assays and Salmonella typhimurium TA1535. The presence of a newly formed covalent bond between the drug and the polymer matrices was confirmed by 1H-NMR and FTIR studies. A drug content (15.6 and 10.2 mole % in the macromolecular conjugates has been determined. The obtained macromolecular products have been subjected to further in vitro release studies. The total percentage of ampicillin released after 21 days of incubation was nearly 60% and 14% and this resulted from the different physicochemical properties of the polymeric matrices. This is the first report on the application of branched biodegradable polymeric matrices for the covalent conjugation of ampicillin. The obtained results showed that the synthesized macromolecular drug-conjugates might slowly release the active drug molecule and improve the pharmacokinetics of ampicillin.

  16. Catalyzed Ester Synthesis Using Candida rugosa Lipase Entrapped by Poly(N-isopropylacrylamide-co-itaconic Acid Hydrogel

    Directory of Open Access Journals (Sweden)

    Nikola Milašinović


    Full Text Available 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.

  17. Gene cloning and molecular characterization of the Talaromyces thermophilus lipase catalyzed efficient hydrolysis and synthesis of esters. (United States)

    Romdhane, Ines Belhaj-Ben; Frikha, Fakher; Maalej-Achouri, Inès; Gargouri, Ali; Belghith, Hafedh


    A genomic bank from Talaromyces thermophilus fungus was constructed and screened using a previously isolated fragment lipase gene as probe. From several clones isolated, the nucleotide sequence of the lipase gene (TTL gene) was completed and sequenced. The TTL coding gene consists of an open reading frame (ORF) of 1083bp encoding a protein of 269 Aa with an estimated molecular mass of 30kDa. The TTL belongs to the same gene family as Thermomyces lanuginosus lipase (TLL, Lipolase®), a well known lipase with multiple applications. The promoter sequence of the TTL gene showed the conservation of known consensus sequences PacC, CreA, Hap2-3-4 and the existence of a particular sequence like the binding sites of Oleate Response Element (ORE) and Fatty acids Responsis Element (FARE) which are similar to that already found to be specific of lipolytic genes in Candida and Fusarium, respectively. Northern blot analysis showed that the TTL expression was much higher on wheat bran than on olive oil as sole carbon source. Compared to the Lipolase®, this enzyme was found to be more efficient for the hydrolysis and the synthesis of esters; and its synthetic efficiency even reached 91.6% from Waste Cooking Oil triglycerides.

  18. Enzymatic synthesis of phytosterol esters catalyzed by Candida rugosa lipase in water-in-[Bmim]PF6 microemulsion. (United States)

    Zeng, Chaoxi; Qi, Suijian; Li, Zhigang; Luo, Riming; Yang, Bo; Wang, Yonghua


    A water-in-ionic liquid microemulsion ([Bmim]PF6/Tween20/H2O) was applied as reusable reaction medium to esterify phytosterols with fatty acid by Candida rugosa lipase (CRL) successfully. Two kinds of commercial CRLs, AY30 and AYS which cannot effectively catalyze esterification in conventional reaction system were found effective in the microemulsion system. Effects of reaction parameters on esterification were investigated; results showed that the conversion rate of 87.9 and 95.1 % was obtained in 24 and 48 h of reaction, respectively, under the optimized condition: the molar ratio of water to Tween 20 (w 0 value) at 5.4, Tween 20 at a concentration of 305 mM, 50 °C,pH 7.4, 10 % of enzyme loading (w/w, with respect to total reactants), and phytosterols/lauric acid molar ratio of 1:2. Moreover, by using n-hexane as the extraction agent, the lipase-encapsulated microemulsion could be reused at least seven times (>168 h) without significant changes in the conversion rate, while achieving a purpose of simple separation and purification. PMID:25575761

  19. Molecular mechanism of acid-catalyzed hydrolysis of peptide bonds using a model compound. (United States)

    Pan, Bin; Ricci, Margaret S; Trout, Bernhardt L


    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

  20. B-N, B-O, and B-CN Bond Formation via Palladium-Catalyzed Cross-Coupling of B-Bromo-Carboranes. (United States)

    Dziedzic, Rafal M; Saleh, Liban M A; Axtell, Jonathan C; Martin, Joshua L; Stevens, Simone L; Royappa, A Timothy; Rheingold, Arnold L; Spokoyny, Alexander M


    Carboranes are boron-rich molecules that can be functionalized through metal-catalyzed cross-coupling. Here, for the first time, we report the use of bromo-carboranes in palladium-catalyzed cross-coupling for efficient B-N, B-O, and unprecedented B-CN bond formation. In many cases bromo-carboranes outperform the traditionally utilized iodo-carborane species. This marked difference in reactivity is leveraged to circumvent multistep functionalization by directly coupling small nucleophiles (-OH, -NH2, and -CN) and multiple functional groups onto the boron-rich clusters. PMID:27384544

  1. Evaluation of the Ser-His Dipeptide, a Putative Catalyst of Amide and Ester Hydrolysis. (United States)

    MacDonald, Melissa J; Lavis, Luke D; Hilvert, Donald; Gellman, Samuel H


    Efficient hydrolysis of amide bonds has long been a reaction of interest for organic chemists. The rate constants of proteases are unmatched by those of any synthetic catalyst. It has been proposed that a dipeptide containing serine and histidine is an effective catalyst of amide hydrolysis, based on an apparent ability to degrade a protein. The capacity of the Ser-His dipeptide to catalyze the hydrolysis of several discrete ester and amide substrates is investigated using previously described conditions. This dipeptide does not catalyze the hydrolysis of amide or unactivated ester groups in any of the substrates under the conditions evaluated. PMID:27400366

  2. Graphene Oxide Catalyzed C-H Bond Activation: The Importance Oxygen Functional Groups for Biaryl Construction

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Yongjun; Tang, Pei; Zhou, Hu; Zhang, Wei; Yang, Hanjun; Yan, Ning; Hu, Gang; Mei, Donghai; Wang, Jianguo; Ma, Ding


    A heterogeneous, inexpensive and environment-friendly carbon catalytic system was developed for the C-H bond arylation of benzene resulting in the subsequent formation of biaryl compounds. The oxygen-containing groups on these graphene oxide sheets play an essential role in the observed catalytic activity. The catalytic results of model compounds and DFT calculations show that these functional groups promote this reaction by stabilization and activation of K ions at the same time of facilitating the leaving of I. And further mechanisms studies show that it is the charge induced capabilities of oxygen groups connected to specific carbon skeleton together with the giant π-reaction platform provided by the π-domain of graphene that played the vital roles in the observed excellent catalytic activity. D. Mei acknowledges the support from the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory.

  3. Iron-Carbonyl-Catalyzed Redox-Neutral [4+2] Annulation of N-H Imines and Internal Alkynes by C-H Bond Activation. (United States)

    Jia, Teng; Zhao, Chongyang; He, Ruoyu; Chen, Hui; Wang, Congyang


    Stoichiometric C-H bond activation of arenes mediated by iron carbonyls was reported by Pauson as early as in 1965, yet the catalytic C-H transformations have not been developed. Herein, an iron-catalyzed annulation of N-H imines and internal alkynes to furnish cis-3,4-dihydroisoquinolines is described, and represents the first iron-carbonyl-catalyzed C-H activation reaction of arenes. Remarkablely, this is also the first redox-neutral [4+2] annulation of imines and alkynes proceeding by C-H activation. The reaction also features only cis stereoselectivity and excellent atom economy as neither base, nor external ligand, nor additive is required. Experimental and theoretical studies reveal an oxidative addition mechanism for C-H bond activation to afford a dinuclear ferracycle and a synergetic diiron-promoted H-transfer to the alkyne as the turnover-determining step.

  4. Directing Group in Decarboxylative Cross-Coupling: Copper-Catalyzed Site-Selective C-N Bond Formation from Nonactivated Aliphatic Carboxylic Acids. (United States)

    Liu, Zhao-Jing; Lu, Xi; Wang, Guan; Li, Lei; Jiang, Wei-Tao; Wang, Yu-Dong; Xiao, Bin; Fu, Yao


    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

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

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


    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

  6. Transition Metal Catalyzed Hydroarylation of Multiple Bonds: Exploration of Second Generation Ruthenium Catalysts and Extension to Copper Systems

    Energy Technology Data Exchange (ETDEWEB)

    T. Brent Gunnoe


    Catalysts provide foundational technology for the development of new materials and can enhance the efficiency of routes to known materials. New catalyst technologies offer the possibility of reducing energy and raw material consumption as well as enabling chemical processes with a lower environmental impact. The rising demand and expense of fossil resources has strained national and global economies and has increased the importance of accessing more efficient catalytic processes for the conversion of hydrocarbons to useful products. The goals of the research are to develop and understand single-site homogeneous catalysts for the conversion of readily available hydrocarbons into useful materials. A detailed understanding of these catalytic reactions could lead to the development of catalysts with improved activity, longevity and selectivity. Such transformations could reduce the environmental impact of hydrocarbon functionalization, conserve energy and valuable fossil resources and provide new technologies for the production of liquid fuels. This project is a collaborative effort that incorporates both experimental and computational studies to understand the details of transition metal catalyzed C-H activation and C-C bond forming reactions with olefins. Accomplishments of the current funding period include: (1) We have completed and published studies of C-H activation and catalytic olefin hydroarylation by TpRu{l_brace}P(pyr){sub 3}{r_brace}(NCMe)R (pyr = N-pyrrolyl) complexes. While these systems efficiently initiate stoichiometric benzene C-H activation, catalytic olefin hydroarylation is hindered by inhibition of olefin coordination, which is a result of the steric bulk of the P(pyr){sub 3} ligand. (2) We have extended our studies of catalytic olefin hydroarylation by TpRu(L)(NCMe)Ph systems to L = P(OCH{sub 2}){sub 3}CEt. Thus, we have now completed detailed mechanistic studies of four systems with L = CO, PMe{sub 3}, P(pyr){sub 3} and P(OCH{sub 2}){sub 3}CEt

  7. The possible participation of esters as well as amides in prebiotic polymers. (United States)

    Rich, A.


    Demonstration that alpha-hydroxy acids may have participated in the formation of prebiological polymers in a manner similar to the participation of alpha-amino acids. Ex periments are described which indicate that the system for forming peptide bonds in present-day biological organisms is equally competent in forming ester and polyester bonds. In particular, the experiments described are directed toward answering questions regarding the action of peptidyl transferase in ester formation. Also, an attempt is made to determine whether a complete protein synthetic system can operate with transfer RNA molecules which have alpha-hydroxyl acids attached to them instead of alpha-amino acids, using both synthetic and natural mRNA. The ability of ribosomal peptidyl transferase to catalyze the formation of an ester bond as well as its normal product, the peptide bond, is demonstrated.

  8. Purification, molecular cloning, and expression of 2-hydroxyphytanoyl- CoA lyase, a peroxisomal thiamine pyrophosphate-dependent enzyme that catalyzes the carbon-carbon bond cleavage during à-oxidation of 3- methyl-branched fatty acids

    CERN Document Server

    Foulon, V; Croes, K; Waelkens, E


    Purification, molecular cloning, and expression of 2-hydroxyphytanoyl- CoA lyase, a peroxisomal thiamine pyrophosphate-dependent enzyme that catalyzes the carbon-carbon bond cleavage during à-oxidation of 3- methyl-branched fatty acids

  9. Transition-metal-catalyzed C-N bond forming reactions using organic azides as the nitrogen source: a journey for the mild and versatile C-H amination. (United States)

    Shin, Kwangmin; Kim, Hyunwoo; Chang, Sukbok


    Owing to the prevalence of nitrogen-containing compounds in functional materials, natural products and important pharmaceutical agents, chemists have actively searched for the development of efficient and selective methodologies allowing for the facile construction of carbon-nitrogen bonds. While metal-catalyzed C-N cross-coupling reactions have been established as one of the most general protocols for C-N bond formation, these methods require starting materials equipped with functional groups such as (hetero)aryl halides or their equivalents, thus generating stoichiometric amounts of halide salts as byproducts. To address this aspect, a transition-metal-catalyzed direct C-H amination approach has emerged as a step- and atom-economical alternative to the conventional C-N cross-coupling reactions. However, despite the significant recent advances in metal-mediated direct C-H amination reactions, most available procedures need harsh conditions requiring stoichiometric external oxidants. In this context, we were curious to see whether a transition-metal-catalyzed mild C-H amination protocol could be achieved using organic azides as the amino source. We envisaged that a dual role of organic azides as an environmentally benign amino source and also as an internal oxidant via N-N2 bond cleavage would be key to develop efficient C-H amination reactions employing azides. An additional advantage of this approach was anticipated: that a sole byproduct is molecular nitrogen (N2) under the perspective catalytic conditions. This Account mainly describes our research efforts on the development of rhodium- and iridium-catalyzed direct C-H amination reactions with organic azides. Under our initially optimized Rh(III)-catalyzed amination conditions, not only sulfonyl azides but also aryl- and alkyl azides could be utilized as facile amino sources in reaction with various types of C(sp(2))-H bonds bearing such directing groups as pyridine, amide, or ketoxime. More recently, a new

  10. Production of oleic acid ethyl ester catalyzed by crude rice bran (Oryza sativa lipase in a modified fed-batch system: problem and its solution

    Directory of Open Access Journals (Sweden)

    Indro Prastowo


    Full Text Available A fed-batch system was modified for the enzymatic production of Oleic Acid Ethyl Ester (OAEE using rice bran (Oryza sativa lipase by retaining the substrate molar ratio (ethanol/oleic acid at 2.05: 1 during the reaction. It resulted in an increase in the ester conversion up to 76.8% in the first 6 h of the reaction, and then followed by a decrease from 76.8% to 22.9% in 6 h later. Meanwhile, the production of water in the reaction system also showed a similar trend to the trend of ester production. The water was hypothesized to lead lipase to reverse the reaction which resulted in a decrease in both (water and esters in the last 6 h of the reaction. In order to overcome the problem, zeolite powders (25 and 50 mg/ml were added into the reaction system at 5 h of the reaction. As the result, final ester conversions increased drastically up to 90 - 95.7% (1.17 – 1.24 times. The addition also proved a hypothesis that the water was involved in reducing the ester conversion in the last 6 h of the reaction. Thus, the combination was effective to produce the high final ester conversion.

  11. Lipase-catalyzed polyester synthesis – A green polymer chemistry (United States)

    Kobayashi, Shiro


    This article is a short comprehensive review describing in vitro polyester synthesis catalyzed by a hydrolysis enzyme of lipase, most of which has been developed for these two decades. Polyesters are prepared by repeated ester bond-formation reactions; they include two major modes, ring-opening polymerization (ROP) of cyclic monomers such as cyclic esters (lactones) and condensation polymerization via the reaction between a carboxylic acid or its ester group and an alcohol group. Polyester synthesis is, therefore, a reaction in reverse way of in vivo lipase catalysis of ester bond-cleavage with hydrolysis. The lipase-catalyzed polymerizations show very high chemo-, regio-, and enantio-selectivities and involve various advantageous characteristics. Lipase is robust and compatible with other chemical catalysts, which allows novel chemo-enzymatic processes. New syntheses of a variety of functional polyesters and a plausible reaction mechanism of lipase catalysis are mentioned. The polymerization characteristics are of green nature currently demanded for sustainable society, and hence, desirable for conducting ‘green polymer chemistry’. PMID:20431260

  12. Metalloradical-Catalyzed Selective 1,2-Rh-H Insertion into the Aliphatic Carbon-Carbon Bond of Cyclooctane

    NARCIS (Netherlands)

    Y.W. Chan; B. de Bruin; K.S. Chan


    The selective aliphatic carboncarbon activation of cyclo-octane (c-octane) was achieved via the Rh-II(ttp)-catalyzed 1,2-addition of Rh(ttp)H to give Rh(ttp)(n-octyl) (ttp = tetratolylporphyrinato dianion) in good yield under mild reaction conditions. This mechanism is further supported by DFT calcu

  13. Copper(I)-catalyzed carbon-halogen bond-selective boryl substitution of alkyl halides bearing terminal alkene moieties


    Iwamoto, Hiroaki; Kubota, Koji; Yamamoto, Eiji; Ito, Hajime


    The selective boryl substitution of alkyl halides bearing terminal C=C double bonds has been achieved using a copper(I)/tricyclohexylphosphine or copper(I)/o-diphenylphosphinophenol catalyst. This reaction represents a useful complementary approach to conventional procedures for the hydroboration of C=C double bonds or the borylative cyclization of alkyl halides bearing terminal alkenes.


    NARCIS (Netherlands)



    Two methods for the separation of cholesterol esters, based on the number of double bonds in their fatty acid moieties, are presented. Silver ion chromatography, usually performed on thin-layer chromatographic plates, was made suitable for high-performance liquid chromatography (HPLC) and solid-phas

  15. Short Synthesis of Sulfur Analogues of Polyaromatic Hydrocarbons through Three Palladium-Catalyzed C-H Bond Arylations. (United States)

    Hagui, Wided; Besbes, Néji; Srasra, Ezzeddine; Roisnel, Thierry; Soulé, Jean-François; Doucet, Henri


    An expeditious synthesis of a wide range of phenanthro[9,10-b]thiophene derivatives, which are a class of polyaromatic hydrocarbon (PAH) containing a sulfur atom, is reported. The synthetic scheme involves only two operations from commercially available thiophenes, 2-bromobenzenesulfonyl chlorides and aryl bromides. In the first step, palladium-catalyzed desulfitative arylation using 2-bromobenzenesulfonyl chlorides allows the synthesis of thiophene derivatives, which are substituted at the C4 position by an aryl group containing an ortho-bromo substituent. Then, a palladium-catalyzed one-pot cascade intermolecular C5-arylation of thiophene using aryl bromides followed by intramolecular arylation led to the corresponding phenanthro[9,10-b]thiophenes in a single operation. In addition, PAHs containing two or three sulfur atoms, as well as both sulfur and nitrogen atoms, were also designed by this strategy. PMID:27550151

  16. High-yield preparation of wax esters via lipase-catalyzed esterification using fatty acids and alcohols from crambe and camelina oils. (United States)

    Steinke, G; Weitkamp, P; Klein, E; Mukherjee, K D


    Fatty acids obtained from seed oils of crambe (Crambe abyssinica) and camelina (Camelina sativa) via alkaline saponification or steam splitting were esterified using lipases as biocatalysts with oleyl alcohol and the alcohols derived from crambe and camelina oils via hydrogenolysis of their methyl esters. Long-chain wax esters were thus obtained in high yields when Novozym 435 (immobilized lipase B from Candida antarctica) and papaya (Carica papaya) latex lipase were used as biocatalysts and vacuum was applied to remove the water formed. The highest conversions to wax esters were obtained with Novozym 435 (> or =95%) after 4-6 h of reaction, whereas with papaya latex lipase such a high degree of conversion was attained after 24 h. Products obtained from stoichiometric amounts of substrates were almost exclusively (>95%) composed of wax esters having compositions approaching that of jojoba (Simmondsia chinensis) oil, especially when crambe fatty acids in combination with camelina alcohols or camelina fatty acids in combination with crambe alcohols were used as substrates.

  17. Lipase-catalyzed synthesis of L-ascorbyl fatty acid esters and D-isoascorbyl fatty acid esters%脂肪酶催化合成L-抗坏血酸脂肪酸酯和D-异抗坏血酸脂肪酸酯

    Institute of Scientific and Technical Information of China (English)

    郑大贵; 祝显虹; 余泗莲; 彭化南; 张小兰


    The lipase-catalyzed synthesis of L.-ascorbyl fatty acid esters and D-isoascorbyl fatty acid esters were studied by direct es-terification and transesterification,respectively. The structures of products were confirmed by IR,1H NMR,13C NMR and MS. It was found that the yield of the direct esterification were higher than that of the corresponding transesterification under the similar synthetic conditions. The raw material fatty acids and fatty acid methyl esters could be recycled and reused.%用固定化脂肪酶Lipozyme 435作催化剂,分别用直接酯化法和酯交换法合成L-抗坏血酸脂肪酸酯和D-异抗坏血酸脂肪酸酯.产物结构经IR、1HNMR、13CNMR和MS表征.结果表明,对于同一目标化合物,相似条件下,直接酯化法的效果优于酯交换法,原料脂肪酸和脂肪酸甲酯均可回收循环使用.

  18. Synthesis of Novel Monophosphoramidite Ligands Derived from L-Proline for Rh-catalyzed Asymmetric Hydrogenation of α-Dehydroamino Acid Esters

    Institute of Scientific and Technical Information of China (English)


    Two novel monophosphoramidites were synthesized through a five-step transformation from commercially available L-proline. In the Ph-catalyzed asymmetric hydrogenation of α-dehydroamino acid derivatives, ligand (Sc,Ra)-1b showed good enantioselectivity and up to 91% e.e. was obtained.

  19. 逆相转移催化合成葵花籽油蔗糖酯%Synthesis of sunflower oil sucrose ester catalyzed by inverse phase - transfer catalyst

    Institute of Scientific and Technical Information of China (English)

    樊国栋; 康丽; 林振宇


    Using water solvent method, sunflower oil sucrose ester was synthesized by inverse phase -transfer catalyst DMAP with sucrose and fatty acid methyl ester prepared by ester - exchange method in the presence of basic catalyst from sunflower oil and methanol. The effects of molar ratio of fatty acids methyl ester to sucrose, catalyst dosage, reaction temperature and reaction time were studied. The results showed that the optimal conditions were as follows; molar ratio of fatty acids methyl ester to sucrose 2.5:1, catalyst dosage 4% , reaction temperature 85 °C and reaction time 7 h. Under the optimal conditions, the conversion rate of sunflower oil fatty acid methyl ester could reach 65. 32%. The final product had good surface activity, the critical micelle concentration(CMC) was 6. 5 g/L, surface tension was 27.41 mN/ m, emulsifying power was 79s, water count was 7. 2 mL, HLB was 10. 1 and iodine value was 126. 9 gI/ 100 g.%先由食用葵花籽油和甲醇在碱性催化剂条件下酯交换反应制得脂肪酸甲酯,然后脂肪酸甲酯与蔗糖通过水溶剂法,以逆相转移催化剂DMAP催化制备蔗糖脂肪酸酯.通过对酯糖摩尔比、催化剂用量、反应温度、反应时间进行考察,确定最佳合成条件为:酯糖摩尔比2.5∶1,催化剂用量4%,反应温度 85℃,反应时间7h.在最佳合成条件下,葵花籽油脂肪酸甲酯的转化率高达65.32%,所得产品具有良好的表面活性,其临界胶束质量浓度(CMC)为6.5 g/L,表面张力为27.41 mN/m,乳化力为79 s,浊点指数为7.2 mL,HLB值为10.1,碘值(Ⅰ)为126.9 g/100 g.

  20. Direct Synthesis of Protoberberine Alkaloids by Rh-Catalyzed C-H Bond Activation as the Key Step. (United States)

    Jayakumar, Jayachandran; Cheng, Chien-Hong


    A one-pot reaction of substituted benzaldehydes with alkyne-amines by a Rh-catalyzed C-H activation and annulation to afford various natural and unnatural protoberberine alkaloids is reported. This reaction provides a convenient route for the generation of a compound library of protoberberine salts, which recently have attracted great attention because of their diverse biological activities. In addition, pyridinium salt derivatives can also be formed in good yields from α,β-unsaturated aldehydes and amino-alkynes. This reaction proceeds with excellent regioselectivity and good functional group compatibility under mild reaction conditions by using O2 as the oxidant. PMID:26689172

  1. Comparison of estimation capabilities of response surface methodology (RSM with artificial neural network (ANN in lipase-catalyzed synthesis of palm-based wax ester

    Directory of Open Access Journals (Sweden)

    Salleh Abu


    Full Text Available Abstract Background Wax esters are important ingredients in cosmetics, pharmaceuticals, lubricants and other chemical industries due to their excellent wetting property. Since the naturally occurring wax esters are expensive and scarce, these esters can be produced by enzymatic alcoholysis of vegetable oils. In an enzymatic reaction, study on modeling and optimization of the reaction system to increase the efficiency of the process is very important. The classical method of optimization involves varying one parameter at a time that ignores the combined interactions between physicochemical parameters. RSM is one of the most popular techniques used for optimization of chemical and biochemical processes and ANNs are powerful and flexible tools that are well suited to modeling biochemical processes. Results The coefficient of determination (R2 and absolute average deviation (AAD values between the actual and estimated responses were determined as 1 and 0.002844 for ANN training set, 0.994122 and 1.289405 for ANN test set, and 0.999619 and 0.0256 for RSM training set respectively. The predicted optimum condition was: reaction time 7.38 h, temperature 53.9°C, amount of enzyme 0.149 g, and substrate molar ratio 1:3.41. The actual experimental percentage yield was 84.6% at optimum condition, which compared well to the maximum predicted value by ANN (83.9% and RSM (85.4%. The order of effective parameters on wax ester percentage yield were; respectively, time with 33.69%, temperature with 30.68%, amount of enzyme with 18.78% and substrate molar ratio with 16.85%, whereas R2 and AAD were determined as 0.99998696 and 1.377 for ANN, and 0.99991515 and 3.131 for RSM respectively. Conclusion Though both models provided good quality predictions in this study, yet the ANN showed a clear superiority over RSM for both data fitting and estimation capabilities.

  2. Synthesis of Bioactive 2-(Arylaminothiazolo[5,4-f]-quinazolin-9-ones via the Hügershoff Reaction or Cu- Catalyzed Intramolecular C-S Bond Formation

    Directory of Open Access Journals (Sweden)

    Damien Hédou


    Full Text Available A library of thirty eight novel thiazolo[5,4-f]quinazolin-9(8H-one derivatives (series 8, 10, 14 and 17 was prepared via the Hügershoff reaction and a Cu catalyzed intramolecular C-S bond formation, helped by microwave-assisted technology when required. The efficient multistep synthesis of the key 6-amino-3-cyclopropylquinazolin-4(3H-one (3 has been reinvestigated and performed on a multigram scale from the starting 5-nitroanthranilic acid. The inhibitory potency of the final products was evaluated against five kinases involved in Alzheimer’s disease and showed that some molecules of the 17 series described in this paper are particularly promising for the development of novel multi-target inhibitors of kinases.

  3. Water as a green solvent for efficient synthesis of isocoumarins through microwave-accelerated and Rh/Cu-catalyzed C-H/O-H bond functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Li, Qiu; Yan, Yunnan; Wang, Xiaowei; Gong, Binwei; Tang, Xiaobo; Shi, JingJing; Xu, H. Eric; Yi, Wei [Shenyang; (Gannan); (Van Andel); (UST - China); (Chinese Aca. Sci.)


    Green chemistry that uses water as a solvent has recently received great attention in organic synthesis. Here we report an efficient synthesis of biologically important isocoumarins through direct cleavage of C–H/O–H bonds by microwave-accelerated and Rh/Cu-catalyzed oxidative annulation of various substituted benzoic acids, where water is used as the only solvent in the reactions. The remarkable features of this “green” methodology include high product yields, wide tolerance of various functional groups as substrates, and excellent region-/site-specificities, thus rendering this methodology a highly versatile and eco-friendly alternative to the existing methods for synthesizing isocoumarins and other biologically important derivatives such as isoquinolones.

  4. Transition metal-catalyzed oxidative double bond cleavage of simple and bio-derived alkenes and unsaturated fatty acids

    NARCIS (Netherlands)

    Spannring, Peter; Bruijnincx, Pieter C. A.; Weckhuysen, Bert. M.; Klein Gebbink, Bert


    The oxidative cleavage of the C=C double bond in unsaturated fatty acids into aldehydes or carboxylic acids is a reaction of current interest in biomass valorization. The products of this reaction, which is currently being performed on an industrial scale by means of ozonolysis, can be applied for t

  5. Ruthenium-Catalyzed Transfer Hydrogenation for C-C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs. (United States)

    Perez, Felix; Oda, Susumu; Geary, Laina M; Krische, Michael J


    Merging the chemistry of transfer hydrogenation and carbonyl or imine addition, a broad new family of redox-neutral or reductive hydrohydroxyalkylations and hydroaminomethylations have been developed. In these processes, hydrogen redistribution between alcohols and π-unsaturated reactants is accompanied by C-C bond formation, enabling direct conversion of lower alcohols to higher alcohols. Similarly, hydrogen redistribution between amines to π-unsaturated reactants results in direct conversion of lower amines to higher amines. Alternatively, equivalent products of hydrohydroxyalkylation and hydroaminomethylation may be generated through the reaction of carbonyl compounds or imines with π-unsaturated reactants under the conditions of 2-propanol-mediated reductive coupling. Finally, using vicinally dioxygenated reactants, that is, diol, ketols, or diones, successive transfer hydrogenative coupling occurs to generate 2 C-C bonds, resulting in products of formal [4+2] cycloaddition. PMID:27573275

  6. Transfer Hydrogenation of C= C Double Bonds Catalyzed by Ruthenium Amido-Complexes:Scopes, Limitation and Enantioselectivity

    Institute of Scientific and Technical Information of China (English)

    XUE,Dong; CHENG,Ying-Chun; CUI,Xin; WANG,Qi-Wei; ZHU,Jin; DENG,Jin-Gen


    @@ The reduction of C = C double bonds is one of the most fundamental synthetic transformations and plays a key role in the manufacturing of a wide variety of bulk and fine chemicals. Hydrogenation of olefinic substrates can be achieved readily with molecular hydrogen in many cases, but transfer hydrogenation methods using suitable donor molecules such as formic acid or alcohols are receiving increasing attention as possible synthetic alternatives because it requires no special equipment and avoids the handling of potentially hazardous gaseous hydrogen.

  7. Rhodotorula glutinis Phenylalanine/Tyrosine Ammonia Lyase Enzyme Catalyzed Synthesis of the Methyl Ester of para-Hydroxycinnamic Acid and its Potential Antibacterial Activity (United States)

    MacDonald, Marybeth C.; Arivalagan, Pugazhendhi; Barre, Douglas E.; MacInnis, Judith A.; D’Cunha, Godwin B.


    Biotransformation of L-tyrosine methyl ester (L-TM) to the methyl ester of para- hydroxycinnamic acid (p-HCAM) using Rhodotorula glutinis yeast phenylalanine/tyrosine ammonia lyase (PTAL; EC enzyme was successfully demonstrated for the first time; progress of the reaction was followed by spectrophotometric determination at 315 nm. The following conditions were optimized for maximal formation of p-HCAM: pH (8.5), temperature (37°C), speed of agitation (50 rpm), enzyme concentration (0.080 μM), and substrate concentration (0.50 mM). Under these conditions, the yield of the reaction was ∼15% in 1 h incubation period and ∼63% after an overnight (∼18 h) incubation period. The product (p-HCAM) of the reaction of PTAL with L-TM was confirmed using Nuclear Magnetic Resonance spectroscopy (NMR). Fourier Transform Infra-Red spectroscopy (FTIR) was carried out to rule out potential hydrolysis of p-HCAM during overnight incubation. Potential antibacterial activity of p-HCAM was tested against several strains of Gram-positive and Gram-negative bacteria. This study describes a synthetically useful transformation, and could have future clinical and industrial applications. PMID:27014206

  8. Rhodotorulaglutinis phenylalanine/tyrosine ammonia lyase enzyme catalyzed synthesis of the methyl ester of para-hydroxycinnamic acid and its potential antibacterial activity

    Directory of Open Access Journals (Sweden)

    Marybeth C MacDonald


    Full Text Available Biotransformation of L-tyrosine methyl ester (L-TM to the methyl ester of para- hydroxycinnamic acid (p-HCAM using Rhodotorula glutinis yeast phenylalanine/tyrosine ammonia lyase (PTAL; EC enzyme was successfully demonstrated for the first time; progress of the reaction was followed by spectrophotometric determination at 315 nm. The following conditions were optimized for maximal formation of p-HCAM: pH (8.5, temperature (37 C, speed of agitation (50 rpm, enzyme concentration (0.080 µM, and substrate concentration (0.50 mM. Under these conditions, the yield of the reaction was ~15% in 1 h incubation period and ~63% after an overnight (~18 h incubation period. The product (p-HCAM of the reaction of PTAL with L-TM was confirmed using Nuclear Magnetic Resonance spectroscopy (NMR. Fourier Transform Infra-Red spectroscopy (FTIR was carried out to rule out potential hydrolysis of p-HCAM during overnight incubation. Potential antibacterial activity of p-HCAM was tested against several strains of Gram positive and Gram negative bacteria. This study describes a synthetically useful transformation, and could have future clinical and industrial applications.

  9. Rhodotorula glutinis Phenylalanine/Tyrosine Ammonia Lyase Enzyme Catalyzed Synthesis of the Methyl Ester of para-Hydroxycinnamic Acid and its Potential Antibacterial Activity. (United States)

    MacDonald, Marybeth C; Arivalagan, Pugazhendhi; Barre, Douglas E; MacInnis, Judith A; D'Cunha, Godwin B


    Biotransformation of L-tyrosine methyl ester (L-TM) to the methyl ester of para- hydroxycinnamic acid (p-HCAM) using Rhodotorula glutinis yeast phenylalanine/tyrosine ammonia lyase (PTAL; EC enzyme was successfully demonstrated for the first time; progress of the reaction was followed by spectrophotometric determination at 315 nm. The following conditions were optimized for maximal formation of p-HCAM: pH (8.5), temperature (37°C), speed of agitation (50 rpm), enzyme concentration (0.080 μM), and substrate concentration (0.50 mM). Under these conditions, the yield of the reaction was ∼15% in 1 h incubation period and ∼63% after an overnight (∼18 h) incubation period. The product (p-HCAM) of the reaction of PTAL with L-TM was confirmed using Nuclear Magnetic Resonance spectroscopy (NMR). Fourier Transform Infra-Red spectroscopy (FTIR) was carried out to rule out potential hydrolysis of p-HCAM during overnight incubation. Potential antibacterial activity of p-HCAM was tested against several strains of Gram-positive and Gram-negative bacteria. This study describes a synthetically useful transformation, and could have future clinical and industrial applications.

  10. Nickel-Catalyzed Carbon–Carbon Bond-Forming Reactions of Unactivated Tertiary Alkyl Halides: Suzuki Arylations


    Zultanski, Susan L.; Fu, Gregory C.


    The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr[subscript 2]·diglyme/4,4′-di-tert-butyl-2,2′-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C–C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group,...

  11. Enantio- and Periselective Nitroalkene Diels-Alder Reactions Catalyzed by Helical-Chiral Hydrogen Bond Donor Catalysts

    Directory of Open Access Journals (Sweden)

    Zhili Peng


    Full Text Available Helical-chiral double hydrogen bond donor catalysts promote the nitroalkene Diels-Alder reaction in an enantio- and periselective manner. This represents the first asymmetric catalytic nitroalkene Diels-Alder reaction via LUMO-lowering catalysis. To gain an insight into this new process, the substrate scope of our catalyst was investigated by exploiting readily available 5-substituted pentamethylcyclopentadienes. The catalyst was found to tolerate dienes with different steric demands as well as dienes substituted with heteroatoms. The synthetic utility of 5-substituted pentamethylcyclopentadienes is rather limited, and thus we have developed a three-step route to 1,4,5,5-tetrasubstituted cyclopentadienes from commercially available ketones.

  12. Enantio- and periselective nitroalkene Diels-Alder reactions catalyzed by helical-chiral hydrogen bond donor catalysts. (United States)

    Peng, Zhili; Narcis, Maurice J; Takenaka, Norito


    Helical-chiral double hydrogen bond donor catalysts promote the nitroalkene Diels-Alder reaction in an enantio- and periselective manner. This represents the first asymmetric catalytic nitroalkene Diels-Alder reaction via LUMO-lowering catalysis. To gain an insight into this new process, the substrate scope of our catalyst was investigated by exploiting readily available 5-substituted pentamethylcyclopentadienes. The catalyst was found to tolerate dienes with different steric demands as well as dienes substituted with heteroatoms. The synthetic utility of 5-substituted pentamethylcyclopentadienes is rather limited, and thus we have developed a three-step route to 1,4,5,5-tetrasubstituted cyclopentadienes from commercially available ketones. PMID:23966083

  13. Rh(I)-Catalyzed Arylation of Heterocycles via C-H Bond Activation: Expanded Scope Through Mechanistic Insight

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Berman, Ashley; Bergman, Robert; Ellman, Jonathan


    A practical, functional group tolerant method for the Rh-catalyzed direct arylation of a variety of pharmaceutically important azoles with aryl bromides is described. Many of the successful azole and aryl bromide coupling partners are not compatible with methods for the direct arylation of heterocycles using Pd(0) or Cu(I) catalysts. The readily prepared, low molecular weight ligand, Z-1-tert-butyl-2,3,6,7-tetrahydrophosphepine, which coordinates to Rh in a bidentate P-olefin fashion to provide a highly active yet thermally stable arylation catalyst, is essential to the success of this method. By using the tetrafluoroborate salt of the corresponding phosphonium, the reactions can be assembled outside of a glove box without purification of reagents or solvent. The reactions are also conducted in THF or dioxane, which greatly simplifies product isolation relative to most other methods for direct arylation of azoles employing high-boiling amide solvents. The reactions are performed with heating in a microwave reactor to obtain excellent product yields in two hours.

  14. Ruthenium-Catalyzed Asymmetric Hydrohydroxyalkylation of Butadiene: The Role of the Formyl Hydrogen Bond in Stereochemical Control (United States)

    Grayson, Matthew N.; Krische, Michael J.; Houk, K. N.


    The catalyst generated in situ from RuH2(CO)(PPh3)3, (S)-SEGPHOS, and a chiral phosphoric acid promotes asymmetric hydrohydroxyalkylation of butadiene and affords enantioenriched α-methyl homoallylic alcohols. The observed diastereo- and enantioselectivities are determined by both the chiral phosphine and chiral phosphate ligands. Density functional theory calculations (M06/SDD-6-311G(d,p)-IEFPCM(acetone)//B3LYP/SDD-6-31G(d)) predict that the product distribution is controlled by the kinetics of carbon-carbon bond formation, and this process occurs via a closed-chair Zimmerman-Traxler-type transition structure (TS). Chiral phosphate-dependent stereoselectivity arising from this TS is enabled through a hydrogen bond between the phosphoryl oxygen and the aldehyde formyl proton present in TADDOL-derived catalysts. This interaction is absent in the corresponding BINOL-derived systems and the opposite sense of attack on the aldehyde occurs. Additional factors influencing stereochemical control are determined. PMID:26107070

  15. Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

    Energy Technology Data Exchange (ETDEWEB)

    Klobukowski, Erik [Iowa State Univ., Ames, IA (United States)


    conditions, it was found that the oxidative dehydrogenation of dibenzylamine to Nbenzylidenebenzylamine, with N-methylmorpholine N-oxide (NMMO), was nearly quantitative (96%) within 24 h. However, the reaction with oxygen was much slower, with only a 52% yield of imine product over the same time period. Moreover, the rate of reaction was found to be influenced by the nature of the amine N-oxide. For example, the use of the weakly basic pyridine N-oxide (PyNO) led to an imine yield of only 6% after 24 h. A comparison of amine N-oxide and O2 was also examined in the oxidation of PhCH{sub 2}OH to PhCHO catalyzed by bulk gold. In this reaction, a 52% yield of the aldehyde was achieved when NMMO was used, while only a 7% product yield was afforded when O{sub 2} was the oxidant after 48 h. The bulk gold-catalyzed oxidative dehydrogenation of cyclic amines generates amidines, which upon treatment with Aerosil and water were found to undergo hydrolysis to produce lactams. Moreover, 5-, 6-, and 7-membered lactams could be prepared through a one-pot reaction of cyclic amines by treatment with oxygen, water, bulk gold, and Aerosil. This method is much more atom economical than industrial processes, does not require corrosive acids, and does not generate undesired byproducts. Additionally, the gold and Aerosil catalysts can be readily separated from the reaction mixture. The second project involved studying iron(III) tetraphenylporphyrin chloride, Fe(TPP)Cl, as a homogeneous catalyst for the generation of carbenes from diazo reagents and their reaction with heteroatom compounds. Fe(TPP)Cl, efficiently catalyzed the insertion of carbenes derived from methyl 2-phenyldiazoacetates into O-H bonds of aliphatic and aromatic alcohols. Fe(TPP)Cl was also found to be an effective catalyst for tandem N-H and O-H insertion/cyclization reactions when 1,2-diamines and 1,2-alcoholamines were treated with diazo reagents. This approach provides a one-pot process for synthesizing piperazinones and

  16. Lewis酸性离子液体催化合成丁二酸二异丙酯%Synthesis of succinic acid diisopropyl ester catalyzed by Lewis acid ionic liquids

    Institute of Scientific and Technical Information of China (English)

    赵地顺; 葛京京; 翟建华; 张娟; 刘猛帅; 李俊盼


    采用两步法制备了9种不同的Lewis酸性离子液体,采用1H NMR、FT-IR对离子液体的结构进行了表征,并系统地考察了其对丁二酸和异丙醇酯化反应的催化性能。结果表明,离子液体随着卤化物用量增加表现出更强的酸性。其中[Bmim]Br-Fe2Cl6催化合成丁二酸二异丙酯效果良好,催化剂用量为丁二酸质量的10.0%,反应温度100℃,反应时间4 h,酸醇摩尔比为1:5,丁二酸二异丙酯收率为88.9%,酯化率达92.7%。离子液体重复使用6次后,产品收率下降1.7%。%Nine kinds of different Lewis acid ionic liquids were synthesized by two-step process and their structures were characterized with 1H NMR and FT-IR. Lewis acid ionic liquids prepared were used to catalyze the esterification reaction of succinic acid and isopropyl alcohol. With the increase of dosage of halide, the ionic liquids showed stronger acidity. [Bmim]Br-Fe2Cl6 had the best catalytic performance, and optimal conditions for the synthesis of succinic acid diisopropyl ester were obtained as follows, amount of catalyst 10.0%(g/g)of succinic acid, reaction temperature 100℃ and reaction time 4 h, succinic acid and isopropyl alcohol ratio 1:5. Under the optimal conditions, the yield of succinic acid diisopropyl ester was up to 88.9%, esterification rate was 92.7%.The catalyst was recycled 6 times, and the yield of succinic acid diisopropyl ester only decreased by 1.7%.

  17. Synthesis of Structured Lipids by Lipase-Catalyzed Interesterification of Triacetin with Camellia Oil Methyl Esters and Preliminary Evaluation of their Plasma Lipid-Lowering Effect in Mice

    Directory of Open Access Journals (Sweden)

    Xiaoning Wang


    Full Text Available Structured lipids (SLCTs triacylglycerols with short- and long-chain acyl residues were synthesized by interesterification of triacetin and fatty acid methyl esters (FAMEs from camellia oil, followed by molecular distillation for purification. Different commercial immobilized lipases (Lipozyme RM IM and Novozyme 435, the substrate molar ratios of FAMEs to triacetin, the reaction temperatures and the lipase amounts were studied for their efficiency in producing SLCTs. Results showed that Novozyme 435 was more suitable for this reaction system. Moreover, the optimal reaction conditions for the highest conversion of FAMEs and the highest LLS-TAGs (triacylglycerols with one short- and two long-chain acyl residues yields were achieved at a molar ratio of FAMEs to triacetin of 3:1, 50 °C of reaction temperature and a lipase amount of 4% (w/v. Scale-up was conducted based on the optimized reaction conditions. Results showed that after 24 h of reaction , the conversion rate of FAMEs was 82.4% and the rate of disubstituted triacetin was 52.4 mol%. The final product yield rate was 94.6%. The effects of the synthesized SLCTs on the plasma lipid level of fasting mice were also studied. The SLCTs could effectively lessen the total triacylglycerol levels in plasma compared to the triacylglycerol group in fasting NIH mice. It suggested that this type of structured lipid might be beneficial for human health, especially for the prevention of obesity.

  18. Sonolytic and Silent Polymerization of Methacrlyic Acid Butyl Ester Catalyzed by a New Onium Salt with bis-Active Sites in a Biphasic System — A Comparative Investigation

    Directory of Open Access Journals (Sweden)

    Perumberkandgai A. Vivekanand


    Full Text Available Currently, ingenious new analytical and process experimental techniques which are environmentally benign techniques, viz., ultrasound irradiation, have become immensely popular in promoting various reactions. In this work, a novel soluble multi-site phase transfer catalyst (PTC viz., 1,4-bis-(propylmethyleneammounium chloridebenzene (BPMACB was synthesized and its catalytic efficiency was assessed by observing the kinetics of sonolytic polymerization of methacrylic acid butyl ester (MABE using potassium persulphate (PPS as an initiator. The ultrasound–multi-site phase transfer catalysis (US-MPTC-assisted polymerization reaction was compared with the silent (non-ultrasonic polymerization reaction. The effects of the catalyst and various reaction parameters on the catalytic performance were in detail investigated by following the kinetics of polymerization of MABE in an ethyl acetate-water biphasic system. From the detailed kinetic investigation we propose a plausible mechanism. Further the kinetic results demonstrate clearly that ultrasound-assisted phase-transfer catalysis significantly increased the reaction rate when compared to silent reactions. Notably, this environmentally benign and cost-effective process has great potential to be applied in various polymer industries.

  19. A pinoresinol-lariciresinol reductase homologue from the creosote bush (Larrea tridentata) catalyzes the efficient in vitro conversion of p-coumaryl/coniferyl alcohol esters into the allylphenols chavicol/eugenol, but not the propenylphenols p-anol/isoeugenol. (United States)

    Vassão, Daniel G; Kim, Sung-Jin; Milhollan, Jessica K; Eichinger, Dietmar; Davin, Laurence B; Lewis, Norman G


    The creosote bush (Larrea tridentata) accumulates a complex mixture of 8-8' regiospecifically linked lignans, of which the potent antioxidant nordihydroguaiaretic acid (NDGA) is the most abundant. Its tetra-O-methyl derivative (M4N) is showing considerable promise in the treatment of refractory (hard-to-treat) brain and central nervous system tumors. NDGA and related 9,9'-deoxygenated lignans are thought to be formed by dimerization of allyl/propenyl phenols, phenylpropanoid compounds that lack C-9 oxygenation, thus differentiating them from the more common monolignol-derived lignans. In our ongoing studies dedicated towards elucidating the biochemical pathway to NDGA and its congeners, a pinoresinol-lariciresinol reductase homologue was isolated from L. tridentata, with the protein obtained in functional recombinant form. This protein efficiently catalyzes the conversion of p-coumaryl and coniferyl alcohol esters into the corresponding allylphenols, chavicol and eugenol; neither of their propenylphenol regioisomers, p-anol and isoeugenol, are formed during this enzyme reaction.

  20. The Molybdenum Active Site of Formate Dehydrogenase Is Capable of Catalyzing C-H Bond Cleavage and Oxygen Atom Transfer Reactions. (United States)

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


    Formate dehydrogenases (FDHs) are capable of performing the reversible oxidation of formate and are enzymes of great interest for fuel cell applications and for the production of reduced carbon compounds as energy sources from CO2. Metal-containing FDHs in general contain a highly conserved active site, comprising a molybdenum (or tungsten) center coordinated by two molybdopterin guanine dinucleotide molecules, a sulfido and a (seleno-)cysteine ligand, in addition to a histidine and arginine residue in the second coordination sphere. So far, the role of these amino acids in catalysis has not been studied in detail, because of the lack of suitable expression systems and the lability or oxygen sensitivity of the enzymes. Here, the roles of these active site residues is revealed using the Mo-containing FDH from Rhodobacter capsulatus. Our results show that the cysteine ligand at the Mo ion is displaced by the formate substrate during the reaction, the arginine has a direct role in substrate binding and stabilization, and the histidine elevates the pKa of the active site cysteine. We further found that in addition to reversible formate oxidation, the enzyme is further capable of reducing nitrate to nitrite. We propose a mechanistic scheme that combines both functionalities and provides important insights into the distinct mechanisms of C-H bond cleavage and oxygen atom transfer catalyzed by formate dehydrogenase. PMID:27054466

  1. Degradation of phthalate esters and acetaminophen in river sediments using the electrokinetic process integrated with a novel Fenton-like process catalyzed by nanoscale schwertmannite. (United States)

    Yang, Gordon C C; Huang, Sheng-Chih; Wang, Chih-Lung; Jen, Yu-Sheng


    The main objective of this study was to develop and establish an in situ remediation technology coupling nano-schwertmannite/H2O2 process and electrokinetic (EK) process for the removal of phthalates (PAEs) and acetaminophen in river sediments. Test results are given as follows: (1) injection of nano-schwertmannite slurry and H2O2 (collectively, "novel oxidant") into the anode reservoir would yield ·OH radicals that then will be diffused into the sediment compartment and further transported by the electroosmotic flow and/or electrophoresis from the anode end toward the cathode to degrade PAEs and pharmaceuticals in the sediment if any; (2) an electric potential gradient of 1.5 V cm(-1) would help the removal of PAEs and acetaminophen in the blank test, which no "novel oxidants" was added to the remediation system; (3) the practice of electrode polarity reversal would maintain neutral pH for sediment after remediation; (4) injection of equally divided dose of 10 mL novel oxidant into the anode reservoir and four injection ports on the top of sediment chamber would further enhance the removal efficiency; and (5) an extension of treatment time from 14 d to 28 d is beneficial to the removal efficiency as expected. In comparison, the remediation performance obtained by the EK-assisted nano-SHM/H2O2 oxidation process is superior to that of the batch degradation test, but is comparable with other EK integrated technologies for the treatment of same contaminants. Thus, it is expected that the EK-assisted nano-SHM/H2O2 oxidation process is a viable technology for the removal of phthalate esters and pharmaceuticals from river sediments in large-scale operations. PMID:27309673

  2. Degradation of phthalate esters and acetaminophen in river sediments using the electrokinetic process integrated with a novel Fenton-like process catalyzed by nanoscale schwertmannite. (United States)

    Yang, Gordon C C; Huang, Sheng-Chih; Wang, Chih-Lung; Jen, Yu-Sheng


    The main objective of this study was to develop and establish an in situ remediation technology coupling nano-schwertmannite/H2O2 process and electrokinetic (EK) process for the removal of phthalates (PAEs) and acetaminophen in river sediments. Test results are given as follows: (1) injection of nano-schwertmannite slurry and H2O2 (collectively, "novel oxidant") into the anode reservoir would yield ·OH radicals that then will be diffused into the sediment compartment and further transported by the electroosmotic flow and/or electrophoresis from the anode end toward the cathode to degrade PAEs and pharmaceuticals in the sediment if any; (2) an electric potential gradient of 1.5 V cm(-1) would help the removal of PAEs and acetaminophen in the blank test, which no "novel oxidants" was added to the remediation system; (3) the practice of electrode polarity reversal would maintain neutral pH for sediment after remediation; (4) injection of equally divided dose of 10 mL novel oxidant into the anode reservoir and four injection ports on the top of sediment chamber would further enhance the removal efficiency; and (5) an extension of treatment time from 14 d to 28 d is beneficial to the removal efficiency as expected. In comparison, the remediation performance obtained by the EK-assisted nano-SHM/H2O2 oxidation process is superior to that of the batch degradation test, but is comparable with other EK integrated technologies for the treatment of same contaminants. Thus, it is expected that the EK-assisted nano-SHM/H2O2 oxidation process is a viable technology for the removal of phthalate esters and pharmaceuticals from river sediments in large-scale operations.

  3. Synthesis of amide-functionalized cellulose esters by olefin cross-metathesis. (United States)

    Meng, Xiangtao; Edgar, Kevin J


    Cellulose esters with amide functionalities were synthesized by cross-metathesis (CM) reaction of terminally olefinic esters with different acrylamides, catalyzed by Hoveyda-Grubbs 2nd generation catalyst. Chelation by amides of the catalyst ruthenium center caused low conversions using conventional solvents. The effects of both solvent and structure of acrylamide on reaction conversion were investigated. While the inherent tendency of acrylamides to chelate Ru is governed by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides, from 50% to up to 99%. Homogeneous hydrogenation using p-toluenesulfonyl hydrazide successfully eliminated the α,β-unsaturation of the CM products to give stable amide-functionalized cellulose esters. The amide-functionalized product showed higher Tg than its starting terminally olefinic counterpart, which may have resulted from strong hydrogen bonding interactions of the amide functional groups.

  4. Synthesis of amide-functionalized cellulose esters by olefin cross-metathesis. (United States)

    Meng, Xiangtao; Edgar, Kevin J


    Cellulose esters with amide functionalities were synthesized by cross-metathesis (CM) reaction of terminally olefinic esters with different acrylamides, catalyzed by Hoveyda-Grubbs 2nd generation catalyst. Chelation by amides of the catalyst ruthenium center caused low conversions using conventional solvents. The effects of both solvent and structure of acrylamide on reaction conversion were investigated. While the inherent tendency of acrylamides to chelate Ru is governed by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides, from 50% to up to 99%. Homogeneous hydrogenation using p-toluenesulfonyl hydrazide successfully eliminated the α,β-unsaturation of the CM products to give stable amide-functionalized cellulose esters. The amide-functionalized product showed higher Tg than its starting terminally olefinic counterpart, which may have resulted from strong hydrogen bonding interactions of the amide functional groups. PMID:26256383

  5. InX3(X=F,Br)催化N-甲基吲哚与酮酸酯不对称合成机理的研究%Investigation on the Mechanism for N-Methylindole and Keto Ester Catalyzed by InX3(X=F,Br)

    Institute of Scientific and Technical Information of China (English)

    王薇; 毛双; 彭丹; 李来才


    The reaction mechanism for N-methylindole and keto ester catalyzed by InX3 (X=F,Br) was studied by the density functional theory (DFT).The geometries and the frequencies of reactants,intermediates,transition states,and products have been calculated at the B3LYP/6-31 +G(d,p) level,dichloroethane (DCE) is used as a solvent and the LanL2DZ basis has been used for In atom.Transition states have been confirmed by the corresponding vibration analysis and intrinsic reaction coordinate (IRC).In addition,nature bond orbital (NBO) and atoms in molecules (AIM) theories have been used to analyze orbital interactions and bond natures.The results showed that the activation energies of rate-determining steps in which N-methylindole reacted with keto ester to form 1,2-adduct and 1,4-adduct were 25.62 and 12.52 kcal/mol catalyzed by InF3 while those were 26.87 and 13.95 kcal/mol when the reaction was catalyzed by InBr3 under the same conditions.Comparing the results of our research,InF3 can effectively catalyze the reaction,and the 1,4-adduct was more likely to be produced.The final result of our theory study agreed with the experimental data,meanwhile,self-consistent reaction field (SCRF) was carried out using the polarized continuum model (PCM) at the same theoretical level for geometry optimizations and frequency calculations in five different salvations.We predicted that the productivity to form 1,4-adduct was more higher catalyzed by InF3 in the solvent of dimethyl sulfoxide (DMSO).%采用密度泛函理论(DFT)中的B3LYP方法,在B3LYP/6-31+ G(d,p)基组水平上(In采用赝势基组LanL2DZ),二氯乙烷(DCE)作为溶剂,研究了InX3 (X=F,Br)催化N-甲基吲哚与酮酸酯不对称合成微观反应机理,对反应通道上反应物、中间体、过渡态和产物进行了结构优化,通过能量和振动频率分析以及内禀反应坐标(IRC)计算证实了过渡态和中间体的合理性,并且在相同基组水平上,通过自然键轨道(NBO)理论和原子理论

  6. Synthesis of trimethylolpropane esters by powdered lipase-catalyzed esterification%脂肪酶粉催化酯化合成三羟甲基丙烷酯

    Institute of Scientific and Technical Information of China (English)

    王娟; 陈必强; 谭天伟


    以辛酸、癸酸和三羟甲基丙烷作为反应底物,利用Candida sp.99-125脂肪酶粉催化反应,研究了反应条件对酶法合成三羟甲基丙烷三辛癸酸酯的影响,并在实验中找到一种可以提高酶粉稳定性的添加剂β-环糊精.结果表明,加入0.01 mol三羟甲基丙烷(TMP) (1.34g),n三羟甲基丙烷/n(癸酸+辛酸)=1∶4,其中n癸酸∶n辛酸=1∶1,添加水的质量分数为0.05%(以底物总质量为基准)、脂肪酶粉的质量分数为12%(以底物总质量为基准)、β-环糊精的质量为酶粉质量的1.5倍,40℃下在恒温摇床中,振荡反应130h,转速130 r/min.在此条件下,反应产物三羟甲基丙烷三辛癸酸酯(三羟基酯)的质量分数可达到80%左右,酸与酯分离后收率可达96%;连续使用6批添加了β-环糊精的脂肪酶粉,三羟基酯的质量分数可保持在60%以上,与固定化酶的使用寿命相当.%The enzymatic production of trimethylolpropane (TMP) esters from the reaction of octanoic acid and de-canoic acid with TMP in the presence of powdered lipase Candida sp. 99-125 in a solvent-free system has been studied. The effects of varying the experimental conditions were studied in order to optimize the process. A maximum mass fraction of 80% of triesters was obtained after 130 h under the following optimized conditions; 0. 01 mol TMP, nTMP/n(octanoic acid +decanoic acid) =1: 4, noctanoic acid /ndecanoic acid = 1: 1, 0.05% (mass fraction) of added water (based on the weight of total substrate) , 12% (mass fraction) of powdered lipase (based on the weight of total substrate) , with added β-cyclodextrin (1.5 times the mass of powdered lipase) , at 40 ℃. After separating the products, the yield of triester reached 96% . Moreover, the powdered lipase with added β-cyclodextrin could be used continuously in six batches with the final mass fraction of triester remaining over 60% .

  7. 固体碱催化合成中碳链脂肪酸聚甘油酯%Synthesis of polyglycerol medium chain fatty acid ester catalyzed by solid base catalyst

    Institute of Scientific and Technical Information of China (English)

    曾哲灵; 邹强; 聂蓉蓉; 龙俊敏; 张驰


    以聚甘油、樟树籽仁油脂肪酸为原料,固体碱KOH/Al2O3为催化剂,催化酯化合成中碳链脂肪酸聚甘油酯.采用单因素试验研究反应温度、反应时间、聚甘油与中碳链脂肪酸质量比、催化剂用量对酯化率的影响,通过正交试验优化中碳链脂肪酸聚甘油酯的合成工艺.最优合成工艺条件为反应温度220℃、反应时间2.5h、聚甘油与中碳链脂肪酸质量比2∶1、催化剂用量4.5%,该条件下酯化率为87.5%,所得中碳链脂肪酸聚甘油酯的酸值(KOH)、皂化值(KOH)、碘值(Ⅰ)、熔点分别为1.86 mg/g、148.4 mg/g、2.9 g/100 g、47.3℃.%The solid base KOH/A12O3 was used as catalyst to catalyze esterification of polyglycerol and fatty acids of camphor tree seed kernel oil to synthesize polyglycerol medium chain fatty acid ester. The effects of reaction temperature, reaction time, mass ratio of polyglycerol to medium chain fatty acid and dosage of catalyst on esterification rate were studied by single factor tests, and the synthesis technology of polyglycerol medium chain fatty acid ester was optimized by an orthogonal test. The optimal synthesis conditions were as follows: reaction temperature 220 °C , reaction time 2. 5 h, mass ratio of polyglycerol to medium chain fatty acid 2:1, dosage of catalyst 4. 5%. Under the optimal conditions, the esterification yield reached 87. 5% , and the acid value, saponification value, iodine value, and melting point of the product were 1.86 mgKOH/g,148.4 mgKOH/g, 2.9 gl/100 g and 47. 3 °C , respectively.

  8. Synthesis and Characteristics of an Aspartame Analogue, L-Asparaginyl L-3-Phenyllactic Acid Methyl Ester

    Institute of Scientific and Technical Information of China (English)

    Hu TAO; Da-Fu CUI; You-Shang ZHANG


    An aspartame analogue,L-asparaginyl L-3-phenyllactic acid methyl ester was synthesized with aspartic acid replaced by asparagine and peptide bond replaced by ester bond.The aspartic acid of aspartame could be replaced by asparagine as reported in the literature.In this analogue,the hydrogen ofamide group could still form a hydrogen bond with the oxygen of ester bond and the ester bond was isosteric with peptide bond.However,the product was not sweet,showing that the peptide bond could not be replaced by ester bond.The peptide C-N bond behaves as a double bond that is not free to rotate and the C,O,N and H atoms are in the same plane.The replacement of peptide bond by ester bond destroyed the unique conformation of peptide bond,resulting in the loss of sweet taste.

  9. Synthesis and characteristics of an aspartame analogue, L-asparaginyl L-3-phenyllactic acid methyl ester. (United States)

    Tao, Hu; Cui, Da-Fu; Zhang, You-Shang


    An aspartame analogue, L-asparaginyl L-3-phenyllactic acid methyl ester was synthesized with aspartic acid replaced by asparagine and peptide bond replaced by ester bond. The aspartic acid of aspartame could be replaced by asparagine as reported in the literature. In this analogue, the hydrogen of amide group could still form a hydrogen bond with the oxygen of ester bond and the ester bond was isosteric with peptide bond. However, the product was not sweet, showing that the peptide bond could not be replaced by ester bond. The peptide C-N bond behaves as a double bond that is not free to rotate and the C, O, N and H atoms are in the same plane. The replacement of peptide bond by ester bond destroyed the unique conformation of peptide bond, resulting in the loss of sweet taste.

  10. Valyl benzyl ester chloride

    Directory of Open Access Journals (Sweden)

    Grzegorz Dutkiewicz


    Full Text Available In the title compound (systematic name: 1-benzyloxy-3-methyl-1-oxobutan-2-aminium chloride, C12H18NO2+·Cl−, the ester group is approximately planar, with a maximum deviation of 0.040 (2 Å from the least-squares plane, and makes a dihedral angle of 28.92 (16° with the phenyl ring. The crystal structure is organized by N—H...Cl hydrogen bonds which join the two components into a chain along the b axis. Pairs of chains arranged antiparallel are interconnected by further N—H...Cl hydrogen bonds, forming eight-membered rings. Similar packing modes have been observed in a number of amino acid ester halides with a short unit-cell parameter of ca 5.5 Å along the direction in which the chains run.

  11. Recent Progress in the Research of Transition-Metal-Catalyzed C-CN Bond Cleavage%过渡金属催化的C—CN键断裂的研究进展

    Institute of Scientific and Technical Information of China (English)

    寇学振; 范佳骏; 童晓峰; 沈增明


    有机氰化物是一种重要的合成中间体,在药物、农药、染料和活性物质中都有应用.使用廉价、简单、低毒的氰基化合物在过渡金属的催化下通过C-CN键断裂生成复杂的氰化物是合成有机氰化物的重要手段之一.综述了不同过渡金属(如Ni,Pd,Rh,Cu,Ru,Fe,Mo,Co等)催化不同种类的氰基化合物C-CN键断裂的最新研究进展,如含C(sp1)-CN键化合物、C(sp2)-CN键化合物以及C(sp3)-CN键化合物,并对有关的反应机理及C-CN键断裂机理的进展进行了探讨.%Nitriles are an important class of organic compounds which can be found in pharmaceuticals,agrochemicals,dyes,and bioactive compounds.Transition-metal-catalyzed C-CN bond cleavage using inexpensive,simple and less toxic nitriles is one of the most attractive modem methods for the synthesis of complicated organic cyanides.Research progress of transition-metal-catalyzed (Ni,Pd,Rh,Cu,Ru,Fe,Mo,Co) different types of C-CN bond cleavage is reviewed,which includes some organic cyanides containing C(sp1)—CN bond,C(sp2)—CN bond and C(sp3)—CN bond.The C-CN cleavage mechanisms are also discussed in this review.

  12. Gold-Catalyzed Synthesis of Heterocycles (United States)

    Arcadi, Antonio


    The following sections are included: * Introduction * Synthesis of Heterocycles via Gold-Catalyzed Heteroatom Addition to Unsaturated C-C Bonds * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cyclization of Polyunsaturated Compounds * Synthesis of Heterocyclic Compounds via α-Oxo Gold Carbenoid * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cycloaddition Reactions * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Activation of Carbonyl Groups and Alcohols * Synthesis of Heterocyclic Compounds through Gold-Mediated C-H Bond Functionalization * Gold-Catalyzed Domino Cyclization/Oxidative Coupling Reactions * Conclusions * References

  13. Ester Exchange Polymerization of 3-Hydroxyl Propionic Acid Methyl Ester Catalyzed by SO3 H-functionalized Ionic Liquids%磺酸功能化离子液体催化3-羟基丙酸甲酯酯交换聚合反应

    Institute of Scientific and Technical Information of China (English)

    徐国荣; 刘建华; 宋大勇; 陈静; 夏春谷


    Employing SO3 H-functionalized ionic liquids as catalysts, the biodegradable poly [ 3-hydroxypropionic acid] (PHP) was obtained by ester exchange polymerization of 3-Hydroxyl propionie acid methyl ester(3-HPM). The effects of various ionic liquids, reaction temperature and reaction time on the polymerization performance were discussed in detail. Meanwhile, the FFIR, NMR and TG-DSC were applied to characterize the products. The PHP with Mw above 1.0×104 and yield above 82% could be obtained when catalyzed by [ BsMIm] [ OTf] under the opti- mal reaction conditions. In addition, the catalyst in the polymer could be removed completely after washing with water, efficiently avoiding the pollution of the product.%以磺酸功能化咪唑离子液体为催化剂,以3-羟基丙酸甲酯为原料,采用自身酯交换法合成了具有生物可降解性能的聚羟基脂肪酸酯.系统考察了离子液体种类、反应温度以及聚合反应时间对反应性能的影响,同时采用红外、核磁、热分析等手段对产物进行表征.研究结果表明:阴离子为CF3SO-3的磺酸功能化离子液体在120℃的低温下催化聚合反应所得聚酯Mw可达10 159,收率82.1%;通过水洗方法可有效去除产物中的离子液体催化剂,从而避免催化剂污染产物.

  14. Palladium-catalyzed Cs2CO3-promoted arylation of unactivated C(sp(3))-H bonds by (diacetoxyiodo)arenes: shifting the reactivity of (diacetoxyiodo)arenes from acetoxylation to arylation. (United States)

    Gou, Quan; Zhang, Zhao-Fu; Liu, Zhi-Cheng; Qin, Jun


    PdCl2(CH3CN)2-catalyzed arylation of unactivated C(sp(3))-H bonds using (diacetoxyiodo)arenes as arylation reagents is reported. The reactivity of (diacetoxyiodo)arenes as arylation reagents is enabled in the presence of Cs2CO3 under the reaction conditions. This arylation method is highly efficient and occurs without the use of silver salt. The reaction tolerates a broad substrate scope that was not demonstrated by other silver salt-free C(sp(3))-H bond arylation conditions. The synthetic utility of the method is further illustrated in the synthesis of the psychotropic drug phenibut. A detailed mechanism study has been conducted to understand the reaction pathway. PMID:25763683

  15. C8-Selective Acylation of Quinoline N-Oxides with α-Oxocarboxylic Acids via Palladium-Catalyzed Regioselective C-H Bond Activation. (United States)

    Chen, Xiaopei; Cui, Xiuling; Wu, Yangjie


    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

  16. Efficient C-O and C-N bond forming cross-coupling reactions catalyzed by core-shell structured Cu/Cu2O nanowires

    KAUST Repository

    Elshewy, Ahmed M.


    Oxygen and Nitrogen containing compounds are of utmost importance due to their interesting and diverse biological activities. The construction of the C-O and C–N bonds is of significance as it opens avenues for the introduction of ether and amine linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts or ligands in many cases. Thus, it is a challenge to develop alternative, milder, cheaper and more reproducible methodologies for the construction of these types of bonds. Herein, we introduce a new efficient ligand free catalytic system for C-O and C-N bond formation reactions.

  17. Metal-catalyzed C-C bond cleavage in alkanes: effects of methyl substitution on transition-state structures and stability. (United States)

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


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

  18. Antibody-Catalyzed Degradation of Cocaine (United States)

    Landry, Donald W.; Zhao, Kang; Yang, Ginger X.-Q.; Glickman, Michael; Georgiadis, Taxiarchis M.


    Immunization with a phosphonate monoester transition-state analog of cocaine provided monoclonal antibodies capable of catalyzing the hydrolysis of the cocaine benzoyl ester group. An assay for the degradation of radiolabeled cocaine identified active enzymes. Benzoyl esterolysis yields ecgonine methyl ester and benzoic acid, fragments devoid of cocaine's stimulant activity. Passive immunization with such an artificial enzyme could provide a treatment for dependence by blunting reinforcement.

  19. Synthesis of Free Amino Acid Esters Co-catalyzed by Ionic Liquid%离子液体协同催化合成游离氨基酸酯

    Institute of Scientific and Technical Information of China (English)

    尚岩; 贾俊英; 高海鹏; 裴蕾; 仲昭琪


    以L-氨基酸和醇为原料,酸性离子液体辅以少量强酸性阳离子交换树脂作催化剂,直接酯化合成了8种游离的L-氨基酸酯,并用1HNMR对产物进行了表征.通过L-苯丙氨酸正丁酯的合成对离子液体的活性进行了考察,结果表明,所选用的11种离子液体在反应过程中均起到了一定的催化作用和助溶作用.其中,[Hmim][HSO4]效果较好,在重复使用后,显示了较好的稳定性,是氨基酸酯化反应理想的催化剂和助溶剂.%Eight kinds of free L-amino acid esters including L-phenylalanine ethyl ester, L-phenylalanine n-butyl ester, L-phenylalanine i-butyl ester, L-tyrosine n-butyl ester, L-tyrosine i-butyl ester, L-tyrosine i-amyl ester, L-aspartic n-butyl diester and L-aspartic i-butyl diester were synthesized by direct esterification of L-amino acid and alcohol with acidic ionic liquid assisted by strong acidic cation resin as catalyst. The structures of free L-amino acid esters were characterized by 1HNMR.Optimal reaction conditions were obtained when synthesizing L-phenylalanine n-butyl ester. Among eleven kinds of the acidic ionic liquids used in this case, [Hmim] [ HSO4 ] indicated excellent activity and the catalyst is easily regenerated and reused. By this token, it exhibits its potential application as catalyst and co-solvent in the esterification of amino acid.

  20. Papain-Catalyzed Synthesis of Polyglutamate Containing a Nylon Monomer Unit

    Directory of Open Access Journals (Sweden)

    Kenjiro Yazawa


    Full Text Available Peptides have the potential to serve as an alternative for petroleum-based polymers to support a sustainable society. However, they lack thermoplasticity, owing to their strong intermolecular interactions. In contrast, nylon is famous for its thermoplasticity and chemical resistance. Here, we synthesized peptides containing a nylon unit to modify their thermal properties by using papain-catalyzed chemoenzymatic polymerization. We used l-glutamic acid alkyl ester as the amino acid monomer and nylon 1, 3, 4, and 6 alkyl esters as the nylon unit. Papain catalyzed the copolymerization of glutamic acid with nylon 3, 4, and 6 alkyl esters, whereas the nylon 1 unit could not be copolymerized. Other proteases used in this study, namely, bromelain, proteinase K, and Candida antarctica lipase (CALB, were not able to copolymerize with any nylon units. The broad substrate specificity of papain enabled the copolymerization of l-glutamic acid with a nylon unit. The peptides with nylon units demonstrated different thermal profiles from that of oligo(l-glutamic acid. Therefore, the resultant peptides with various nylon units are expected to form fewer intermolecular hydrogen bonds, thus altering their thermal properties. This finding is expected to broaden the applications of peptide materials and chemoenzymatic polymerization.

  1. Cobalt-Catalyzed Cyclization of N-Methoxy Benzamides with Alkynes using an Internal Oxidant through C-H/N-O Bond Activation. (United States)

    Sivakumar, Ganesan; Vijeta, Arjun; Jeganmohan, Masilamani


    The cyclization of substituted N-methoxy benzamides with alkynes in the presence of an easily affordable cobalt complex and NaOAc provides isoquinolone derivatives in good to excellent yields. The cyclization reaction is compatible with a range of functional group-substituted benzamides, as well as ester- and alcohol-substituted alkynes. The cobalt complex [Co(III) Cp*(OR)2 ] (R=Me or Ac) serves as an efficient catalyst for the cyclization reaction. Later, isoquinolone derivatives were converted into 1-chloro and 1-bromo substituted isoquinoline derivatives in excellent yields in the presence of POCl3 or PBr3 . PMID:26951887

  2. Research progress of lipase-catalyzed synthesis of L-ascorbyl organic acid ester%脂肪酶催化合成L-抗坏血酸有机酸酯的研究进展

    Institute of Scientific and Technical Information of China (English)

    蒋相军; 胡燚; 刘维明; 黄和


    To broaden the applications of L-ascorbic acid, it is an economical and feasible way to convert L-aseorbic acid into L-ascorbyl organic acid ester. The recent research progress of enzymatic synthesis of L-ascorbyl organic acid ester is summarized, by focusing on enzymatic synthesis of L-ascorbyl saturated fatty acid ester, unsaturated fatty acid ester and mixed fatty acid ester in organic solvents. The types of lipase, organic solvents and methods of separation and purification in the synthesis are discussed. Furthermore, the prospect of enzymatic synthesis of L-ascorbyl organic acid ester is also presented.%为了拓宽L-抗坏血酸酯在维护人体健康中的应用,将L-抗坏血酸转化成L-抗坏血酸酯是经济可行的手段。综述了近年来酶催化L-抗坏血酸有机酸酯的研究进展,重点介绍了有机相中L-抗坏血酸饱和脂肪酸酯、不饱和脂肪酸酯、脂肪酸混合酯的酶促合成,对于酶的种类、有机溶剂的选择及分离纯化方法进行了探讨,并对酶催化L-抗坏血酸有机酸酯合成前景进行了展望。

  3. 离子液体中6-O-(11-十二烯酸)葡萄糖酯的脂肪酶催化合成及其表征%Lipase-catalyzed synthesis and characterization of 6-O-(11-dodecenoic)-glucose ester in ionic liquids

    Institute of Scientific and Technical Information of China (English)

    黄广君; 韦超; 姚评佳; 魏远安


    In order to investigate the lipase-catalyzed selective transesterification of glucose with 11-dodecenoic ethyl ester in ionic liquids, the single-factor method was used to optimize the reaction conditions and determined various factors on the yield such as ionic liquids, temperature, molar rati-o, water content and enzyme concentration. The synthetic product structure was characterized by FT-IR, HPLC, MS and NMR. The results showed that the highest yield of sugar ester was obtained in 1-butyl-3-methyl imidazolium tetrailuoroborate [Bmitn] [BF4] under such conditions as the reaction temperature at 55 ℃, the enzyme concentration at 20 mg/mL, the mole ratio of glucose over 11 -dodecenoic ethyl ester at 1:2, and the water content of the system at 2% . Lipase Novozym-435 can be used 7 times repeatedly. The catalyzed product by Novozym-435 lipase in selective transesterification in [Bmim]BF4 was 6-O-(11-dodecenoic)-glucose ester.%为了探索脂肪酶在离子液体中选择性地催化葡萄糖与11-十二烯酸乙酯的转酯化反应,通过不同脂肪酶在不同离子液体中进行转酯化反应,并用单因素法研究离子液体种类、温度、底物的比例、体系含水量和脂肪酶含量对反应产率的影响,优化反应条件.反应产物的结构通过红外光谱、高效液相色谱、质谱和核磁共振等表征.结果表明:脂肪酶Novozym - 435在离子液体1-正丁基-3-甲基咪唑氟硼酸盐[BMIM][BF4]中,当反应温度为55℃、酶浓度20mgnmL、葡萄糖/11 -十二烯酸乙酯的摩尔比1∶2、体系的水含量为2%时,获得糖酯的产率最高,Novozym - 435可以重复使用7次.脂肪酶Novozym - 435在离子液体[BMIM][BF4]中选择性转酯化反应的产物为6-O-(11-十二烯酸)葡萄糖单酯.

  4. 离子液体中葡萄糖棕榈酸酯的酶法合成及表征%Enzyme-catalyzed synthesis and characterization of palmitoly glucose ester in ionic liquids

    Institute of Scientific and Technical Information of China (English)

    曾文恬; 姚评佳; 魏远安


    In the synthesis of palmitolyglucose ester, Candida antarctica lipase B was used as catalyst for the synthesis of palmitolyglucose ester by glucose and palmitic acid vinyl ester in ionic liquids. The effects of substrate ratio, lipase content and temperature were studied. The highest yield of sugar ester was obtained in [ Bmim ] [ TfO ] under such conditions as the reaction temperature of 40 C, the enzyme concentration of 50 mg/mL, the mole ratio of glucose/vinyl palmitate of 1: 3. The structure of products was characterized by FT-IR, HPLC, MS and NMR. The results showed that the product is 6-O-palmitolyglucose ester.%以南极假丝酵母脂肪酶(Candida antarctica lipase B)为催化剂、葡萄糖和棕榈酸乙烯酯为原料,在离子液体中合成葡萄糖棕榈酸酯.并研究了最佳反应条件,结果表明,以离子液体1-丁基-3-甲基咪唑三氟甲磺酸盐([Bmim][TfO])为介质的最佳条件为:温度40℃、酶浓度为50mg/mL、糖酯摩尔比1∶3.产物用傅里叶变换红外光谱(FT-IR)、高效液相色谱(HPLC)、质谱(MS)和核磁共振(NMR)进行了表征,结果表明是6-O-葡萄糖棕榈酸酯.

  5. Density functional study of electronic, charge density, and chemical bonding properties of 9-methyl-3-Thiophen-2-YI-Thieno [3,2-e] [1, 2, 4] Thriazolo [4,3-c] pyrimidine-8-Carboxylic acid ethyl ester crystals

    Energy Technology Data Exchange (ETDEWEB)

    Reshak, A.H., E-mail: [New Technologies – Research Center, University of West Bohemia, Univerzitni 8, 306 14 Pilsen (Czech Republic); Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia); Kamarudin, H. [Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia); Alahmed, Z.A. [Department of Physics and Astronomy, King Saud University, Riyadh 11451 (Saudi Arabia); Auluck, S. [CSIR-National Physical Laboratory, Dr. K S Krishnan Marg, New Delhi 110012 (India); Chyský, Jan [Department of Instrumentation and Control Engineering, Faculty of Mechanical Engineering, CTU in Prague, Technicka 4, 166 07 Prague 6 (Czech Republic)


    A comprehensive theoretical density functional investigation of the electronic crystal structure, chemical bonding, and the electron charge densities of 9-Methyl-3-Thiophen-2-YI-Thieno [3, 2-e] [1, 2, 4] Thriazolo [4,3-c] Pyrimidine-8-Carboxylic Acid Ethyl Ester (C{sub 15}H{sub 12}N{sub 4}O{sub 2}S{sub 2}) is performed. The density of states at Fermi level equal to 5.50 (3.45) states/Ry cell, and the calculated bare electronic specific heat coefficient is found to be 0.95 (0.59) mJ/mole-K{sup 2} for the local density approximation (Engel–Vosko generalized gradient approximation). The electronic charge density space distribution contours in (1 0 0) and (1 1 0) planes were calculated. We find that there are two independent molecules (A and B) in the asymmetric unit exhibit intramolecular C–H…O, C–H…N interactions. This intramolecular interaction is different in molecules A and B, where A molecule show C–H…O interaction while B molecule exhibit C–H…N interaction. We should emphasis that there is π–π interaction between the pyrimidine rings of the two neighbors B molecules gives extra strengths and stabilizations to the superamolecular structure. The calculated distance between the two neighbors pyrimidine rings found to be 3.345 Å, in good agreement with the measured one (3.424(1) Å). - Highlights: • Electronic structure, chemical bonding, and electron charge density were studied. • Density of states at Fermi level is 5.50 (3.45) states/Ry cell, for LDA (EVGGA). • Bare electronic specific heat coefficient is 0.95 (0.59) mJ/mole-K{sup 2} for LDA(EVGGA). • There are two independent molecules (A and B) in the asymmetric unit.

  6. The origin of enantioselectivity in the l-threonine-derived phosphine-sulfonamide catalyzed aza-Morita-Baylis-Hillman reaction: Effects of the intramolecular hydrogen bonding

    KAUST Repository

    Lee, Richmond


    l-Threonine-derived phosphine-sulfonamide 4 was identified as the most efficient catalyst to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions, affording the desired aza-MBH adducts with excellent enantioselectivities. Density functional theory (DFT) studies were carried out to elucidate the origin of the observed enantioselectivity. The importance of the intramolecular N-H⋯O hydrogen-bonding interaction between the sulfonamide and enolate groups was identified to be crucial in inducing a high degree of stereochemical control in both the enolate addition to imine and the subsequent proton transfer step, affording aza-MBH reactions with excellent enantioselectivity. © 2013 The Royal Society of Chemistry.

  7. Ruthenium(II)-catalyzed synthesis of pyrrole- and indole-fused isocoumarins by C-H bond activation in DMF and water

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Sawant, S.G.; Dixneuf, P.H.

    : ChemCatChem, vol.8(6); 2016; 1046-1050 Ruthenium(II) catalysed synthesis of pyrrole and indole fused isocoumarins via C-H bond activation in DMF and water† Keisham S. Singh*,a Sneha G. Sawanta, Pierre H. Dixneuf*,b Abstract: Pyrrole and indole... isocoumarins from simple 1-methyl pyrrole-2- carboxylic acid and 1-methylindole-3-carboxylic acid via annulation with alkyne in the presence ruthenium(II) catalyst based on [RuCl2(p-cymene)]2 and Cu(OAc)2.H2O as oxidant in DMF. This ruthenium(II) catalysed...

  8. Ligand-Mediated and Copper-Catalyzed C(sp3)-H Bond Functionalization of Aryl Ketones with Sodium Sulfinates under Mild Conditions (United States)

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


    A novel and convenient copper (II) bromide and 1,8-diazabicyclo[5.4.1]undec-7-ene (DBU) or 1,10-phenanthroline catalysis protocol for the construction of α-alkyl-β-keto sulfones via C(sp3)-H bond functionalization followed by C(sp3)-S bond formation between aryl ketones and sodium sulfinates at room temperature has been developed. This method is applicable to a wide range of aryl ketones and sodium sulfinates. The electronic effects of aryl ketones and ligands effects of the copper salts are crucial for this transformation. Typically, substituted aryl ketones with electron-withdrawing group do not need any ligand to give a good to excellent yield, while substituted aryl ketones with electron-donating group and electron-rich heteroaromatic ketones offer a good to excellent yield only under the nitrogen-based ligands. The practical value of this transformation highlights the efficient and robust one-pot synthesis of α-alkyl-β-keto sulfones.

  9. FINAL TECHNICAL REPORT for grant DE-FG02-93ER14353 "Carbon-Hydrogen Bond Functionalization Catalyzed by Transition Metal Systems"

    Energy Technology Data Exchange (ETDEWEB)

    Goldman, Alan S


    Alkanes are our most abundant organic resource but are highly resistant to selective chemical transformations. Alkenes (olefins) by contrast are the single most versatile class of molecules for selective transformations, and are intermediates in virtually every petrochemical process as well as a vast range of commodity and fine chemical processes. Over the course of this project we have developed the most efficient catalysts to date for the selective conversion of alkanes to give olefins, and have applied these catalysts to other dehydrogenation reactions. We have also developed some of the first efficient catalysts for carbonylation of alkanes and arenes to give aldehydes. The development of these catalysts has been accompanied by elucidation of the mechanism of their operation and the factors controlling the kinetics and thermodynamics of C-H bond activation and other individual steps of the catalytic cycles. This fundamental understanding will allow the further improvement of these catalysts, as well as the development of the next generation of catalysts for the functionalization of alkanes and other molecules containing C-H bonds.

  10. Highly Efficient C--N Bond Forming Reactions in Water Catalyzed by Copper(I) Iodide with Calix[4]arene Supported Amino Acid Ionic Liquid%Highly Efficient C--N Bond Forming Reactions in Water Catalyzed by Copper(I) Iodide with Calix[4]arene Supported Amino Acid Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    黄利; 金灿; 苏为科


    A novel and effective protocol has been developed for the Ullmann-type C--N coupling reaction catalyzed by calix[4]arene supported amino acid ionic liquid and copper(I) iodide in water under microwave irradiation condition The protocol uses ealix[4]arene supported amino acid ionic liquid as double function of the ligand and phase-transfer catalyst, and shows good tolerance in good to excellent yields.


    Institute of Scientific and Technical Information of China (English)



    在无溶剂体系中用脂肪酶Lipase LVK、Lipase AY 30G及LipaseF-AP15催化红花油水解,测试了水解产物中脂肪酸与酯的碘值及酯中单甘酯的含量,研究了脂肪酶对脂肪酸种类的选择性以及对甘油酯键位置的选择性.结果表明,脂肪酶Lipase LVK、Lipase AY30G没有位置选择性和脂肪酸选择性,而Lipase F-AP15无脂肪酸选择性,但有一定的位置选择性.%Enzymatic hydrolysis of safflower oil catalyzed by Lipase LVK 、 Lipase AY 30G and Lipase F-AP15 was investigated in a solvent-free system. The selectivity of the lipase was also examined by testing the monoglycerides content in the ester and the iodine values (IV) of the fatty acid and the ester. The experiment showed that Lipase LVK and Lipase AY 30G has no selectivity on either the fatty acid or the site of the ester bond on the acylg-lycerol,while Lipase F-AP15 has some selectivity on the site of the ester bond on the acylg-lycerol but it has no selectivity on the fatty acid either.

  12. Iron-Catalyzed Ortho C-H Methylation of Aromatics Bearing a Simple Carbonyl Group with Methylaluminum and Tridentate Phosphine Ligand. (United States)

    Shang, Rui; Ilies, Laurean; Nakamura, Eiichi


    Iron-catalyzed C-H functionalization of aromatics has attracted widespread attention from chemists in recent years, while the requirement of an elaborate directing group on the substrate has so far hampered the use of simple aromatic carbonyl compounds such as benzoic acid and ketones, much reducing its synthetic utility. We describe here a combination of a mildly reactive methylaluminum reagent and a new tridentate phosphine ligand for metal catalysis, 4-(bis(2-(diphenylphosphanyl)phenyl)phosphanyl)-N,N-dimethylaniline (Me2N-TP), that allows us to convert an ortho C-H bond to a C-CH3 bond in aromatics and heteroaromatics bearing simple carbonyl groups under mild oxidative conditions. The reaction is powerful enough to methylate all four ortho C-H bonds in benzophenone. The reaction tolerates a variety of functional groups, such as boronic ester, halide, sulfide, heterocycles, and enolizable ketones.

  13. 油包水微乳液中抗体酶催化布洛芬酯选择性水解的酶学特性%Enzymological Characteristics of Catalytic Antibody-catalyzed enantioselective Hydrolysis of Ibuprofen Ester in Water-in-oil microemulsion

    Institute of Scientific and Technical Information of China (English)

    杨根生; 戚映丹; 欧志敏; 姚善泾


    The asymmetric hydrolyzation of racemic ibuprofen ester is one of the most important methods for chiral separation of ibuprofen. A catalytic antibody that accelerates the rate of enantioselective hydrolysis of ibuprofen methyl ester was successfully elicited against an immunogen consisting of tetrahedral sulfate hapten attached to bovine serum albumin (BSA). The rate constant enhancement factor Kcat/Kuncat was about 1.6x104. The catalytic activity of the catalytic antibody in a reverse micelle reaction system based on sodium b/s (2-ethylhexyl) sodium sulfosuccinate (AOT) in isooctane was studied. Kinetic analysis of the catalytic antibody-catalyzed reaction was found to be possible in this system. Kinetic studies showed that hydrolysis in the microemulsion system follow Michaelis-Menten kinetics. The catalytic antibody can also accelerate catalysis of S-ibuprofen methyl ester in the microemulsion system. Temperature effects, the pH profile, Km,app and Kcat were determined. The dependence of the catalytic antibody hydrolytic activity on the Wo (molar ratio of water to surfactant) showed a bell-shaped curve, presenting a maximum at about wo = 21.%根据过渡态理论设计和合成了能诱导产生催化选择性水解布洛芬甲酯的催化抗体的四面体硫酸盐半抗原,并与牛血清白蛋白(BSA)偶联制备成免疫源,通过免疫手段成功筛选出具有加速选择性水解生成S-布洛芬的特异性催化抗体.其Kcat,app/Kuncat,app达1.6x104.进一步地将催化抗体运用到W/O微乳体系(反胶束)中进行布洛芬酯的选择性水解研究,其动力学研究证明其催化过程同样遵循Michaelis.Menten方程.考察了pH值和温度对催化初速度影响,Wo(体系中水和琥珀酸二辛酯磺酸钠(AOT)的摩尔比)对催化初速度影响呈现为钟罩型,最适的Wo.为21.

  14. Dimethyl carbonate-mediated lipid extraction and lipase-catalyzed in situ transesterification for simultaneous preparation of fatty acid methyl esters and glycerol carbonate from Chlorella sp. KR-1 biomass. (United States)

    Jo, Yoon Ju; Lee, Ok Kyung; Lee, Eun Yeol


    Fatty acid methyl esters (FAMEs) and glycerol carbonate were simultaneously prepared from Chlorella sp. KR-1 containing 40.9% (w/w) lipid using a reactive extraction method with dimethyl carbonate (DMC). DMC was used as lipid extraction agent, acyl acceptor for transesterification of the extracted triglycerides, substrate for glycerol carbonate synthesis from glycerol, and reaction medium for the solvent-free reaction system. For 1g of biomass, 367.31 mg of FAMEs and 16.73 mg of glycerol carbonate were obtained under the optimized conditions: DMC to biomass ratio of 10:1 (v/w), water content of 0.5% (v/v), and Novozyme 435 to biomass ratio of 20% (w/w) at 70°C for 24h. The amount of residual glycerol was only in the range of 1-2.5mg. Compared to conventional method, the cost of FAME production with the proposed technique could be reduced by combining lipid extraction with transesterification and omitting the extraction solvent recovery process. PMID:24583221

  15. Dimethyl carbonate-mediated lipid extraction and lipase-catalyzed in situ transesterification for simultaneous preparation of fatty acid methyl esters and glycerol carbonate from Chlorella sp. KR-1 biomass. (United States)

    Jo, Yoon Ju; Lee, Ok Kyung; Lee, Eun Yeol


    Fatty acid methyl esters (FAMEs) and glycerol carbonate were simultaneously prepared from Chlorella sp. KR-1 containing 40.9% (w/w) lipid using a reactive extraction method with dimethyl carbonate (DMC). DMC was used as lipid extraction agent, acyl acceptor for transesterification of the extracted triglycerides, substrate for glycerol carbonate synthesis from glycerol, and reaction medium for the solvent-free reaction system. For 1g of biomass, 367.31 mg of FAMEs and 16.73 mg of glycerol carbonate were obtained under the optimized conditions: DMC to biomass ratio of 10:1 (v/w), water content of 0.5% (v/v), and Novozyme 435 to biomass ratio of 20% (w/w) at 70°C for 24h. The amount of residual glycerol was only in the range of 1-2.5mg. Compared to conventional method, the cost of FAME production with the proposed technique could be reduced by combining lipid extraction with transesterification and omitting the extraction solvent recovery process.

  16. 微波辐射硫酸氢钠催化合成对氨基苯甲酸苄酯%Synthesis of 4-aminobenzoic acid benzyl ester catalyzed by sodium bisulfate under microwave radiation

    Institute of Scientific and Technical Information of China (English)

    杨晓军; 李西安


    在微波辐射下,以一水合硫酸氢钠为催化剂,对氨基苯甲酸和苯甲醇为原料,合成对氨基苯甲酸苄酯.结果表明,当微波辐射功率为500W,0.05mol对氨基苯甲酸为基准,催化剂的用量为1.6 g,酸醇的摩尔比为1∶1.2,反应时间14 min时,醋化率达93.8%.%The 4-aminobcnzoic acid benzyl ester was synthesized under microwave radiacion from 4-aminobenzoic acid and benzyl alcohol using sodium bisulfate as catalyst. When the power of microwave radiation was 500 W, amount of catalyst was 1. 6 g, the molar ratio of acid to alcohol was 1∶ 1.2( using 0. 05 mol of 4-aminobenzoic acid ) and reaction time was 14 min, the yield reached 93. 8% .

  17. Iodine-catalyzed coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Joseph, J.T.; Duffield, J.E.; Davidson, M.G. (Amoco Oil Company, Naperville, IL (USA). Research and Development Dept.)

    Coals of two different ranks were liquefied in high yields using catalytic quantities of elemental iodine or iodine compounds. Iodine monochloride was found to be especially effective for enhancing both coal conversion and product quality. It appears that enhancement in coal conversion is due to the unique ability of iodine to catalyze radical-induced bond scission and hydrogen addition to the coal macromolecule or coal-derived free radicals. The starting iodine can be fully accounted for in the reaction products as both organic-bound and water-soluble forms. Unconverted coal and the heavy product fractions contain the majority of the organic-bound iodine. The results of iodine-catalyzed coal reactions emphasize the need for efficient hydrogen atom transfer along with bond scission to achieve high conversion and product quality. 22 refs., 12 tabs.

  18. 苯乙胺衍生的手性膦-亚磷酰胺酯配体在Rh-催化α-烯醇酯膦酸酯的不对称氢化反应中的应用%Rh-Catalyzed Asymmetric Hydrogenation of α-Enol Ester Phosphonates with 1-Phenylethylamine-Derived Phosphine-Phosphoramidite Ligands

    Institute of Scientific and Technical Information of China (English)

    胡娟; 王道永; 郑卓; 胡向平


    A series of phosphine-phosphoramidite ligands derived from commercially available,inexpensive chiral 1-phenylethylamine were employed in the Rh-catalyzed asymmetric hydrogenation of various α-enol ester phosphonates.The results indicated that the ligand(Sc,Sa)-2b bearing a Me-group on amino moiety exhibited similar enantioselectivity but superior catalytic activity to(Rc,Ra)-THNAPhos.Excellent enantioselectivities(up to 99% ee) and high catalytic activity(S/C up to 5 000) have been achieved in the hydrogenation of various β-alkyl and β-aryl substituted substrates,demonstrating the high potential of this phosphine-phosphoramidite ligand in the preparation of optically active α-hydroxyphosphonates%将苯乙胺衍生的手性膦-亚磷酰胺酯配体应用在Rh-催化α-烯醇酯膦酸酯的不对称氢化反应中,考察了配体结构及反应条件对反应结果的影响,并在优化的条件下研究了各种底物的适用范围,产物的对映选择性最高〉99%ee.

  19. A Convenient, General Synthesis of 1,1-Dimethylallyl Esters as Protecting Groups for Carboxylic Acids (United States)

    Sedighi, Minoo; Lipton, Mark A.


    Carboxylic acids were converted in high yield to their 1,1-dimethylallyl (DMA) esters in two steps. Palladium-catalyzed deprotection of DMA esters was shown to be compatible with tert-butyl, benzyl and Fmoc protecting groups, and Fmoc deprotection could be carried out selectively in the presence of DMA esters. DMA esters were also shown to be resistant to nucleophilic attack, suggesting that they will serve as alternatives to tert-butyl esters when acidic deprotection conditions need to be avoided. PMID:15816730

  20. A convenient, general synthesis of 1,1-dimethylallyl esters as protecting groups for carboxylic acids. (United States)

    Sedighi, Minoo; Lipton, Mark A


    [reaction: see text] Carboxylic acids were converted in high yield to their 1,1-dimethylallyl (DMA) esters in two steps. Palladium-catalyzed deprotection of DMA esters was shown to be compatible with tert-butyl, benzyl, and Fmoc protecting groups, and Fmoc deprotection could be carried out selectively in the presence of DMA esters. DMA esters were also shown to be resistant to nucleophilic attack, suggesting that they will serve as alternatives to tert-butyl esters when acidic deprotection conditions need to be avoided.

  1. Highly efficient synthesis of β-amino esters via Mannich-type reaction under solvent-free conditions using ZnCl2 catalyst

    Institute of Scientific and Technical Information of China (English)

    Xue Ming Chen; Xing Shu Li; Albert S.C. Chan


    β-Amino esters were synthesized via ZnCl2-catalyzed Mannich-type reaction of imines and malonate esters under solvent-free conditions in 6 min.The β-amino ester was converted into the corresponding aspartic acid derivatives.

  2. Thermodynamic Strategies for C-O Bond Formation and Cleavage via Tandem Catalysis. (United States)

    Lohr, Tracy L; Li, Zhi; Marks, Tobin J


    To reduce global reliance on fossil fuels, new renewable sources of energy that can be used with the current infrastructure are required. Biomass represents a major source of renewable carbon based fuel; however, the high oxygen content (∼40%) limits its use as a conventional fuel. To utilize biomass as an energy source, not only with current infrastructure, but for maximum energy return, the oxygen content must be reduced. One method to achieve this is to develop selective catalytic methods to cleave C-O bonds commonly found in biomass (aliphatic and aromatic ethers and esters) for the eventual removal of oxygen in the form of volatile H2O or carboxylic acids. Once selective methods of C-O cleavage are understood and perfected, application to processing real biomass feedstocks such as lignin can be undertaken. This Laboratory previously reported that recyclable "green" lanthanide triflates are excellent catalysts for C-O bond-forming hydroalkoxylation reactions. Based on the virtues of microscopic reversibility, the same lanthanide triflate catalyst should catalyze the reverse C-O cleavage process, retrohydroalkoxylation, to yield an alcohol and an alkene. However, ether C-O bond-forming (retrohydroalkoxylation) to form an alcohol and alkene is endothermic. Guided by quantum chemical analysis, our strategy is to couple endothermic, in tandem, ether C-O bond cleavage with exothermic alkene hydrogenation, thereby leveraging the combined catalytic cycles thermodynamically to form an overall energetically favorable C-O cleavage reaction. This Account reviews recent developments on thermodynamically leveraged tandem catalysis for ether and more recently, ester C-O bond cleavage undertaken at Northwestern University. First, the fundamentals of lanthanide-catalyzed hydroelementation are reviewed, with particular focus on ether C-O bond formation (hydroalkoxylation). Next, the reverse C-O cleavage/retrohydroalkoxylation processes enabled by tandem catalysis are

  3. Thermodynamic Strategies for C-O Bond Formation and Cleavage via Tandem Catalysis. (United States)

    Lohr, Tracy L; Li, Zhi; Marks, Tobin J


    To reduce global reliance on fossil fuels, new renewable sources of energy that can be used with the current infrastructure are required. Biomass represents a major source of renewable carbon based fuel; however, the high oxygen content (∼40%) limits its use as a conventional fuel. To utilize biomass as an energy source, not only with current infrastructure, but for maximum energy return, the oxygen content must be reduced. One method to achieve this is to develop selective catalytic methods to cleave C-O bonds commonly found in biomass (aliphatic and aromatic ethers and esters) for the eventual removal of oxygen in the form of volatile H2O or carboxylic acids. Once selective methods of C-O cleavage are understood and perfected, application to processing real biomass feedstocks such as lignin can be undertaken. This Laboratory previously reported that recyclable "green" lanthanide triflates are excellent catalysts for C-O bond-forming hydroalkoxylation reactions. Based on the virtues of microscopic reversibility, the same lanthanide triflate catalyst should catalyze the reverse C-O cleavage process, retrohydroalkoxylation, to yield an alcohol and an alkene. However, ether C-O bond-forming (retrohydroalkoxylation) to form an alcohol and alkene is endothermic. Guided by quantum chemical analysis, our strategy is to couple endothermic, in tandem, ether C-O bond cleavage with exothermic alkene hydrogenation, thereby leveraging the combined catalytic cycles thermodynamically to form an overall energetically favorable C-O cleavage reaction. This Account reviews recent developments on thermodynamically leveraged tandem catalysis for ether and more recently, ester C-O bond cleavage undertaken at Northwestern University. First, the fundamentals of lanthanide-catalyzed hydroelementation are reviewed, with particular focus on ether C-O bond formation (hydroalkoxylation). Next, the reverse C-O cleavage/retrohydroalkoxylation processes enabled by tandem catalysis are

  4. QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis (United States)

    Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.


    Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of catonic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrogen hydrolysis rate constant.

  5. Lipase catalyzed synthesis of epoxy-fatty acids

    Institute of Scientific and Technical Information of China (English)

    CHEN, Qian; LI, Zu-Yi


    Lipase catalyzed synthesis of epoxy-fatty acidas from unsaturated carboxylic acids was investigated.Under mild conditions unsaturated arboxylic acids were convcveed to peroxide,then the unsaturated peroxycarboxylic acids epoxidised the C=C bond of themselves

  6. Synthesis of 2-oxindoles via 'transition-metal-free' intramolecular dehydrogenative coupling (IDC) of sp2 C–H and sp3 C–H bonds (United States)

    Bhunia, Subhajit


    Summary The synthesis of a variety of 2-oxindoles bearing an all-carbon quaternary center at the pseudo benzylic position has been achieved via a ‘transition-metal-free’ intramolecular dehydrogenative coupling (IDC). The construction of 2-oxindole moieties was carried out through formation of carbon–carbon bonds using KOt-Bu-catalyzed one pot C-alkylation of β-N-arylamido esters with alkyl halides followed by a dehydrogenative coupling. Experimental evidences indicated toward a radical-mediated path for this reaction. PMID:27559367

  7. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter


    The atom-efficiency of one of the most widely used catalytic reactions for forging C-C bonds, the Tsuji-Trost reaction, is limited by the need of preoxidized reagents. This limitation can be overcome by utilization of the recently discovered palladium-catalyzed C-H activation, the allylic C...

  8. Rhodium-catalyzed restructuring of carbon frameworks. (United States)

    Murakami, Masahiro


    Metal-catalyzed reactions involving an elementary step which cleaves a carbon-carbon bond provide unique organic transformations. Restructuring reactions recently developed in our laboratory, through which the carbon framework of a starting substance is restructured into a totally different carbon framework, are discussed, with the possibility of applying such methods to the synthesis of natural products.

  9. Polyhydroxyester films obtained by non-catalyzed melt-polycondensation of natural occurring fatty polyhydroxyacids.

    Directory of Open Access Journals (Sweden)

    Jose Jesus Benitez


    Full Text Available Free-standing polyesters films from mono and polyhydroxylated fatty acids (C16 and C18 have been obtained by non-catalyzed melt-condensation polymerization in air at 150°C. Chemical characterization by Fourier Transform Infrared Spectroscopy (FTIR and 13C Magic Angle Spinning Nuclear Magnetic Resonance (13C MAS-NMR has confirmed the formation of the corresponding esters and the occurrence of hydroxyl partial oxidation which extent depends on the type of hydroxylation of the monomer (primary or secondary. Generally, polyester films obtained are hydrophobic, insoluble in common solvents, amorphous and infusible as revealed by X-ray Diffraction (XRD and Differential Scanning Calorimetry (DSC. In -polyhydroxy acids, esterification reaction with primary hydroxyls is preferential and, therefore, the structure can be defined as linear with variable branching depending on the amount of esterified secondary hydroxyls. The occurrence side oxidative reactions like the diol cleavage are responsible for chain cross-linking. Films are thermally stable up to 200-250°C though this limit can be extended up to 300°C in the absence of ester bonds involving secondary hydroxyls. By analogy with natural occurring fatty polyesters (i.e. cutin in higher plants these polymers are proposed as biodegradable and non-toxic barrier films or coatings to be used, for instance, in food packing

  10. Selective conversion of polyenes to monoenes by RuCl(3) -catalyzed transfer hydrogenation: the case of cashew nutshell liquid. (United States)

    Perdriau, Sébastien; Harder, Sjoerd; Heeres, Hero J; de Vries, Johannes G


    Cardanol, a constituent of cashew nutshell liquid (CNSL), was subjected to transfer hydrogenation catalyzed by RuCl(3) using isopropanol as a reductant. The side chain of cardanol, which is a mixture of a triene, a diene, and a monoene, was selectively reduced to the monoene. Surprisingly, it is the C8-C9 double bond that is retained with high selectivity. A similar transfer hydrogenation of linoleic acid derivatives succeeded only if the substrate contained an aromatic ring, such as a benzyl ester. TEM and a negative mercury test showed that the catalyst was homogeneous. By using ESI-MS, ruthenium complexes were identified that contained one, two, or even three molecules of substrate, most likely as allyl complexes. The interaction between ruthenium and the aromatic ring determines selectivity in the hydrogenation reaction. PMID:23060315

  11. Interaction of ester functional groups with aluminum oxide surfaces studied using infrared reflection absorption spectroscopy. (United States)

    van den Brand, J; Blajiev, O; Beentjes, P C J; Terryn, H; de Wit, J H W


    The bonding of two types of ester group-containing molecules with a set of different oxide layers on aluminum has been investigated using infrared reflection absorption spectroscopy. The different oxide layers were made by giving typical surface treatments to the aluminum substrate. The purpose of the investigation was to find out what type of ester-oxide bond is formed and whether this is influenced by changes in the composition and chemistry of the oxide. The extent by which these bonded ester molecules resisted disbondment in water or substitution by molecules capable of chemisorption was also investigated. The ester groups were found to show hydrogen bonding with hydroxyls on the oxide surfaces through their carbonyl oxygens. For all oxides, the ester groups showed the same nu(C = O) carbonyl stretching vibration after adsorption, indicating very similar bonding occurs. However, the oxides showed differences in the amount of molecules bonded to the oxide surface, and a clear relation was observed with the hydroxyl concentration present on the oxide surface, which was determined from XPS measurements. The two compounds showed differences in the free to bonded nu(C = O) infrared peak shift, indicating differences in bonding strength with the oxide surface between the two types of molecules. The bonding of the ester groups with the oxide surfaces was found to be not stable in the presence of water and also not in the presence of a compound capable of chemisorption with the aluminum oxide surface. PMID:15248718

  12. Linear and cyclic ester Oligomers of succinic acid and 1,4-butanediol: Biocatalytic synthesis and characterization

    NARCIS (Netherlands)

    Habeych Narvaez, D.I.; Eggink, G.; Boeriu, C.G.


    The lipase-catalyzed synthesis of cyclic ester oligomers from non-activated succinic acid (A) and 1,4-butanediol (B) in the presence of immobilized Candida antarctica lipase B was investigated. Batch and pulse fed-batch systems were implemented to increase the formation of cyclic ester products. The

  13. Regulatory link between steryl ester formation and hydrolysis in the yeast Saccharomyces cerevisiae. (United States)

    Ploier, Birgit; Korber, Martina; Schmidt, Claudia; Koch, Barbara; Leitner, Erich; Daum, Günther


    Steryl esters and triacylglycerols are the major storage lipids of the yeast Saccharomyces cerevisiae. Steryl esters are formed in the endoplasmic reticulum by the two acyl-CoA:sterol acyltransferases Are1p and Are2p, whereas steryl ester hydrolysis is catalyzed by the three steryl ester hydrolases Yeh1p, Yeh2p and Tgl1p. To shed light on the regulatory link between steryl ester formation and hydrolysis in the maintenance of cellular sterol and free fatty acid levels we employed yeast mutants which lacked the enzymes catalyzing the degradation of steryl esters. These studies revealed feedback regulation of steryl ester formation by steryl ester hydrolysis although in a Δtgl1Δyeh1Δyeh2 triple mutant the gene expression levels of ARE1 and ARE2 as well as protein levels and stability of Are1p and Are2p were not altered. Nevertheless, the capacity of the triple mutant to synthesize steryl esters was significantly reduced as shown by in vitro and in vivo labeling of lipids with [(14)C]oleic acid and [(14)C]acetate. Enzymatic analysis revealed that inhibition of steryl ester formation occurred at the enzyme level. As the amounts and the formation of sterols and fatty acids were also decreased in the triple mutant we concluded that defects in steryl ester hydrolysis also caused feedback inhibition on the formation of sterols and fatty acids which serve as precursors for steryl ester formation. In summary, this study demonstrates a regulatory link within the steryl ester metabolic network which contributes to non-polar lipid homeostasis in yeast cells.

  14. Gold-catalyzed naphthalene functionalization

    Directory of Open Access Journals (Sweden)

    Iván Rivilla


    Full Text Available The complexes IPrMCl (IPr = 1,3-bis(diisopropylphenylimidazol-2-ylidene, M = Cu, 1a; M = Au, 1b, in the presence of one equiv of NaBAr'4 (Ar' = 3,5-bis(trifluoromethylphenyl, catalyze the transfer of carbene groups: C(RCO2Et (R = H, Me from N2C(RCO2Et to afford products that depend on the nature of the metal center. The copper-based catalyst yields exclusively a cycloheptatriene derivative from the Buchner reaction, whereas the gold analog affords a mixture of products derived either from the formal insertion of the carbene unit into the aromatic C–H bond or from its addition to a double bond. In addition, no byproducts derived from carbene coupling were observed.

  15. Recent advances in osmium-catalyzed hydrogenation and dehydrogenation reactions. (United States)

    Chelucci, Giorgio; Baldino, Salvatore; Baratta, Walter


    CONSPECTUS: A current issue in metal-catalyzed reactions is the search for highly efficient transition-metal complexes affording high productivity and selectivity in a variety of processes. Moreover, there is also a great interest in multitasking catalysts that are able to efficiently promote different organic transformations by careful switching of the reaction parameters, such as temperature, solvent, and cocatalyst. In this context, osmium complexes have shown the ability to catalyze efficiently different types of reactions involving hydrogen, proving at the same time high thermal stability and simple synthesis. In the catalytic reduction of C═X (X = O, N) bonds by both hydrogenation (HY) and transfer hydrogenation (TH) reactions, the most interest has been focused on homogeneous systems based on rhodium, iridium, and in particular ruthenium catalysts, which have proved to catalyze chemo- and stereoselective hydrogenations with remarkable efficiency. By contrast, osmium catalysts have received much less attention because they are considered less active on account of their slower ligand exchange kinetics. Thus, this area remained almost neglected until recent studies refuted these prejudices. The aim of this Account is to highlight the impressive developments achieved over the past few years by our and other groups on the design of new classes of osmium complexes and their applications in homogeneous catalytic reactions involving the hydrogenation of carbon-oxygen and carbon-nitrogen bonds by both HY and TH reactions as well as in alcohol deydrogenation (DHY) reactions. The work described in this Account demonstrates that osmium complexes are emerging as powerful catalysts for asymmetric and non-asymmetric syntheses, showing a remarkably high catalytic activity in HY and TH reactions of ketones, aldehydes, imines, and esters as well in DHY reactions of alcohols. Thus, for instance, the introduction of ligands with an NH function, possibly in combination with a

  16. Biodiesel production by enzyme-catalyzed transesterification

    Directory of Open Access Journals (Sweden)

    Stamenković Olivera S.


    Full Text Available The principles and kinetics of biodiesel production from vegetable oils using lipase-catalyzed transesterification are reviewed. The most important operating factors affecting the reaction and the yield of alkyl esters, such as: the type and form of lipase, the type of alcohol, the presence of organic solvents, the content of water in the oil, temperature and the presence of glycerol are discussed. In order to estimate the prospects of lipase-catalyzed transesterification for industrial application, the factors which influence the kinetics of chemically-catalysed transesterification are also considered. The advantages of lipase-catalyzed transesterification compared to the chemically-catalysed reaction, are pointed out. The cost of down-processing and ecological problems are significantly reduced by applying lipases. It was also emphasized that lipase-catalysed transesterification should be greatly improved in order to make it commercially applicable. The further optimization of lipase-catalyzed transesterification should include studies on the development of new reactor systems with immobilized biocatalysts and the addition of alcohol in several portions, and the use of extra cellular lipases tolerant to organic solvents, intracellular lipases (i.e. whole microbial cells and genetically-modified microorganisms ("intelligent" yeasts.

  17. Cooperative catalysis of metal and O-H···O/sp3-C-H···O two-point hydrogen bonds in alcoholic solvents: Cu-catalyzed enantioselective direct alkynylation of aldehydes with terminal alkynes. (United States)

    Ishii, Takaoki; Watanabe, Ryo; Moriya, Toshimitsu; Ohmiya, Hirohisa; Mori, Seiji; Sawamura, Masaya


    Catalyst-substrate hydrogen bonds in artificial catalysts usually occur in aprotic solvents, but not in protic solvents, in contrast to enzymatic catalysis. We report a case in which ligand-substrate hydrogen-bonding interactions cooperate with a transition-metal center in alcoholic solvents for enantioselective catalysis. Copper(I) complexes with prolinol-based hydroxy amino phosphane chiral ligands catalytically promoted the direct alkynylation of aldehydes with terminal alkynes in alcoholic solvents to afford nonracemic secondary propargylic alcohols with high enantioselectivities. Quantum-mechanical calculations of enantiodiscriminating transition states show the occurrence of a nonclassical sp(3)-C-H···O hydrogen bond as a secondary interaction between the ligand and substrate, which results in highly directional catalyst-substrate two-point hydrogen bonding.

  18. Gas chromatography-mass spectrometric analysis of bonded long chain fatty acids in a single zebrafish egg by ultrasound-assisted one-step transmethylation and extraction

    Energy Technology Data Exchange (ETDEWEB)

    Li Jianjian; Yue Yingxia; Li Tingting; Hu Xuejiao [Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079 (China); Zhong Hongying, E-mail: [Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079 (China)


    Changes in the level of lipid composition in a single zebrafish egg have been involved in biological responses to chemical exposures. In this paper, an one-step transmethylation of lipids and simultaneous extraction of resultant fatty acid methyl esters followed by gas chromatography-mass spectrometric analysis was developed for the identification of bonded long chain fatty acids in a single zebrafish egg. The efficiency of transmethylation under different experimental conditions has been investigated. Dried egg homogenates were directly mixed with either 0.5 M NaOH or 1% H{sub 2}SO{sub 4} or 4% HCl solution of methanol and then an n-hexane solution was added on the top. Ultrasonication of this immiscible liquid-liquid-solid system produces high velocity impacts between solid particles and liquid phases and thus promotes mass transfer among phases. It was demonstrated that ultrasound irradiation has strong effect on the alkaline-catalyzed transmethylation of lipids but cannot significantly change the acid-catalyzed transmethylation of lipids. With the aid of ultrasonication, transmethylation can be combined with simultaneous extraction of the resultant fatty acid methyl esters into n-hexane phase. This approach simplifies the sample preparation procedure, shortens the reaction time but improves the efficiency of the transmethylation of lipids and reduces sample losses, especially for small size samples. It has been applied to determine bonded fatty acids in a single zebrafish egg. In total, 28 fatty acids from a single zebrafish egg have been identified reproducibly.

  19. Gas chromatography-mass spectrometric analysis of bonded long chain fatty acids in a single zebrafish egg by ultrasound-assisted one-step transmethylation and extraction

    International Nuclear Information System (INIS)

    Changes in the level of lipid composition in a single zebrafish egg have been involved in biological responses to chemical exposures. In this paper, an one-step transmethylation of lipids and simultaneous extraction of resultant fatty acid methyl esters followed by gas chromatography-mass spectrometric analysis was developed for the identification of bonded long chain fatty acids in a single zebrafish egg. The efficiency of transmethylation under different experimental conditions has been investigated. Dried egg homogenates were directly mixed with either 0.5 M NaOH or 1% H2SO4 or 4% HCl solution of methanol and then an n-hexane solution was added on the top. Ultrasonication of this immiscible liquid-liquid-solid system produces high velocity impacts between solid particles and liquid phases and thus promotes mass transfer among phases. It was demonstrated that ultrasound irradiation has strong effect on the alkaline-catalyzed transmethylation of lipids but cannot significantly change the acid-catalyzed transmethylation of lipids. With the aid of ultrasonication, transmethylation can be combined with simultaneous extraction of the resultant fatty acid methyl esters into n-hexane phase. This approach simplifies the sample preparation procedure, shortens the reaction time but improves the efficiency of the transmethylation of lipids and reduces sample losses, especially for small size samples. It has been applied to determine bonded fatty acids in a single zebrafish egg. In total, 28 fatty acids from a single zebrafish egg have been identified reproducibly.

  20. Enzymatic synthesis and application of fatty acid ascorbyl esters


    Stojanović Marija M.; Carević Milica B.; Mihailović Mladen D.; Knežević-Jugović Zorica D.; Petrović Slobodan D.; Bezbradica Dejan I.


    Fatty acid ascorbyl esters are liposoluble substances that possess good antioxidative properties. These compounds could be synthesized by using various acyl donors for acylation of vitamin C in reaction catalyzed by chemical means or lipases. Enzymatic process is preferred since it is regioselective, performed under mild reaction conditions, with the obtained product being environmentally friendly. Polar organic solvents, ionic liquids, and supercritical fluids has been successfully use...

  1. Pd-Catalyzed sequential β-C(sp(3))-H arylation and intramolecular amination of δ-C(sp(2))-H bonds for synthesis of quinolinones via an N,O-bidentate directing group. (United States)

    Guan, Mingyu; Pang, Yubo; Zhang, Jingyu; Zhao, Yingsheng


    The pharmacological importance of 2-quinolinone derivatives is well known. Herein, we developed an effective protocol for the synthesis of 2-quinolinone derivatives by palladium-catalyzed sequential β-C(sp(3))-H arylation and selective intramolecular C(sp(2))-H/N-H amination starting with aryl iodides and carboxylic acids. A novel directing group, glycine dimethylamide, was used in the synthesis. We synthesized various quinolinone derivatives, including 5-substituted quinolinones, which are difficult to obtain using the traditional pathway. The directing group could be easily removed and could be readily transformed into other useful functional groups. PMID:27161570

  2. Azobenzene dye-coupled quadruply hydrogen-bonding modules as colorimetric indicators for supramolecular interactions

    Directory of Open Access Journals (Sweden)

    Yagang Zhang


    Full Text Available The facile coupling of azobenzene dyes to the quadruply hydrogen-bonding modules 2,7-diamido-1,8-naphthyridine (DAN and 7-deazaguanine urea (DeUG is described. The coupling of azobenzene dye 2 to mono-amido DAN units 4, 7, and 9 was effected by classic 4-(dimethylaminopyridine (DMAP-catalyzed peptide synthesis with N-(3-dimethylaminopropyl-N’-ethyl carbodiimide hydrochloride (EDC as activating agent, affording the respective amide products 5, 8, and 10 in 60–71% yield. The amide linkage was formed through either the aliphatic or aromatic ester group of 2, allowing both the flexibility and absorption maximum to be tuned. Azobenzene dye 1 was coupled to the DeUG unit 11 by Steglich esterification to afford the product amide 12 in 35% yield. Alternatively, azobenzene dye 16 underwent a room-temperature copper-catalyzed azide–alkyne Huisgen cycloaddition with DeUG alkyne 17 to give triazole 18 in 71% yield. Azobenzene coupled DAN modules 5, 8, and 10 are bright orange–red in color, and azobenzene coupled DeUG modules 12 and 18 are orange–yellow in color. Azobenzene coupled DAN and DeUG modules were successfully used as colorimetric indicators for specific DAN–DeUG and DAN–UPy (2-ureido-4(1H-pyrimidone quadruply hydrogen-bonding interactions.

  3. Neutral lipid biosynthesis in engineered Escherichia coli: jojoba oil-like wax esters and fatty acid butyl esters. (United States)

    Kalscheuer, Rainer; Stöveken, Tim; Luftmann, Heinrich; Malkus, Ursula; Reichelt, Rudolf; Steinbüchel, Alexander


    Wax esters are esters of long-chain fatty acids and long-chain fatty alcohols which are of considerable commercial importance and are produced on a scale of 3 million tons per year. The oil from the jojoba plant (Simmondsia chinensis) is the main biological source of wax esters. Although it has a multitude of potential applications, the use of jojoba oil is restricted, due to its high price. In this study, we describe the establishment of heterologous wax ester biosynthesis in a recombinant Escherichia coli strain by coexpression of a fatty alcohol-producing bifunctional acyl-coenzyme A reductase from the jojoba plant and a bacterial wax ester synthase from Acinetobacter baylyi strain ADP1, catalyzing the esterification of fatty alcohols and coenzyme A thioesters of fatty acids. In the presence of oleate, jojoba oil-like wax esters such as palmityl oleate, palmityl palmitoleate, and oleyl oleate were produced, amounting to up to ca. 1% of the cellular dry weight. In addition to wax esters, fatty acid butyl esters were unexpectedly observed in the presence of oleate. The latter could be attributed to solvent residues of 1-butanol present in the medium component, Bacto tryptone. Neutral lipids produced in recombinant E. coli were accumulated as intracytoplasmic inclusions, demonstrating that the formation and structural integrity of bacterial lipid bodies do not require specific structural proteins. This is the first report on substantial biosynthesis and accumulation of neutral lipids in E. coli, which might open new perspectives for the biotechnological production of cheap jojoba oil equivalents from inexpensive resources employing recombinant microorganisms.

  4. Theoretical Investigation of the Structures of Borate Esters and Their Bonding Interaction with RDX%硼酸酯键合剂分子结构及其与RDX晶面相互作用的理论研究

    Institute of Scientific and Technical Information of China (English)

    崔瑞禧; 张炜


    运用量子化学方法计算了5种硼酸酯键合剂(BEBA)的分子结构和分子轨道,发现5种BEBA分子硼原子所处空轨道的能级较高.利用晶面吸附模型和分子动力学方法研究了上述键合剂与RDX(210)、RDX(200)晶面之间的相互作用能,发现键合剂在不同RDX晶面上的结合模式不同且具有选择性.键合剂与RDX(200)晶面的结合能大于其与RDX(210)晶面的结合能.BEBA_1和BEBA_2能够在两个晶面上获得较好的结合能力.BEBA 5在RDX(210)和RDX(200)晶面上相对结合能力相反,即在RDX(210)/BEBA_5中结合最好.推测由于RDX (200)晶面最表层氧原子含量相对较少,有利于甲酰丙酮基上的羰基与RDX上的NO2产生诱导效应,产生很强的结合作用,抵消并补偿了由于BEBA_5中胺氮负电荷减少而造成结合能的降低.%Theoretical calculation was used to investigate the molecular structures and orbitals of five BEBA molecules. Relative to trimethyl borate, the lowest unoccupied molecular orbital ( LUMO) images of five BEBAs (1 -5 ) molecules show that the orbitals do not appear around borate groups, and their energy levels of those unoccupied molecular orbitals around boron atom are higher. Molecular dynamics simulation was performed to investigate the interaction between title borate esters and RDX(210) as well as RDX(210) crystal faces. An obvious binding selectivity of these borate esters on RDX crystal surfaces is found. The binding energies of RDX (200 )/BEBAs are higher than that of RDX ( 210 )/BEBA ( 1 -5). The theoretical evaluation for the binding performances of BEBA1 and BEBA_2 with RDX are good enough, whereas the binding performances of RDX(210) /BEBA_5 and RDX(200)/BEBA_5 are contrary. It is speculated that less oxygen content of the most superficial surface of RDX(200) is benefit of forming induced effects between carbonyl of BEBA_5 and NO2 in RDX. Such a strong combination between them offsets or even compensates the lowering of binding

  5. Synthesis of some glucose-fatty acid esters by lipase from Candida antarctica and their emulsion functions. (United States)

    Ren, Kangzi; Lamsal, Buddhi P


    The synthesis of glucose esters with palmitic acid, lauric acid and hexanoic acid using lipase enzyme was studied and their emulsion functionality in oil-in-water system were compared. Reactions at 3:1M ratio of fatty acids-to-glucose had the highest conversion percentages (over 90% for each of the fatty acid). Initial conversion rate increased as substrate solubility increased. Ester bond formation was confirmed by nuclear magnetic resonance technique that the chemical shifts of glucose H-6 and α-carbon protons of fatty acids in the ester molecules shifted to the higher fields. Contact angle of water on esters' pelleted surface increased as the hydrophobicity increased. Glucose esters' and commercial sucrose esters' functionality as emulsifiers were compared. Glucose esters delayed, but did not prevent coalescence, because the oil droplets diameter doubled during 7days. Sucrose esters prevented coalescence during 7days since the droplets diameter did not have significant change. PMID:27507510

  6. Enantioconvergent synthesis by sequential asymmetric Horner-Wadsworth-Emmons and palladium-catalyzed allylic substitution reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Hansen, E. Louise; Kane, John;


    A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different $alpha@-oxygen-substituted, racemic aldehydes were initially transformed by...... asymmetric HWE reactions into mixtures of two major $alpha@,$beta@-unsaturated esters, possessing opposite configurations at their allylic stereocenters as well as opposite alkene geometry. Subsequently, these isomeric mixtures of alkenes could be subjected to palladium-catalyzed allylic substitution...

  7. Apomorphine and its esters

    DEFF Research Database (Denmark)

    Borkar, Nrupa; Chen, Zhizhong; Saaby, Lasse;


    Oral delivery of apomorphine via prodrug principle may be a potential treatment for Parkinson's disease. The purpose of this study was to investigate the transport and stability of apomorphine and its esters across Caco-2 cell monolayer and their affinity towards chylomicrons. Apomorphine...

  8. Cobalt catalyzed hydroesterification of a wide range of olefins

    Energy Technology Data Exchange (ETDEWEB)

    Van Rensburg, H.; Hanton, M.; Tooze, R.P.; Foster, D.F. [Sasol Technology UK, St Andrews (United Kingdom)


    Petrochemical raw materials are an essential raw material for the production of detergents with a substantial portion of synthetic fatty alcohols being produced via hydroformylation of oil or coal derived olefins. Carbonylation processes other than hydroformylation have to date not been commercially employed for the production of fatty esters or alcohols. In this document we highlight the opportunities of converting olefins to esters using cobalt catalyzed alkoxycarbonylation. This process is highly versatile and applicable to a wide range of olefins, linear or branched, alpha or internal in combination with virtually any chain length primary or secondary alcohol allowing the synthesis of a diverse array of compounds such as ester ethoxylated surfactants, methyl branched detergents, lubricants and alkyl propanoates. Furthermore, alkoxycarbonylation of a broad olefin/paraffin hydrocarbon range could be used to produce the corresponding broad cut detergent alcohols. (orig.)

  9. Lubricants based on synthetic esters; Schmierstoffe auf Basis synthetischer Ester

    Energy Technology Data Exchange (ETDEWEB)

    Fahl, J. [Forschung und Entwicklung Kaeltemaschinenoele, Fuchs DEA Schmierstoffe GmbH, Hamburg (Germany)


    This article describes the synthetic esters that are being used in refrigeration applications that use chlorine-free working fluids. The chemical basics involved in these high-performance lubricants, their manufacture and their lubricating properties are looked at in detail. The history of their development from their use as machining oils, lubricants for weapons and two-stroke engines through to turbine lubricants and as hydraulic oil in aeronautics is reviewed. Modern neopentyl-polyol esters used in refrigeration applications are described. Further, the chemical structures and applications of complex esters, carbonate esters, aromatic and silicate esters are looked at.

  10. Phosphate Esters, Thiophosphate Esters and Metal Thiophosphates as Lubricant Additives

    Directory of Open Access Journals (Sweden)

    David W. Johnson


    Full Text Available Phosphate esters, thiophosphate esters and metal thiophosphates have been used as lubricant additives for over 50 years. While their use has been extensive, a detailed knowledge of how they work has been a much more recent development. In this paper, the use of phosphate esters and thiophosphate esters as anti-wear or extreme pressure additives is reviewed with an emphasis on their mechanism of action. The review includes the use of alkyl phosphates, triaryl phosphates and metal containing thiophosphate esters. The mechanisms of these materials interacting with a range of iron and steel based bearing material are examined.

  11. Recent advances in copper-catalyzed asymmetric coupling reactions

    Directory of Open Access Journals (Sweden)

    Fengtao Zhou


    Full Text Available Copper-catalyzed (or -mediated asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C–C, C–N, C–O and other carbon–heteroatom bonds as well as for the construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C–C and carbon–heteroatom bonds.

  12. Nickel-Catalyzed Aromatic C-H Functionalization. (United States)

    Yamaguchi, Junichiro; Muto, Kei; Itami, Kenichiro


    Catalytic C-H functionalization using transition metals has received significant interest from organic chemists because it provides a new strategy to construct carbon-carbon bonds and carbon-heteroatom bonds in highly functionalized, complex molecules without pre-functionalization. Recently, inexpensive catalysts based on transition metals such as copper, iron, cobalt, and nickel have seen more use in the laboratory. This review describes recent progress in nickel-catalyzed aromatic C-H functionalization reactions classified by reaction types and reaction partners. Furthermore, some reaction mechanisms are described and cutting-edge syntheses of natural products and pharmaceuticals using nickel-catalyzed aromatic C-H functionalization are presented. PMID:27573407

  13. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kate; Elgqvist, Emma; Walker, Andy; Cutler, Dylan; Olis, Dan; DiOrio, Nick; Simpkins, Travis


    This poster details how screenings done with REopt - NREL's software modeling platform for energy systems integration and optimization - are helping to catalyze the development of hundreds of megawatts of renewable energy.

  14. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik


    This paper describes how environmental management systems (EMS) spur the circulation of processes that support the constitution of environmental issues as specific environ¬mental objects and objectives. EMS catalyzes alignmentprocesses that produce coherence among the different elements involved ...

  15. Muon Catalyzed Fusion (United States)

    Armour, Edward A.G.


    Muon catalyzed fusion is a process in which a negatively charged muon combines with two nuclei of isotopes of hydrogen, e.g, a proton and a deuteron or a deuteron and a triton, to form a muonic molecular ion in which the binding is so tight that nuclear fusion occurs. The muon is normally released after fusion has taken place and so can catalyze further fusions. As the muon has a mean lifetime of 2.2 microseconds, this is the maximum period over which a muon can participate in this process. This article gives an outline of the history of muon catalyzed fusion from 1947, when it was first realised that such a process might occur, to the present day. It includes a description of the contribution that Drachrnan has made to the theory of muon catalyzed fusion and the influence this has had on the author's research.

  16. Palladium-Catalyzed Cross-Coupling Reaction of Organoboron Compounds with Carboxylic Derivatives%钯催化的有机硼化物与羧酸衍生物的交叉偶联反应

    Institute of Scientific and Technical Information of China (English)

    杨军; 邓敏智; 于涛


    钯催化的交叉偶联反应是构建C—C键的常用方法,近年来,钯催化的有机硼化物与羧酸衍生物的交叉偶联反应已成为偶联反应研究中的热点.本文综述了最近十几年多种有机硼化物与酰氯、酸酐、羧酸、氯甲酸衍生物、羧酸活性酯、羧酸硫酯的交叉偶联反应研究进展,并对该反应在有机合成中的应用进行了讨论.%Palladium-catalyzed cross-coupling reaction has emerged as an important strategy to the formation of C-C bond. Recently, palladium-catalyzed cross-coupling reaction between organoboron compounds and carboxylic derivatives has become a hotspot of organic chemistry. In this paper, recent researches of organoboron compounds with acyl chlorides, acid anhydrides, carboxylic acids, chloroformic derivatives, carboxylic esters and thiol esters in Suzuki cross-coupling are summarized, and the examples of these reactions in synthesis are also discussed.

  17. Synthesis of the Fatty Esters of Solketal and Glycerol-Formal: Biobased Specialty Chemicals

    Directory of Open Access Journals (Sweden)

    Alvise Perosa


    Full Text Available The caprylic, lauric, palmitic and stearic esters of solketal and glycerol formal were synthesized with high selectivity and in good yields by a solvent-free acid catalyzed procedure. No acetal hydrolysis was observed, notwithstanding the acidic reaction conditions.

  18. Synthesis of the Fatty Esters of Solketal and Glycerol-Formal: Biobased Specialty Chemicals. (United States)

    Perosa, Alvise; Moraschini, Andrea; Selva, Maurizio; Noè, Marco


    The caprylic, lauric, palmitic and stearic esters of solketal and glycerol formal were synthesized with high selectivity and in good yields by a solvent-free acid catalyzed procedure. No acetal hydrolysis was observed, notwithstanding the acidic reaction conditions. PMID:26840287

  19. Reversible derivatization to enhance enzymatic synthesis: Chemoenzymatic synthesis of Doxorubicin-14-O-Esters (United States)

    An efficient three-step, chemoenzymatic synthesis of unprotected doxorubicin-14-O-esters from doxorubicin hydrochloride salt is described. The key step is a lipase-catalyzed regioselective transesterification/esterification using commercially-available acyl donors and doxorubicin reversibly derivat...

  20. A Conformational Model for MTPA Esters of Chiral N-(2-Hydroxyalkylacrylamides

    Directory of Open Access Journals (Sweden)

    Eduardo M. Rustoy


    Full Text Available The absolute stereochemistry of novel chiral N-(2-hydroxylalkylacrylamides prepared by a lipase-catalyzed resolution was successfully determined by 1H NMR of their MTPA esters. The method was validated for this particular case by computational experiments.

  1. Synthesis of Versatile Building Blocks through Asymmetric Hydrogenation of Functionalized Itaconic Acid Mono-Esters

    NARCIS (Netherlands)

    Hekking, Koen F.W.; Lefort, Laurent; Vries, André H.M. de; Delft, Floris L. van; Schoemaker, Hans E.; Vries, Johannes G. de; Rutjes, Floris P.J.T.


    The rhodium-catalyzed asymmetric hydrogenation of several β-substituted itaconic acid mono-esters, using a library of monodentate phosphoramidite and phosphite ligands is described. Two β-alkyl-substituted substrates were readily hydrogenated by the rhodium complex Rh(COD)2BF4 in combination with (S

  2. Transition Metal Catalyzed Synthesis of Aryl Sulfides

    Directory of Open Access Journals (Sweden)

    Chad C. Eichman


    Full Text Available The presence of aryl sulfides in biologically active compounds has resulted in the development of new methods to form carbon-sulfur bonds. The synthesis of aryl sulfides via metal catalysis has significantly increased in recent years. Historically, thiolates and sulfides have been thought to plague catalyst activity in the presence of transition metals. Indeed, strong coordination of thiolates and thioethers to transition metals can often hinder catalytic activity; however, various catalysts are able to withstand catalyst deactivation and form aryl carbon-sulfur bonds in high-yielding transformations. This review discusses the metal-catalyzed arylation of thiols and the use of disulfides as metal-thiolate precursors for the formation of C-S bonds.

  3. Raman spectroscopic analysis of isomers of biliverdin dimethyl ester. (United States)

    Matysik, J; Hildebrandt, P; Smit, K; Mark, F; Gärtner, W; Braslavsky, S E; Schaffner, K; Schrader, B


    The constitutional isomers of biliverdin dimethyl ester, IX alpha and XIII alpha, were studied by resonance Raman spectroscopy. The far-reaching spectral similarities suggest that despite the different substitution patterns, the compositions of the normal modes are closely related. This conclusion does not hold only for the parent state (ZZZ, sss configuration) but also for the configurational isomers which were obtained upon double-bond photoisomerization. Based on a comparison of the resonance Raman spectra, a EZZ configuration is proposed for one of the two photoisomers of biliverdin dimethyl ester IX alpha, while a ZZE, ssa configuration has been assigned previously to the second isomer. PMID:9226559

  4. Synthesis of 2-Cyclopentenone Derivatives via Palladium-Catalyzed Intramolecular Carbonyl α-Alkenylation. (United States)

    Chen, Panpan; Meng, Yinggao; Wang, Han; Han, Feipeng; Wang, Yulong; Song, Chuanjun; Chang, Junbiao


    2-Cyclopentenone derivatives have been efficiently synthesized from 5-bromo-5-hexen-2-ones via palladium-catalyzed intramolecular carbonyl α-alkenylation followed by double-bond migration under mild reaction conditions. PMID:27463262

  5. In situ lipase-catalyzed reactive extraction of oilseeds with short-chained dialkyl carbonates for biodiesel production. (United States)

    Su, Erzheng; You, Pengyong; Wei, Dongzhi


    Dimethyl/diethyl carbonate was adopted as extraction solvent and transesterification reagent at the same time for in situ lipase-catalyzed reactive extraction of oilseeds for biodiesel production in this work. Fatty acid methyl esters and ethyl esters were respectively obtained with higher yields than those achieved by conventional two-step extraction/transesterification. The augment ranged from 15.7% to 31.7%. The key parameters such as solvent/seed ratio and water content were further investigated to find their effects on the in situ reactive extraction. The highest yields of Pistacia chinensis Bunge methyl ester, P. chinensis Bunge ethyl ester, Jatropha curcas L methyl ester and J. curcas L ethyl ester could attain 89.6%, 90.7%, 95.9% and 94.5%, respectively under the optimized conditions. PMID:19615896

  6. Efficient Synthesis of β-Acetamido Ketones and Esters Using Aluminum Chloride as an Inexpensive and Green Catalyst%Efficient Synthesis of β-Acetamido Ketones and Esters Using Aluminum Chloride as an Inexpensive and Green Catalyst

    Institute of Scientific and Technical Information of China (English)

    Mohammad Ali, Zolfigol; Ardeshir, Khazaei; Mohammad, Mokhlesi; Abdolkarim, Zare; Maliheh, Safaiee; Fatemeh, Derakhshan-Panah; Hassan, Keypour; Ahmad, Ali Dehghani-Firouzabadi; Maria, Merajoddin


    Aluminum chloride (AlCl3) efficiently catalyzes one-pot multicomponent condensation of enolizable ketones or alkyl acetoacetates with aldehydes, acetonitrile and acetyl chloride to afford β-acetamido ketone or ester derivatives in high to excellent yields and in relatively short reaction times. Moreover, by this synthetic method, some novel β-acetamido ketones and esters (i.e. one complex structure) are prepared.

  7. Effect of enzyme dehydration on alcalase-catalyzed dipeptide synthesis in near-anhydrous organic media.

    NARCIS (Netherlands)

    Vossenberg, P.; Beeftink, H.H.; Cohen Stuart, M.A.; Tramper, J.


    The effect of enzyme dehydration by molecular sieves on the coupling of phenylalanine amide and the carbamoylmethyl ester of N-protected phenylalanine in near-anhydrous tetrahydrofuran was investigated. This coupling was catalyzed by Alcalase covalently immobilized onto macroporous acrylic beads (Co

  8. Kinetics of Alcalase-catalyzed dipeptide synthesis in near-anhydrous organic media

    NARCIS (Netherlands)

    Vossenberg, P.; Beeftink, H.H.; Cohen Stuart, M.A.; Tramper, J.


    The coupling kinetics of phenylalanine amide and the carbamoylmethyl ester of N-protected phenylalanine in near-anhydrous tetrahydrofuran were investigated. This coupling was catalyzed by Alcalase covalently immobilized onto macroporous acrylic beads; these immobilized enzymes were hydrated prior to

  9. Iridium‐Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols with the Liberation of Syngas

    DEFF Research Database (Denmark)

    Olsen, Esben Paul Krogh; Madsen, Robert


    to excellent yields. Ethers, esters, imides, and aryl halides are stable under the reaction conditions, whereas olefins are partially saturated. The reaction is believed to proceed by two consecutive organometallic transformations that are catalyzed by the same iridium(I)–BINAP species. First, dehydrogenation...

  10. Preparation of fluorinated biaryls through direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates

    KAUST Repository

    Fang, Xin


    The direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates gave the desired products of fluorinated biaryls in good to excellent yields. A diverse set of important functional groups including methoxy, aldehyde, ester, nitro and halide can be well tolerated in the protocol. © 2013 Elsevier B.V. All rights reserved.

  11. Method of making alkyl esters (United States)

    Elliott, Brian


    Methods of making alkyl esters are described herein. The methods are capable of using raw, unprocessed, low-cost feedstocks and waste grease. Generally, the method involves converting a glyceride source to a fatty acid composition and esterifying the fatty acid composition to make alkyl esters. In an embodiment, a method of making alkyl esters comprises providing a glyceride source. The method further comprises converting the glyceride source to a fatty acid composition comprising free fatty acids and less than about 1% glyceride by mass. Moreover, the method comprises esterifying the fatty acid composition in the presence of a solid acid catalyst at a temperature ranging firm about C. to about C. to produce alkyl esters, such that at least 85% of the free fatty acids are converted to alkyl esters. The method also incorporates the use of packed bed reactors for glyceride conversion and/or fatty acid esterification to make alkyl esters.

  12. Mechanistic approaches to palladium-catalyzed alkene difunctionalization reactions


    Jensen, Katrina H.; Sigman, Matthew S.


    Alkene difunctionalization, the addition of two functional groups across a double bond, exemplifies a class of reactions with significant synthetic potential. This emerging area examines recent developments of palladium-catalyzed difunctionalization reactions, with a focus on mechanistic strategies that allow for functionalization of a common palladium alkyl intermediate.

  13. Study of intermolecular interactions in the system of equilibrium catalytic transesterification of esters. 4. Fourier IR studies of the interaction of alcohols with esters

    International Nuclear Information System (INIS)

    Interaction of alcohols ROH with esters PhCOOR (R = Me, n-Bu, n-C7H15) in binary mixtures and in solutions in non-polar solvents was studies over a wide temperature range by means of Fourier IR spectroscopy. Even with alcohol taken in a great excess, two bands are observed in the region of ΝCO vibrations. The low-frequency band, correspond to the ester molecules bonded by hydrogen bonds of the C=O...HO type. The high-frequence band is shifted by 3-5 cm-1 with respect to the ester ΝCO band. The discreteness of the shift, indicates that an H-complex of one more type is formed between the alcohol and the ester. The analysis of data available allows one to conclude that the complex formation involves the alkoxyl oxygen atom of the ester. The formation enthalpies were determined for H-bond of n-BuOH with the esters and with transesterification catalysts B(OBu)3

  14. Bond Issues. (United States)

    Pollack, Rachel H.


    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  15. Muon catalyzed fusion

    Energy Technology Data Exchange (ETDEWEB)

    Ishida, K. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Nagamine, K. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Matsuzaki, T. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Kawamura, N. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan)


    The latest progress of muon catalyzed fusion study at the RIKEN-RAL muon facility (and partly at TRIUMF) is reported. The topics covered are magnetic field effect, muon transfer to {sup 3}He in solid D/T and ortho-para effect in dd{mu} formation.

  16. A density functional theory model of mechanically activated silyl ester hydrolysis

    International Nuclear Information System (INIS)

    To elucidate the mechanism of the mechanically activated dissociation of chemical bonds between carboxymethylated amylose (CMA) and silane functionalized silicon dioxide, we have investigated the dissociation kinetics of the bonds connecting CMA to silicon oxide surfaces with density functional calculations including the effects of force, solvent polarizability, and pH. We have determined the activation energies, the pre-exponential factors, and the reaction rate constants of candidate reactions. The weakest bond was found to be the silyl ester bond between the silicon and the alkoxy oxygen atom. Under acidic conditions, spontaneous proton addition occurs close to the silyl ester such that neutral reactions become insignificant. Upon proton addition at the most favored position, the activation energy for bond hydrolysis becomes 31 kJ mol−1, which agrees very well with experimental observation. Heterolytic bond scission in the protonated molecule has a much higher activation energy. The experimentally observed bi-exponential rupture kinetics can be explained by different side groups attached to the silicon atom of the silyl ester. The fact that different side groups lead to different dissociation kinetics provides an opportunity to deliberately modify and tune the kinetic parameters of mechanically activated bond dissociation of silyl esters


    Directory of Open Access Journals (Sweden)

    Tjahjono Herawan


    Full Text Available Lipase-catalyzed transesterifications-especially in a solvent-free medium-are important for industrial applications because such systems would have an enormous advantage by avoiding the problem of separation, toxicity and flammability of organic solvents. However, the organic solvent-free alcoholysis, especially methanolysis, does not give high conversions. The same problem also occurs when ethyl or methyl acetate are used as acyl acceptors. The main problems of lipase-catalyzed organic solvent-free alcoholysis are first, the solubility of the plant oil in the substrate or solvent and second, the fact that transesterification is an equilibrium reaction. Dialkyl carbonates, versatile compounds due to their chemical reactivity and physical properties, may provide an alternative to solve both problems. Using dialkyl carbonates transesterification is not an equilibrium reaction, because the intermediate compound immediately decomposes to carbon dioxide and an alcohol. Moreover, dialkyl carbonates (especially dimethyl carbonate are cheap and widely available. For single step lipase-catalyzed transesterification of palm kernel oil, diakyl carbonates (in this case dimethyl and diethyl carbonate gave better yields compared to those of short chain alcohols. The rate of ester formation with dialkyl carbonates as substrate was about 6-7 times higher than that obtained with short chain alcohols. The formation of esters was gradually increased by a higher enzyme amount from 5-20% (w/w of oil for 8 h reaction time. However from the economic point of view, an enzyme amount of 10% on the weight base of oil was proposed for further reaction. Generally, the highest ester formation was observed when a temperature of 60°C was used. However, in the case of dimethyl carbonate little difference was observed at reaction temperatures of 60 and 70oC and the reactions proceeded nearly identically. The esters formation increased drastically up to more than 70% when water

  18. Enzymatic synthesis and application of fatty acid ascorbyl esters

    Directory of Open Access Journals (Sweden)

    Stojanović Marija M.


    Full Text Available Fatty acid ascorbyl esters are liposoluble substances that possess good antioxidative properties. These compounds could be synthesized by using various acyl donors for acylation of vitamin C in reaction catalyzed by chemical means or lipases. Enzymatic process is preferred since it is regioselective, performed under mild reaction conditions, with the obtained product being environmentally friendly. Polar organic solvents, ionic liquids, and supercritical fluids has been successfully used as a reaction medium, since commonly used solvents with high Log P values are inapplicable due to ascorbic acid high polarity. Acylation of vitamin C using fatty acids, their methyl-, ethyl-, and vinyl esters, as well as triglycerides has been performed, whereas application of the activated acyl donors enabled higher molar conversions. In each case, majority of authors reported that using excessive amount of the acyl donor had positive effect on yield of product. Furthermore, several strategies have been employed for shifting the equilibrium towards the product by water content control. These include adjusting the initial water activity by pre-equilibration of reaction mixture, enzyme preparation with water vapor of saturated salt solutions, and the removal of formed water by the addition of molecular sieves or salt hydrate pairs. The aim of this article is to provide a brief overview of the procedures described so far for the lipase-catalyzed synthesis of fatty acid ascorbyl esters with emphasis on the potential application in food, cosmetics, and pharmaceutics. Furthermore, it has been pointed out that the main obstacles for process commercialization are long reaction times, lack of adequate purification methods, and high costs of lipases. Thus, future challenges in this area are testing new catalysts, developing continuous processes for esters production, finding cheaper acyl donors and reaction mediums, as well as identifying standard procedures for

  19. Mechanism of Imidazole-Promoted Ligation of Peptide Phenyl Esters

    Institute of Scientific and Technical Information of China (English)

    王晨; 刘磊


    Imidazole-promoted ligation of peptide phenyl esters was recently found to be a complementary method for protein chemical synthesis. Theoretical calculations have been carried out to understand the detailed mechanism of this particular ligation process. It is found that both the reaction of the phenyl ester with imidazole and the reaction of the acyl imidazole intermediate with cysteine proceed through an addition-elimination mechanism. The cleavage of the C--O bond in the reaction between the phenyl ester and imidazole is the rate-limiting step of the overall liga- tion process. Interestingly, although the imidazole-promoted phenyl ester ligation has a higher free energy barrier than the conventional thiophenol-promoted native chemical ligation for a sterically less hindered C-terminal amino acid (e.g. gylcine), for a sterically hindered C-terminal amino acid (e.g. proline) the imidazole-promoted phenyl ester ligation is calculated to be more favorable than the conventional thiophenol-promoted native chemical ligation.

  20. [(NHC)AuI]-catalyzed formation of conjugated enones and enals: an experimental and computational study. (United States)

    Marion, Nicolas; Carlqvist, Peter; Gealageas, Ronan; de Frémont, Pierre; Maseras, Feliu; Nolan, Steven P


    The [(NHC)AuI]-catalyzed (NHC=N-heterocyclic carbene) formation of alpha,beta-unsaturated carbonyl compounds (enones and enals) from propargylic acetates is described. The reactions occur at 60 degrees C in 8 h in the presence of an equimolar mixture of [(NHC)AuCl] and AgSbF6 and produce conjugated enones and enals in high yields. Optimization studies revealed that the reaction is sensitive to the solvent, the NHC, and, to a lesser extent, to the silver salt employed, leading to the use of [(ItBu)AuCl]/AgSbF6 in THF as an efficient catalytic system. This transformation proved to have a broad scope, enabling the stereoselective formation of (E)-enones and -enals with great structural diversity. The effect of substitution at the propargylic and acetylenic positions has been investigated, as well as the effect of aryl substitution on the formation of cinnamyl ketones. The presence or absence of water in the reaction mixture was found to be crucial. From the same phenylpropargyl acetates, anhydrous conditions led to the formation of indene compounds via a tandem [3,3] sigmatropic rearrangement/intramolecular hydroarylation process, whereas simply adding water to the reaction mixture produced enone derivatives cleanly. Several mechanistic hypotheses, including the hydrolysis of an allenol ester intermediate and SN2' addition of water, were examined to gain an insight into this transformation. Mechanistic investigations and computational studies support [(NHC)AuOH], produced in situ from [(NHC)AuSbF6] and H2O, instead of cationic [(NHC)AuSbF6] as the catalytically active species. Based on DFT calculations performed at the B3LYP level of theory, a full catalytic cycle featuring an unprecedented transfer of the OH moiety bound to the gold center to the C[triple chemical bond]C bond leading to the formation of a gold-allenolate is proposed. PMID:17530724

  1. The effects of zeolite and silica gel on synthesis of amylisobutyrate catalyzed by lipase from Candida rugosa


    Stojaković Sanja B.; Bezbradica Dejan I.; Mijin Dušan Ž.; Knežević Zorica D.; Šiler-Marinković Slavica S.


    Lipase-catalyzed synthesis of esters has been widely investigated due to numerous advantages in comparison with the conventional chemical process catalyzed with concentrated acids since use of chemical catalysts leads to several problems. The most important disadvantages are corrosion of equipment, hazards of handling of the corrosive acids that are not reused, loss of conversion, yield and selectivity. The activity of water in reaction mixture seems to be one of the crucial factors affecting...

  2. Altering small and medium alcohol selectivity in the wax ester synthase. (United States)

    Barney, Brett M; Ohlert, Janet M; Timler, Jacobe G; Lijewski, Amelia M


    The bifunctional wax ester synthase/acyl-coenzyme A:diacylglycerol acyltransferase (WS/DGAT or wax ester synthase) catalyzes the terminal reaction in the bacterial wax ester biosynthetic pathway, utilizing a range of alcohols and fatty acyl-CoAs to synthesize the corresponding wax ester. The wild-type wax ester synthase Maqu_0168 from Marinobacter aquaeolei VT8 exhibits a preference for longer fatty alcohols, while applications with smaller alcohols would yield products with desired biotechnological properties. Small and medium chain length alcohol substrates are much poorer substrates for the native enzyme, which may hinder broad application of the wax ester synthase in many proposed biosynthetic schemes. Developing approaches to improve enzyme activity toward specific smaller alcohol substrates first requires a clear understanding of which amino acids of the primary sequences of these enzymes contribute to substrate specificity in the native enzyme. In this report, we surveyed a range of potential residues and identified the leucine at position 356 and methionine at position 405 in Maqu_0168 as residues that affected selectivity toward small, branched, and aromatic alcohols when substituted with different amino acids. This analysis provides evidence of residues that line the binding site for wax ester synthase, which will aid rational approaches to improve this enzyme with specific substrates.

  3. Adipocyte protein modification by Krebs cycle intermediates and fumarate ester-derived succination. (United States)

    Manuel, Allison M; Frizzell, Norma


    Protein succination, the non-enzymatic modification of cysteine residues by fumarate, is distinguishable from succinylation, an enzymatic reaction forming an amide bond between lysine residues and succinyl-CoA. Treatment of adipocytes with 30 mM glucose significantly increases protein succination with only a small change in succinylation. Protein succination may be significantly increased intracellularly after treatment with fumaric acid esters, however, the ester must be removed by saponification to permit 2SC-antibody detection of the fumarate adduct.

  4. Process Technology for Immobilized LipaseProcess Technology for Immobilized Lipase-catalyzed

    DEFF Research Database (Denmark)

    Xu, Yuan

    -down experimental work is described in this thesis. The methodology uses economic targets to test options characterized via a set of tools. In order to validate the methodology, two processes based on immobilized lipase-catalysis have been studied: transesterification and esterification of vegetable oils...... for the production of biodiesel. The two processes are focused on the conversion of the two main components of vegetable oil materials, glyceride esters and free fatty acids respectively, into fatty acid alkyl esters. Although biodiesel is conventionally prepared via chemical-catalyzed transesterification...... of vegetable oils with methanol to produce fatty acid methyl esters (FAME), this work has been focused on the production of fatty acid ethyl esters (FAEE) with bioethanol due to the expected improved sustainability of this type of biodiesel. A key reaction characteristic of the immobilized lipase...

  5. Tritium catalyzed deuterium tokamaks

    International Nuclear Information System (INIS)

    A preliminary assessment of the promise of the Tritium Catalyzed Deuterium (TCD) tokamak power reactors relative to that of deuterium-tritium (D-T) and catalyzed deuterium (Cat-D) tokamaks is undertaken. The TCD mode of operation is arrived at by converting the 3He from the D(D,n)3He reaction into tritium, by neutron capture in the blanket; the tritium thus produced is fed into the plasma. There are three main parts to the assessment: blanket study, reactor design and economic analysis and an assessment of the prospects for improvements in the performance of TCD reactors (and in the promise of the TCD mode of operation, in general)

  6. Parental Bonding

    Directory of Open Access Journals (Sweden)

    T. Paul de Cock


    Full Text Available Estimating the early parent–child bonding relationship can be valuable in research and practice. Retrospective dimensional measures of parental bonding provide a means for assessing the experience of the early parent–child relationship. However, combinations of dimensional scores may provide information that is not readily captured with a dimensional approach. This study was designed to assess the presence of homogeneous groups in the population with similar profiles on parental bonding dimensions. Using a short version of the Parental Bonding Instrument (PBI, three parental bonding dimensions (care, authoritarianism, and overprotection were used to assess the presence of unobserved groups in the population using latent profile analysis. The class solutions were regressed on 23 covariates (demographics, parental psychopathology, loss events, and childhood contextual factors to assess the validity of the class solution. The results indicated four distinct profiles of parental bonding for fathers as well as mothers. Parental bonding profiles were significantly associated with a broad range of covariates. This person-centered approach to parental bonding has broad utility in future research which takes into account the effect of parent–child bonding, especially with regard to “affectionless control” style parenting.

  7. Solid acid catalyzed biodiesel production from waste cooking oil

    Energy Technology Data Exchange (ETDEWEB)

    Jacobson, Kathlene; Gopinath, Rajesh; Meher, Lekha Charan; Dalai, Ajay Kumar [Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, SK, S7N 5A9 (Canada)


    Various solid acid catalysts were evaluated for the production of biodiesel from low quality oil such as waste cooking oil (WCO) containing 15 wt.% free fatty acids. The zinc stearate immobilized on silica gel (ZS/Si) was the most effective catalyst in simultaneously catalyzing the transesterification of triglycerides and esterification of free fatty acid (FFA) present in WCO to methyl esters. The optimization of reaction parameters with the most active ZS/Si catalyst showed that at 200 C, 1:18 oil to alcohol molar ratio and 3 wt.% catalysts loading, a maximum ester yield of 98 wt.% could be obtained. The catalysts were recycled and reused many times without any loss in activity. (author)

  8. Sintesis Metil Ester Sulfonat Dari Asam Stearat Dan Metil Ester Sulfonat Dari Asam Oleat


    Samosir, Yustina


    The Synthesis of Methyl Ester Sulfonate (MES) from stearic acid and from oleic acid through the stages of esterification reaction, that are esterification from stearic acid and oleic acid that forms methyl ester stearic acid and methyl ester oleic acid next stage was sulfonating the two of methyl esters to form a methyl ester sulfonate stearic acid and methyl ester oleic acid sulfonate. Furthermore, both fatty acid methyl ester sulfonate is neutralized with NaOH to obtain sulfonate salt. ...

  9. Palladium-Catalyzed Arylation of Fluoroalkylamines (United States)

    Brusoe, Andrew T.; Hartwig, John F.


    We report the synthesis of fluorinated anilines by palladium-catalyzed coupling of fluoroalkylamines with aryl bromides and aryl chlorides. The products of these reactions are valuable because anilines typically require the presence of an electron-withdrawing substituent on nitrogen to suppress aerobic or metabolic oxidation, and the fluoroalkyl groups have steric properties and polarity distinct from those of more common electron-withdrawing amide and sulfonamide units. The fluoroalkylaniline products are unstable under typical conditions for C–N coupling reactions (heat and strong base). However, the reactions conducted with the weaker base KOPh, which has rarely been used in cross-coupling to form C–N bonds, occurred in high yield in the presence of a catalyst derived from commercially available AdBippyPhos and [Pd(allyl)Cl]2. Under these conditions, the reactions occur with low catalyst loadings (<0.50 mol % for most substrates) and tolerate the presence of various functional groups that react with the strong bases that are typically used in Pd-catalyzed C–N cross-coupling reactions of aryl halides. The resting state of the catalyst is the phenoxide complex, (BippyPhosPd(Ar)OPh); due to the electron-withdrawing property of the fluoroalkyl substituent, the turnover-limiting step of the reaction is reductive elimination to form the C–N bond. PMID:26065341

  10. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Qinhua [Iowa State Univ., Ames, IA (United States)


    The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I2, ICl, PhSeCl, PhSCl and p-O2NC6H4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement

  11. Synthesis of thermoplastic poly(ester-olefin elastomers

    Directory of Open Access Journals (Sweden)

    Tanasijević Branka


    Full Text Available A series of thermoplastic poly(ester-olefin elastomers, based on poly(ethylene-stat-butylene, HO-PEB-OH, as the soft segment and poly (butylene terephthalate, PBT, as the hard segment, were synthesized by a catalyzed transesterification reaction in solution. The incorporation of soft hydrogenated poly(butadiene segments into the copolyester backbone was accomplished by the polycondensation of α, ω-dihydroxyl telechelic HO-PEB-OH, (PEB Mn = 3092 g/mol with 1,4-butanediol (BD and dimethyl terephthalate (DMT in the presence of a 50 wt-% high boiling solvent i.e., 1,2,4-trichlorobenzene. The molar ratio of the starting comonomers was selected to result in a constant hard to soft weight ratio of 60:40. The synthesis was optimized in terms of both the concentration of catalyst, tetra-n-butyl-titanate (Ti(OBu4, and stabilizer, N,N'-diphenyl-p-phenylenediamine (DPPD, as well as the reaction time. It was found that the optimal catalyst concentration (Ti(OBu4 for the synthesis of these thermoplastic elastomers was 1.0 mmol/mol ester and the optimal DPPD concentration was 1.0 wt-%. The extent of the reaction was followed by measuring the inherent viscosity of the reaction mixture. The effectiveness of the incorporation of the soft segments into the copolymer chains was proved by Soxhlet extraction with chloroform. The molecular structures, composition and the size of the synthesized poly(ester-butylenes were verified by 1H NMR spectroscopy, viscometry of dilute solutions and the complex dynamic melt viscosity. The thermal properties of poly(ester-olefins were investigated by differential scanning calorimetry (DSC. The degree of crystallinity was also determined by DSC. The thermal and thermo-oxidative stability were investigated by thermogravimetric analysis (TGA. The rheological properties of poly(ester-olefins were investigated by dynamic mechanical spectroscopy in the melt and solid state.

  12. Pt-Catalyzed Synthesis of Functionalized Symmetrical and Unsymmetrical Disilazanes. (United States)

    Kuciński, Krzysztof; Szudkowska-Frątczak, Justyna; Hreczycho, Grzegorz


    In nearly every total synthesis, silylating agents are employed in synthetic steps to protect sensitive functional groups. A Pt-catalyzed hydrosilylation of various unsaturated substrates to prepare novel symmetrical and unsymmetrical disilazanes is described. The developed synthetic methodology is widely applicable and tolerates all manner of functional groups (e.g., amines, ethers, esters, halogens, silanes, etc.). To demonstrate the value of the described method, mono-substituted 1,1,3,3-tetramethyldisilazanes were further selectively converted to completely new unsymmetrical derivatives. PMID:27414042

  13. Optimization of reaction parameters for enzymatic glyceride synthesis from fish oil: Ethyl esters versus free fatty acids

    DEFF Research Database (Denmark)

    Ravn, Helle Christine; Damstrup, Marianne L.; Meyer, Anne S.


    Enzymatic conversion of fish oil free fatty acids (FFA) or fatty acid ethyl esters (FAE) into glycerides via esterification or transesterification was examined. The reactions catalyzed by Lipozyme™ 435, a Candida antarctica lipase, were optimized. Influence on conversion yields of fatty acid chai...

  14. Influence of extended storage on fuel properties of methyl esters prepared from canola, palm, soybean, and sunflower oils (United States)

    Fatty acid methyl esters prepared from canola, palm, soybean, and sunflower oils by homogenous base-catalyzed methanolysis were stored for 12 months at three constant temperatures (-15, 22, and 40 deg C) and properties such as oxidative stability, acid value, kinematic viscosity, low temperature ope...

  15. Enzymatic Synthesis of Palm Alkyl Ester Using Dialkyl Carbonate as an Alkyl Donors

    Directory of Open Access Journals (Sweden)

    Roila Awang


    Full Text Available Problem statement: Though efficient in terms of reaction yield and time, the chemical approach to synthesizing alkyl ester has drawback such as difficulties in the recovery of glycerol and the need for removal of salt residue. On the other hand, biocatalyst allow for synthesis of specific alkyl esters and easy recovery of glycerol. However, the solvent-free alcoholysis, does not give high conversion. The same problem was also found when ethyl or methyl acetate was used as acyl acceptors. Approach: Lipase catalyzed transesterification of oil and dialkyl carbonate was predicted to give higher conversion in solvent free reaction system. Results: Alkyl esters were synthesized enzymatically to overcome the problems associated with chemical processes. In this study, dialkyl carbonates were used as an alkyl donor for the production of alkyl ester. Nine commercial lipases were tested for their suitability for the reaction system. Among the lipase tested, Novozym 435 was chosen for optimization study because of their higher activity. In a solvent-free reaction system, the ester formation using dialkyl carbonate was 6 times higher than using ethanol and methanol. The effect of various reaction parameters such as temperature, amount of enzyme, organic solvent and structure of substrates were studied to determine optimal condition. The optimal conditions of ester formation were reaction temperature at 60°C, reaction time at 8 h, enzyme amount of 10% (w/w of oil and 0.2% wt added water. Conclusion: Solvent-free lipase catalyzed transesterification of palm kernel oil and dialkyl carbonates gave higher conversion of ester compared to the reaction using short chain alcohol as an alkyl donors.

  16. QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis. [quantitative structure-activity relationship, complete neglect of differential overlap (United States)

    Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.


    Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of cationic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR-primeP(O)X, where R and R-prime are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrolysis rate constant.


    Institute of Scientific and Technical Information of China (English)

    Elhussein A.Taha; Jun-tao Wu; Kai Gao; Lin Guo


    Fumed silica/bisphenol A dicyanate ester (BADCy) nanocomposites were prepared by introducing different contents of nano-sized fumed SiO2 into the BADCy matrix.Two different average primary particle diameters of 12 and 40 nm were chosen.Dibutyltindilaurate (DBTDL) catalyst was chosen to catalyze the cyanate ester group into triazine group via cyclotrimerization reaction.The SEM micrographs indicated that the fumed SiO2 particles were homogeneously dispersed in the poly(bisphenol A dicyanate) matrix by means of ultrasonic treatment and the addition of a coupling agent.The FTIR spectroscopy shows that,not only DBTDL catalyzes the polymerization reaction but also-OH groups of the SiO2 particles surface help the catalyst for the complete polymerization of BADCy monomer.The thermal stability of the cured BADCy can be improved by adequate addition of fumed SiO2.A slight increase in the dielectric constant and dielectric loss values were identified by testing the dielectric properties of the prepared nanocomposite samples.By increasing the SiO2 content,there was a slight increasing in the thermal conductivity values of the tested samples.The obtained results proved that the fumed silica/BADCy nanocomposites had good thermal and dielectrical properties and can be used in many applications such as in the thermal insulation field.

  18. Catalyzed Ceramic Burner Material

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, Amy S., Dr.


    Catalyzed combustion offers the advantages of increased fuel efficiency, decreased emissions (both NOx and CO), and an expanded operating range. These performance improvements are related to the ability of the catalyst to stabilize a flame at or within the burner media and to combust fuel at much lower temperatures. This technology has a diverse set of applications in industrial and commercial heating, including boilers for the paper, food and chemical industries. However, wide spread adoption of catalyzed combustion has been limited by the high cost of precious metals needed for the catalyst materials. The primary objective of this project was the development of an innovative catalyzed burner media for commercial and small industrial boiler applications that drastically reduce the unit cost of the catalyzed media without sacrificing the benefits associated with catalyzed combustion. The scope of this program was to identify both the optimum substrate material as well as the best performing catalyst construction to meet or exceed industry standards for durability, cost, energy efficiency, and emissions. It was anticipated that commercial implementation of this technology would result in significant energy savings and reduced emissions. Based on demonstrated achievements, there is a potential to reduce NOx emissions by 40,000 TPY and natural gas consumption by 8.9 TBtu in industries that heavily utilize natural gas for process heating. These industries include food manufacturing, polymer processing, and pulp and paper manufacturing. Initial evaluation of commercial solutions and upcoming EPA regulations suggests that small to midsized boilers in industrial and commercial markets could possibly see the greatest benefit from this technology. While out of scope for the current program, an extension of this technology could also be applied to catalytic oxidation for volatile organic compounds (VOCs). Considerable progress has been made over the course of the grant

  19. Ru/Me-BIPAM-Catalyzed Asymmetric Addition of Arylboronic Acids to Aliphatic Aldehydes and α-Ketoesters

    Directory of Open Access Journals (Sweden)

    Momoko Watanabe


    Full Text Available A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(arylmethanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM achieved excellent enantioselectivities.

  20. Palladium-Catalyzed Modification of Unprotected Nucleosides, Nucleotides, and Oligonucleotides

    Directory of Open Access Journals (Sweden)

    Kevin H. Shaughnessy


    Full Text Available Synthetic modification of nucleoside structures provides access to molecules of interest as pharmaceuticals, biochemical probes, and models to study diseases. Covalent modification of the purine and pyrimidine bases is an important strategy for the synthesis of these adducts. Palladium-catalyzed cross-coupling is a powerful method to attach groups to the base heterocycles through the formation of new carbon-carbon and carbon-heteroatom bonds. In this review, approaches to palladium-catalyzed modification of unprotected nucleosides, nucleotides, and oligonucleotides are reviewed. Polar reaction media, such as water or polar aprotic solvents, allow reactions to be performed directly on the hydrophilic nucleosides and nucleotides without the need to use protecting groups. Homogeneous aqueous-phase coupling reactions catalyzed by palladium complexes of water-soluble ligands provide a general approach to the synthesis of modified nucleosides, nucleotides, and oligonucleotides.

  1. The Structural Basis of Ribozyme-Catalyzed RNA Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Robertson, M.P.; Scott, W.G.; /UC, Santa Cruz


    Life originated, according to the RNA World hypothesis, from self-replicating ribozymes that catalyzed ligation of RNA fragments. We have solved the 2.6 angstrom crystal structure of a ligase ribozyme that catalyzes regiospecific formation of a 5' to 3' phosphodiester bond between the 5'-triphosphate and the 3'-hydroxyl termini of two RNA fragments. Invariant residues form tertiary contacts that stabilize a flexible stem of the ribozyme at the ligation site, where an essential magnesium ion coordinates three phosphates. The structure of the active site permits us to suggest how transition-state stabilization and a general base may catalyze the ligation reaction required for prebiotic RNA assembly.

  2. Bond Boom

    Institute of Scientific and Technical Information of China (English)


    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen, and Zhejiang and Guangdong provinces to issue bonds for the first time. How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the ShanghaiSecuritiesJournal. Edited excerpts follow:

  3. Bond Boom

    Institute of Scientific and Technical Information of China (English)


    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen,and Zhejiang and Guangdong provinces to issue bonds for the first time.How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the Shanghai Securities Journal.Edited excerpts follow.

  4. Enzymatic synthesis of lipophilic rutin and vanillyl esters from fish byproducts. (United States)

    Mbatia, Betty; Kaki, Shiva Shanker; Mattiasson, Bo; Mulaa, Francis; Adlercreutz, Patrick


    Lipase-catalyzed synthesis of lipophilic phenolic antioxidants was carried out with a concentrate of n-3 polyunsaturated fatty acids (PUFAs), recovered from oil extracted from salmon ( Salmon salar ) byproduct. Vanillyl alcohol and rutin were selected for the esterification reaction, and obtained esters yields were 60 and 30%, respectively. The antioxidant activities of the esters were compared with those of commercial butylated hydroxytoluene (BHT) and α-tocopherol using DPPH radical scavenging and thiobarbituric acid assays. In the DPPH assay, rutin esters showed better activity than vanillyl esters, and on the contrary in lipophilic medium, vanillyl esters were found to be superior to rutin esters. In bulk oil system, the antioxidant activities of rutin and vanillyl derivatives were lower than that of BHT and α-tocopherol, but in emulsion, they showed better activity than α-tocopherol. By attaching to natural phenolics, the PUFAs are protected against oxidation, and PUFA improves the hydrophobicity of the phenolic, which could enhance its function in lipid systems. PMID:21630661

  5. Adsorption of diethyl phthalate ester to clay minerals. (United States)

    Wu, Yanhua; Si, Youbin; Zhou, Dongmei; Gao, Juan


    Phthalate esters are a group of plasticizers, which have been widely detected in China's agricultural and industrial soils. In this study, batch adsorption experiments were conducted to investigate the environmental effects on the adsorption of diethyl phthalate ester (DEP) to clay minerals. The results showed that DEP adsorption isotherms were well fitted with the Freundlich model; the interlayer spacing of K(+) saturated montmorillonite (K-mont) was the most important adsorption area for DEP, and di-n-butyl ester (DnBP) was limited to intercalate into the interlayer of K-mont due to the bigger molecular size; there was no significant effect of pH and ionic strength on DEP adsorption to K-mont/Ca-mont, but to Na-mont clay. The adsorption to kaolinite was very limited. Data of X-ray diffraction and FTIR spectra further proved that DEP molecules could intercalate into K-/Ca-mont interlayer, and might interact with clay through H-bonding between carbonyl groups and clay adsorbed water. Coated humic acid on clay surface would enhance DEP adsorption at low concentration, but not at high concentration (eg. Ce>0.26 mM). The calculated adsorption enthalpy (ΔHobs) and adsorption isotherms at varied temperatures showed that DEP could be adsorbed easier as more adsorbed. This study implied that clay type, compound structure, exchangeable cation, soil organic matter and temperature played important roles in phthalate ester's transport in soil.

  6. Iridium-catalyzed intramolecular [4 + 2] cycloadditions of alkynyl halides


    Andrew Tigchelaar; William Tam


    Iridium-catalyzed intramolecular [4 + 2] cycloadditions of diene-tethered alkynyl halides were investigated by using [IrCl(cod)]2 as catalyst, and dppe was found to be the most suitable phosphine ligand for the reaction. No oxidative insertion of the iridium into the carbon–halide bond was observed, and the reactions proceeded to provide the halogenated cycloadducts in good yield (75–94%). These results are the first examples of cycloadditions of alkynyl halides using an iridium c...

  7. Enantiospecific sp2-sp3 coupling of secondary and tertiary boronic esters (United States)

    Bonet, Amadeu; Odachowski, Marcin; Leonori, Daniele; Essafi, Stephanie; Aggarwal, Varinder K.


    The cross-coupling of boronic acids and related derivatives with sp2 electrophiles (the Suzuki-Miyaura reaction) is one of the most powerful C-C bond formation reactions in synthesis, with applications that span pharmaceuticals, agrochemicals and high-tech materials. Despite the breadth of its utility, the scope of this Nobel prize-winning reaction is rather limited when applied to aliphatic boronic esters. Primary organoboron reagents work well, but secondary and tertiary boronic esters do not (apart from a few specific and isolated examples). Through an alternative strategy, which does not involve using transition metals, we have discovered that enantioenriched secondary and tertiary boronic esters can be coupled to electron-rich aromatics with essentially complete enantiospecificity. As the enantioenriched boronic esters are easily accessible, this reaction should find considerable application, particularly in the pharmaceutical industry where there is growing awareness of the importance of, and greater clinical success in, creating biomolecules with three-dimensional architectures.

  8. An Alternative Approach to Aldol Reactions: Gold-Catalyzed Formation of Boron Enolates from Alkynes


    Korner, C; Starkov, P.; Sheppard, T. D.


    A new method for enolate generation via the gold-catalyzed addition of boronic acids to alkynes is reported. The formation of boron enolates from readily accessible ortho-alkynylbenzeneboronic acids proceeds rapidly with 2 mol % PPh3AuNTf2 at ambient temperature. The enolates undergo aldol reaction with an aldehyde present in the reaction mixture to give cyclic boronate esters, which can be subsequently transformed into phenols, biaryls, or dihydrobenzofurans via oxidation, Suzuki-Miyaura, or...

  9. Papain-Catalyzed Synthesis of Polyglutamate Containing a Nylon Monomer Unit


    Kenjiro Yazawa; Keiji Numata


    Peptides have the potential to serve as an alternative for petroleum-based polymers to support a sustainable society. However, they lack thermoplasticity, owing to their strong intermolecular interactions. In contrast, nylon is famous for its thermoplasticity and chemical resistance. Here, we synthesized peptides containing a nylon unit to modify their thermal properties by using papain-catalyzed chemoenzymatic polymerization. We used l-glutamic acid alkyl ester as the amino acid monomer and ...

  10. Lipase-catalyzed highly enantioselective kinetic resolution of boron-containing chiral alcohols. (United States)

    Andrade, Leandro H; Barcellos, Thiago


    The first application of enzymes as catalysts to obtain optically pure boron compounds is described. The kinetic resolution of boron-containing chiral alcohols via enantioselective transesterification catalyzed by lipases was studied. Aromatic, allylic, and aliphatic secondary alcohols containing a boronate ester or boronic acid group were resolved by lipase from Candida antartica (CALB), and excellent E values (E > 200) and high enantiomeric excesses (up to >99%) of both remaining substrates and acetylated product were obtained.

  11. Avocado and olive oil methyl esters

    International Nuclear Information System (INIS)

    Biodiesel, the mono-alkyl esters of vegetable oils, animal fats or other triacylglycerol-containing materials and an alternative to conventional petroleum-based diesel fuel, has been derived from a variety of feedstocks. Numerous feedstocks have been investigated as potential biodiesel sources, including commodity oils, however, the methyl esters of avocado and olive oil would likely be suitable as biodiesel fuel. In order to expand the database and comprehensive evaluation of the properties of vegetable oil esters, in this work the fuel-related properties of avocado and olive oil methyl esters, which exhibit similar fatty acid profiles including high oleic acid content, are determined. The cetane numbers of avocado oil methyl esters and olive oil methyl esters are relatively high, determined as 59.2 and 62.5, respectively, due to their elevated content of methyl oleate. Other properties are well within the ranges specified in biodiesel standards. The cloud points of both esters are slightly above 0 °C due to their content of saturated esters, especially methyl palmitate. Overall, avocado and olive oil yield methyl esters with fuel properties comparable to methyl esters from other commodity vegetable oils. The 1H and 13C NMR spectra of avocado and olive oil methyl esters are reported. -- Highlights: • Methyl esters of avocado and olive oil meet biodiesel fuel standards. • Provides comparison for methyl esters of other vegetable oils with high oleic content. • Discusses and compares present results with prior literature

  12. Environmental effect of rapeseed oil ethyl ester

    International Nuclear Information System (INIS)

    Exhaust emission tests were conducted on rapeseed oil methyl ester (RME), rapeseed oil ethyl ester (REE) and fossil diesel fuel as well as on their mixtures. Results showed that when considering emissions of nitrogen oxides (NOx), carbon monoxide (CO) and smoke density, rapeseed oil ethyl ester had less negative effect on the environment in comparison with that of rapeseed oil methyl ester. When fuelled with rapeseed oil ethyl ester, the emissions of NOx showed an increase of 8.3% over those of fossil diesel fuel. When operated on 25-50% bio-ester mixed with fossil diesel fuel, NOx emissions marginally decreased. When fuelled with pure rapeseed oil ethyl ester, HC emissions decreased by 53%, CO emissions by 7.2% and smoke density 72.6% when compared with emissions when fossil diesel fuel was used. Carbon dioxide (CO2) emissions, which cause greenhouse effect, decreased by 782.87 g/kWh when rapeseed oil ethyl ester was used and by 782.26 g/kWh when rapeseed oil methyl ester was used instead of fossil diesel fuel. Rapeseed oil ethyl ester was more rapidly biodegradable in aqua environment when compared with rapeseed oil methyl ester and especially with fossil diesel fuel. During a standard 21 day period, 97.7% of rapeseed oil methyl ester, 98% of rapeseed oil ethyl ester and only 61.3% of fossil diesel fuel were biologically decomposed. (author)

  13. Lubricating and Waxy Esters. VI. Effect of Symmetry about Ester on Crystallization of Linear Monoester Isomers

    Directory of Open Access Journals (Sweden)

    Laziz Bouzidi


    Full Text Available The crystal structure development of jojoba-like esters incorporating either 1-decenoic acid and/or 1-decenol, namely octadec-9-enyl dec-9-enoate (JLE-281, and its isomer dec-9-enyl oleate (JLE-282 was investigated to reveal the effect of symmetry about the ester group on crystallization of aliphatic fatty monoesters. The phase transformation path was investigated with temperature-time resolved X-ray diffraction during stepped isothermal crystallization, and while cooling from the melt at a fixed rate. Startling differences in phase behavior were uncovered between the isomers. When stepped isothermals were used, selective extinctions occurred at a transition temperature for JLE-281 but not for JLE-282. The extinctions, which are due to dramatic changes in the electronic density of certain families of planes, indicate a phase transition attributed to a brusque rearrangement of the oxygen atoms in the crystal subcell. The phase transition did not occur when the JLEs were cooled continuously. The crucial role played by the position of the alkyl chain and its orientation relative to the easy rotation site of the C–O bond in the phase trajectories of the JLEs was particularly highlighted.

  14. DFT characterization of key intermediates in thiols oxidation catalyzed by amavadin. (United States)

    Bertini, Luca; Barbieri, Valentina; Fantucci, Piercarlo; De Gioia, Luca; Zampella, Giuseppe


    Amavadin is an unusual octa-coordinated V(IV) complex isolated from Amanita muscaria mushrooms. The outer-sphere catalytic properties of such a complex toward several oxidation reactions are well known. Nevertheless, a remarkable example exists, in which the V(V) (d(0)) oxidized form of amavadin is able to electro-catalyze the oxidation of some thiols to the corresponding disulfides through an inner-sphere mechanism (Guedes da Silva et al. J. Am. Chem. Soc.1996, 118, 7568-7573.) The reaction mechanism implies the formation of an amavadin-substrate intermediate, whose half-life is about 0.3 s. By means of Density Functional Theory (DFT) computations and Quantum Theory of Atoms in Molecules (QTAIM) analysis of the electron density, we have first characterized the stereoelectronic features of the V(IV) (inactive) and V(V) (active) states of amavadin. Then, the formation of the V(V) complex with methyl mercaptoacetate (MMA), which has been chosen as a prototypical substrate, has been characterized both thermodynamically and kinetically. DFT results reveal that protonation of V(V) amavadin at a carboxylate oxygen not directly involved in the V coordination, favors MMA binding into the first coordination sphere of vanadium, by substitution of the amavadin carboxylate oxygen with that of the substrate and formation of an S-HO hydrogen bond interaction. The latter interaction can promote SH deprotonation and binding of the thiolate group to vanadium. The kinetic and thermodynamic feasibility of the V(V)-MMA intermediates formation is in agreement, along with electrochemical experimental data, also with the biological role exerted by amavadin. Finally, the presence of an ester functional group as an essential requisite for MMA oxidation has been rationalized. PMID:21625716

  15. Synthesis of substituted 2-cyanoarylboronic esters

    DEFF Research Database (Denmark)

    Lysén, Morten; Hansen, Henriette M; Begtrup, Mikael;


    The synthesis of substituted 2-cyanoarylboronic esters is described via lithiation/in situ trapping of the corresponding methoxy-, trifluoromethyl-, fluoro-, chloro-, and bromobenzonitriles. The crude arylboronic esters were obtained in high yields and purities and with good regioselectivities....

  16. Synthesis, spectroscopic and chromatographic studies of sunflower oil biodiesel using optimized base catalyzed methanolysis. (United States)

    Naureen, Rizwana; Tariq, Muhammad; Yusoff, Ismail; Chowdhury, Ahmed Jalal Khan; Ashraf, Muhammad Aqeel


    Methyl esters from vegetable oils have attracted a great deal of interest as substitute for petrodiesel to reduce dependence on imported petroleum and provide an alternate and sustainable source for fuel with more benign environmental properties. In the present study biodiesel was prepared from sunflower seed oil by transesterification by alkali-catalyzed methanolysis. The fuel properties of sunflower oil biodiesel were determined and discussed in the light of ASTM D6751 standards for biodiesel. The sunflower oil biodiesel was chemically characterized with analytical techniques like FT-IR, and NMR ((1)H and (13)C). The chemical composition of sunflower oil biodiesel was determined by GC-MS. Various fatty acid methyl esters (FAMEs) were identified by retention time data and verified by mass fragmentation patterns. The percentage conversion of triglycerides to the corresponding methyl esters determined by (1)H NMR was 87.33% which was quite in good agreement with the practically observed yield of 85.1%.

  17. Increased production of wax esters in transgenic tobacco plants by expression of a fatty acid reductase:wax synthase gene fusion. (United States)

    Aslan, Selcuk; Hofvander, Per; Dutta, Paresh; Sun, Chuanxin; Sitbon, Folke


    Wax esters are hydrophobic lipids consisting of a fatty acid moiety linked to a fatty alcohol with an ester bond. Plant-derived wax esters are today of particular concern for their potential as cost-effective and sustainable sources of lubricants. However, this aspect is hampered by the fact that the level of wax esters in plants generally is too low to allow commercial exploitation. To investigate whether wax ester biosynthesis can be increased in plants using transgenic approaches, we have here exploited a fusion between two bacterial genes together encoding a single wax ester-forming enzyme, and targeted the resulting protein to chloroplasts in stably transformed tobacco (Nicotiana benthamiana) plants. Compared to wild-type controls, transgenic plants showed both in leaves and stems a significant increase in the total level of wax esters, being eight-fold at the whole plant level. The profiles of fatty acid methyl ester and fatty alcohol in wax esters were related, and C16 and C18 molecules constituted predominant forms. Strong transformants displayed certain developmental aberrations, such as stunted growth and chlorotic leaves and stems. These negative effects were associated with an accumulation of fatty alcohols, suggesting that an adequate balance between formation and esterification of fatty alcohols is crucial for a high wax ester production. The results show that wax ester engineering in transgenic plants is feasible, and suggest that higher yields may become achieved in the near future.

  18. Hydrolyzable polyureas bearing hindered urea bonds. (United States)

    Ying, Hanze; Cheng, Jianjun


    Hydrolyzable polymers are widely used materials that have found numerous applications in biomedical, agricultural, plastic, and packaging industrials. They usually contain ester and other hydrolyzable bonds, such as anhydride, acetal, ketal, or imine, in their backbone structures. Here, we report the first design of hydrolyzable polyureas bearing dynamic hindered urea bonds (HUBs) that can reversibly dissociate to bulky amines and isocyanates, the latter of which can be further hydrolyzed by water, driving the equilibrium to facilitate the degradation of polyureas. Polyureas bearing 1-tert-butyl-1-ethylurea bonds that show high dynamicity (high bond dissociation rate), in the form of either linear polymers or cross-linked gels, can be completely degraded by water under mild conditions. Given the simplicity and low cost for the production of polyureas by simply mixing multifunctional bulky amines and isocyanates, the versatility of the structures, and the tunability of the degradation profiles of HUB-bearing polyureas, these materials are potentially of very broad applications.

  19. Biodiesel With Optimized Fatty Ester Composition (United States)

    Biodiesel is largely composed of the mono-alkyl esters, usually methyl esters, of vegetable oils or animal fats with its fatty acid profile corresponding to that of the parent oil or fat. The different fatty esters have varying properties of relevance to biodiesel. The feedstock-dependent variatio...

  20. Hydrolysis of Dipeptide Heptyl Esters with Newlase F

    Institute of Scientific and Technical Information of China (English)


    Newlase F is a rude enzyme which contains triacylglycerol lipase and acid protease. Hydrolysis of dipeptide heptyl esters with Newlase F was studied in phosphate buffer-organic solvent by HPLC. When the Newlase F's level reached 5 mg/mL under mild condition (pH 7.0, 30°C), the lipase had the highest activity. The reaction was also affected greatly by organic solvents and their concentrations. It is found that protease in Newlase F does not hydrolyze amide bond under this condition (pH 7.0, r.t.).

  1. Improvement in biodiesel production from soapstock oil by one-stage lipase catalyzed methanolysis

    International Nuclear Information System (INIS)

    Highlights: • Soapstock is a less expensive feedstock reservoir for biodiesel production. • Addition of tert-alcohol can enhance the yield of fatty acid methyl ester significantly. • One-stage lipase catalyzed methanolysis of soapstock oil was successfully developed. • FAME yield of 95.2% was obtained with low lipase loading in a shorter reaction time. - Abstract: A major obstacle in the commercialization of biodiesel is its cost of manufacturing, primarily the raw material cost. In order to decrease the cost of biodiesel, soapstock oil was investigated as the feedstock for biodiesel production. Because the soapstock oil containing large amounts of free fatty acids (FFAs) cannot be effectively converted to biodiesel, complicated two-stage process (esterification followed by transesterification) was generally adopted. In this study, simple one-stage lipase catalyzed methanolysis of soapstock oil was developed via one-pot esterification and transesterification. Water produced by lipase catalyzed esterification of FFAs affected the lipase catalyzed transesterification of glycerides in the soapstock oil severely. Addition of tert-alcohol could overcome this problem and enhance the fatty acid methyl ester (FAME) yield from 42.8% to 76.4%. The FAME yield was further elevated to 95.2% by optimizing the methanol/oil molar ratio, lipase amount, and water absorbent. The developed process enables the simple, efficient, and green production of biodiesel from soapstock oil, providing with a potential industrial application

  2. Diffusion bonding (United States)

    Anderson, Robert C.


    1. A method for joining beryllium to beryllium by diffusion bonding, comprising the steps of coating at least one surface portion of at least two beryllium pieces with nickel, positioning a coated surface portion in a contiguous relationship with an other surface portion, subjecting the contiguously disposed surface portions to an environment having an atmosphere at a pressure lower than ambient pressure, applying a force upon the beryllium pieces for causing the contiguous surface portions to abut against each other, heating the contiguous surface portions to a maximum temperature less than the melting temperature of the beryllium, substantially uniformly decreasing the applied force while increasing the temperature after attaining a temperature substantially above room temperature, and maintaining a portion of the applied force at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions.

  3. Clicked Cinnamic/Caffeic Esters and Amides as Radical Scavengers and 5-Lipoxygenase Inhibitors

    Directory of Open Access Journals (Sweden)

    Jérémie A. Doiron


    Full Text Available 5-Lipoxygenase (5-LO is the key enzyme responsible for the conversion of arachidonic acid to leukotrienes, a class of lipid mediators implicated in inflammatory disorders. In this paper, we describe the design, synthesis, and preliminary activity studies of novel clicked caffeic esters and amides as radical scavengers and 5-LO inhibitors. From known 5-LO inhibitor 3 as a lead, cinnamic esters 8a–h and amides 9a–h as well as caffeic esters 15a–h and amides 16a–h were synthesized by Cu(I-catalyzed [1,3]-dipolar cycloaddition with the appropriate azide precursors and terminal alkynes. All caffeic analogs are proved to be good radical scavengers (IC50: 10–20 μM. Esters 15g and 15f possessed excellent 5-LO inhibition activity in HEK293 cells and were equipotent with the known 5-LO inhibitor CAPE and more potent than Zileuton. Several synthesized esters possess activities rivaling Zileuton in stimulated human polymorphonuclear leukocytes.

  4. Acceleration effect of ionic liquids on polycyclotrimerization of dicyanate esters

    Directory of Open Access Journals (Sweden)

    A. Fainleib


    Full Text Available The polycyclotrimerization reaction of dicyanate ester of bisphenol E (DCBE in the presence of varying amounts (from 0.5 to 5 wt% of 1-octyl-3-methylimidazolium tetrafluoroborate ([OMIm][BF4] ionic liquid has been investigated using differential scanning calorimetry (DSC and Fourier transform infrared spectroscopy (FTIR techniques, after a curing stage at 150 °C for 6 h. It is noteworthy that an amount of [OMIm][BF4] as low as 0.5 wt% accelerates dramatically the thermal curing process leading to the formation of a polycyanurate network. The conversion of DCBE increased with increasing [OMIm][BF4] content in the temperature range studied. A reaction mechanism associated with the ionic liquid-catalyzed DCBE polycyclotrimerization is newly proposed via the involvement of a [CN]δ+–[OMIm]δ– complex as a key intermediate.

  5. Sinapate esters in brassicaceous plants: biochemistry, molecular biology, evolution and metabolic engineering. (United States)

    Milkowski, Carsten; Strack, Dieter


    Brassicaceous plants are characterized by a pronounced metabolic flux toward sinapate, produced by the shikimate/phenylpropanoid pathway, which is converted into a broad spectrum of O-ester conjugates. The abundant sinapate esters in Brassica napus and Arabidopsis thaliana reflect a well-known metabolic network, including UDP-glucose:sinapate glucosyltransferase (SGT), sinapoylglucose:choline sinapoyltransferase (SCT), sinapoylglucose:L-malate sinapoyltransferase (SMT) and sinapoylcholine (sinapine) esterase (SCE). 1-O-Sinapoylglucose, produced by SGT during seed development, is converted to sinapine by SCT and hydrolyzed by SCE in germinating seeds. The released sinapate feeds via sinapoylglucose into the biosynthesis of sinapoylmalate in the seedlings catalyzed by SMT. Sinapoylmalate is involved in protecting the leaves against the deleterious effects of UV-B radiation. Sinapine might function as storage vehicle for ready supply of choline for phosphatidylcholine biosynthesis in young seedlings. The antinutritive character of sinapine and related sinapate esters hamper the use of the valuable seed protein of the oilseed crop B. napus for animal feed and human nutrition. Due to limited variation in seed sinapine content within the assortment of B. napus cultivars, low sinapine lines cannot be generated by conventional breeding giving rise to genetic engineering of sinapate ester metabolism as a promising means. In this article we review the progress made throughout the last decade in identification of genes involved in sinapate ester metabolism and characterization of the encoded enzymes. Based on gene structures and enzyme recruitment, evolution of sinapate ester metabolism is discussed. Strategies of targeted metabolic engineering, designed to generate low-sinapate ester lines of B. napus, are evaluated.

  6. Molecular Structures of the Products of a Diphosphonate Ester Building Block with Lewis Bases

    Directory of Open Access Journals (Sweden)

    Yufeng Li


    Full Text Available By treating a suitable Wittig reagent under acid conditions, the phosphonate ester 1,4-bimethylenebenzene phosphonate ethyl ester (H2[BBPE], 1 was obtained. As a building block, compound 1 has been reacted with the Lewis-base N,N-dimethylpiperazine, ammonia and NaOH yielded compounds 2–4. The crystal structures show that a 1D chain forming a tubular channel is constructed through hydrogen bonds in 1; hydrogen bonds form two 1D chains with left-hand and right-hand helixes and form 3D networks in compound 2; 1D hydrogen-bond chains are further connected together to afford a 3D network architecture in compound 3; the phosphonate is coordinated by two Na atoms which present different coordination environments in compound 4. Additionally, the relationships between the structure and fluorescence of the four compounds in the solid state and in different solvents have also been studied at room temperature.

  7. Gold-catalyzed formation of pyrrolo- and indolo-oxazin-1-one derivatives: The key structure of some marine natural products


    Sultan Taskaya; Nurettin Menges; Metin Balci


    Various N-propargylpyrrole and indolecarboxylic acids were efficiently converted into 3,4-dihydropyrrolo- and indolo-oxazin-1-one derivatives by a gold(III)-catalyzed cyclization reaction. Some of the products underwent TFA-catalyzed double bond isomerization and some did not. Cyclization reactions in the presence of alcohol catalyzed by Au(I) resulted in the formation of hemiacetals after cascade reactions.

  8. Gold-catalyzed formation of pyrrolo- and indolo-oxazin-1-one derivatives: The key structure of some marine natural products

    Directory of Open Access Journals (Sweden)

    Sultan Taskaya


    Full Text Available Various N-propargylpyrrole and indolecarboxylic acids were efficiently converted into 3,4-dihydropyrrolo- and indolo-oxazin-1-one derivatives by a gold(III-catalyzed cyclization reaction. Some of the products underwent TFA-catalyzed double bond isomerization and some did not. Cyclization reactions in the presence of alcohol catalyzed by Au(I resulted in the formation of hemiacetals after cascade reactions.

  9. Sesquiterpene Esters from Salvia roborowskii

    Institute of Scientific and Technical Information of China (English)

    Ya LI; Ning LOU; Yan Qi WU; Xian Feng LIN; Yu LI


    Two new sesquiterpene esters, 3β, 6β, 8α-triacetyl-4β, 5α-epoxy -1- oxogermacr-10(14)-ene (1) and 3β, 6β, 8α-triacetyl-4β, 5α-epoxygermacr-1(10)-ene (2) were isolated from the whole plant of Salvia roborowskii Maxim. Their structures were elucidated by means of spectral data (2DNMR and HRMS).

  10. Diastereoselective B(C6F5)3-Catalyzed Reductive Carbocyclization of Unsaturated Carbohydrates. (United States)

    Bender, Trandon A; Dabrowski, Jennifer A; Zhong, Hongyu; Gagné, Michel R


    A B(C6F5)3-catalyzed method for the selective conversion of unsaturated carbohydrates to cyclopentanes and cyclopropanes is disclosed. Catalyst activation of tertiary silanes generates the ion pair [(C6F5)3B-H][ROSi2] whose components synergistically activate C-O bonds for diastereoselective C-C bond formation. Sila-THF cations are invoked as key intermediates facilitating carbocyclizations. Complex chiral synthons are thereby obtained in a single pot.

  11. A tandem Mannich addition–palladium catalyzed ring-closing route toward 4-substituted-3(2H-furanones

    Directory of Open Access Journals (Sweden)

    Jubi John


    Full Text Available A facile route towards highly functionalized 3(2H-furanones via a sequential Mannich addition–palladium catalyzed ring closing has been elaborated. The reaction of 4-chloroacetoacetate esters with imines derived from aliphatic and aromatic aldehydes under palladium catalysis afforded 4-substituted furanones in good to excellent yields. 4-Hydrazino-3(2H-furanones could also be synthesized from diazo esters in excellent yields by utilising the developed strategy. We could also efficiently transform the substituted furanones to aza-prostaglandin analogues.

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

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


    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

  13. Rh(III)-Catalyzed C-C/C-N Coupling of Imidates with α-Diazo Imidamide: Synthesis of Isoquinoline-Fused Indoles. (United States)

    Wang, He; Li, Lei; Yu, Songjie; Li, Yunyun; Li, Xingwei


    Imidate esters and diazo compounds have been established as bifunctional substrates for the construction of biologically active fused heterocycles via rhodium-catalyzed C-H activation and C-C/C-N coupling. This reaction occurs under mild conditions with high efficiency, step economy, and low catalyst loading. PMID:27280947

  14. Retinyl ester hydrolysis and retinol efflux from BFC-1beta adipocytes. (United States)

    Wei, S; Lai, K; Patel, S; Piantedosi, R; Shen, H; Colantuoni, V; Kraemer, F B; Blaner, W S


    Adipose tissue is an important storage depot for retinol, but there are no data regarding retinol mobilization from adipose stores. To address this, dibutyryl cAMP was provided to murine BFC-1beta adipocytes and its effects on retinol efflux assessed. High performance liquid chromatography analysis of retinol and retinyl esters in adipocytes and media indicated that cAMP stimulated, in a time- and dose-dependent manner, retinol accumulation in the culture media and decreased cellular retinyl ester concentrations. Study of adipocyte retinol-binding protein synthesis and secretion indicated that cAMP-stimulated retinol efflux into the media did not result from increased retinol-retinol-binding protein secretion but was dependent on the presence of fetal bovine serum in the culture media. Since our data suggested that retinyl esters can be hydrolyzed by a cAMP-dependent enzyme like hormone-sensitive lipase (HSL), in separate studies, we purified a HSL-containing fraction from BFC-1beta adipocytes and demonstrated that it catalyzed retinyl palmitate hydrolysis. Homogenates of Chinese hamster ovary cells overexpressing HSL catalyzed retinyl palmitate hydrolysis in a time-, protein-, and substrate-dependent manner, with an apparent Km for retinyl palmitate of 161 microM, whereas homogenates from control Chinese hamster ovary cells did not.

  15. Organocatalytic Asymmetric Michael Addition of 4-Hydroxycoumarin to β,γ-Unsaturated α-Keto Esters

    Energy Technology Data Exchange (ETDEWEB)

    Suh, Chang Won; Han, Tae Hyun; Kim, Dae Young [Soonchunhyang Univ., Asan (Korea, Republic of)


    In conclusion, we have developed organocatalytic enantioselective conjugate addition reaction of 4-hydroxycoumarin (1) to β,γ-unsaturated α-keto esters 2 to afford biologically valuable warfarin derivatives 3. The process is efficiently catalyzed by a binaphthyl-modified thiourea organocatalyst. The coumarin core is present as a characteristic structural motif in a large number of natural products and biologically active molecules.1 Particularly, many of these naturally occurring 4-hydroxycoumarin and their synthetic analogues are important precursors for the synthesis of natural products and pharmaceuticals. Enantioselective organocatalytic conjugate addition of 4-hydroxycoumarin to α,β-unsaturated ketones is a straightforward method to access warfarin which is an effective anticoagulants. Although a number of reactions of α,β-unsaturated ketones as Michael acceptors have been reported, the corresponding β,γ-unsaturated α-keto esters have received relatively little attention as Michael acceptors. Recently, several groups have reported the asymmetric Michael addition of 4-hydroxycoumarin to β,γ-unsaturated α-keto esters catalyzed by Cu(II)-bisoxazoline, N,N'-dioxide-Ni(II) complexes, thiourea catalysts. Although several efficient methods have been achieved by these systems, an effective method for the synthesis of warfarin analogues is still a challenge.

  16. Computational probes into the conceptual basis of silver ion chromatography: I. Silver(I) ion complexes of unsaturated fatty acids and esters

    NARCIS (Netherlands)

    Damyanova, B.; Momtchilova, S.; Bakalova, S.; Zuilhof, H.; Christie, W.W.; Kaneti, J.


    Silver ion chromatography of unsaturated fatty acid derivatives can be described satisfactorily by the suggestion of Ag(I) complexation with more than a single bonding site of esters of the 18:1, 18:2, etc. series (that is, one, two, etc. methylene-interrupted double bonds in the C18 hydrocarbon cha

  17. Access to Isoquinolines and Isoquinolin-3-ols via Rh(III)-Catalyzed Coupling/Cyclization Cascade Reaction of Arylimidates and Diazo Compounds. (United States)

    Li, Xing Guang; Sun, Min; Jin, Qiao; Liu, Kai; Liu, Pei Nian


    A Rh(III)-catalyzed coupling/cyclization cascade reaction is described, which involves arylimidates and diazo compounds and proceeds via intermolecular C-C bond formation and subsequent intramolecular C-N bond formation. Mechanistic investigation revealed that the reaction is a two-step process: the initial Rh(III)-catalyzed coupling/cyclization proceeds very fast and the following dehydration is rather slow. The reaction provides a direct approach to isoquinolines and isoquinolin-3-ols without any oxidants. PMID:27042947

  18. Stereoselectivity in (Acyloxy)borane-Catalyzed Mukaiyama Aldol Reactions. (United States)

    Lee, Joshua M; Zhang, Xin; Norrby, Per-Ola; Helquist, Paul; Wiest, Olaf


    The origin of diastereo- and enantioselectivity in a Lewis acid-catalyzed Mukaiyama aldol reaction is investigated using a combination of dispersion corrected DFT calculations and transition state force fields (TSFF) developed using the quantum guided molecular mechanics (Q2MM) method. The reaction proceeds via a closed transition structure involving a nontraditional hydrogen bond that is 3.3 kJ/mol lower in energy than the corresponding open transition structure. The correct prediction of the diastereoselectivity of a Mukaiyama aldol reaction catalyzed by the conformationally flexible Yamamoto chiral (acyloxy) borane (CAB) requires extensive conformational sampling at the transition structure, which is achieved using a Q2MM-derived TSFF, followed by DFT calculations of the low energy conformational clusters. Finally, a conceptual model for the rationalization of the observed diastereo- and enantioselectivity of the reaction using a closed transition state model is proposed. PMID:27247023

  19. Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

    KAUST Repository

    Vummaleti, Sai V. C.


    Density functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pd]/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd center. © 2015 American Chemical Society.

  20. Radiochemical methods for studying lipase-catalyzed interesterification of lipids

    International Nuclear Information System (INIS)

    Reactions involving lipase-catalyzed interesterification of lipids, which are of commendable interest in biotechnology, have been monitored and assayed by radiochemical methods using 14C-labeled substrates. Medium chain (C12 plus C14) triacylglycerols were reacted in the presence of an immobilized lipase from Mucor miehei and hexane at 450C with methyl [1-14C]oleate, [1-14C]oleic acid, [carboxyl-14C]trioleoylglycerol, [1-14C]octadecenyl alcohol, and [U-14C]glycerol, each of known specific activity. The reactions were monitored and the rate of interesterification determined by radio thin layer chromatography from the incorporation of radioactivity into acyl moieties of triacylglycerols (from methyl oleate, oleic acid, and trioleoylglycerol), alkyl moieties of wax esters (from octadecenyl alcohol), and into glycerol backbone of monoacylglycerols and diacylglycerols (from glycerol). (orig.)

  1. Retinyl Ester Formation by Lecithin:Retinol Acyltransferase Is a Key Regulator of Retinoid Homeostasis in Mouse Embryogenesis* s


    Kim, Youn-Kyung; Wassef, Lesley; Hamberger, Leora; Piantedosi, Roseann; Palczewski, Krzysztof; Blaner, William S.; Quadro, Loredana


    The developing mammalian embryo is entirely dependent on the maternal circulation for its supply of retinoids (vitamin A and its metabolites). The mechanisms through which mammalian developing tissues maintain adequate retinoid levels in the face of suboptimal or excessive maternal dietary vitamin A intake have not been established. We investigated the role of retinyl ester formation catalyzed by lecithin:retinol acyltransferase (LRAT) in regulating retinoid homeostasis during embryogenesis. ...

  2. Regiospecific synthesis of new fatty N-acyl trihalomethylated pyrazoline derivatives from fatty acid methyl esters (FAMEs)

    Energy Technology Data Exchange (ETDEWEB)

    Beck, Paulo; Santos, Juliane M. dos; D' Oca, Marcelo G. M.; Piovesan, Luciana A., E-mail: [Universidade Federal do Rio Grande (UFRS), RS (Brazil). Escola de Quimica e Alimentos; Kuhn, Bruna L.; Moreira, Dayse N.; Flores, Alex F.C.; Martins, Marcos A.P. [Universidade Federal de Santa Maria (UFSM), RS (Brazil). Dept. de Quimica


    A series of new fatty N-acyl trihalomethylated pyrazoline derivatives from fatty acid methyl esters was synthesized by the cyclo condensation of respective fatty hydrazides with 4-alkoxy- 1,1,1-trial omethyl-3-alquen-2-ones. Efficient and regiospecific cyclizations catalyzed by BF{sub 3}-MeOH gave the desired products in good to excellent yields and at high purity. (author)

  3. Enantioselective copper catalyzed allylic alkylation using Grignard reagents; Applications in synthesis

    NARCIS (Netherlands)

    Zijl, Anthoni Wouter van


    Enantioselective copper catalyzed allylic alkylation is a powerful carbon-carbon bond forming reaction. In this thesis the development of a new catalyst for the use of Grignard reagents in this reaction is described. This catalyst is based on copper and the ligand Taniaphos. The high regio- and enan

  4. Palladium-Catalyzed Intermolecular Aerobic Annulation of o-Alkenylanilines and Alkynes for Quinoline Synthesis. (United States)

    Zheng, Jia; Li, Zun; Huang, Liangbin; Wu, Wanqing; Li, Jianxiao; Jiang, Huanfeng


    A new approach to construct 2,3-disubstituted quinolines is described via Pd-catalyzed oxidative cyclization of o-vinylanilines and alkynes with molecular oxygen. This transformation is supposed to undergo intermolecular amination of alkyne, insertion of the olefin, and oxidative cleavage of C-C bond sequence. PMID:27418021

  5. Regio- and Diasteroselectivity of Rhodium-catalyzed Ring Opening Reaction of Oxabenzonorbornadienes with Heteroatom Nucleophiles

    Institute of Scientific and Technical Information of China (English)


    A new rhodium catalyzed ring opening reaction of oxabenzonorbornadienes and its derivatives was described. This reaction forms a new carbon-nitrogen bond via an intermolecular allylic displacement of the bridgehead oxygen with a piperazine's derivatives, which proceeds with very high regioselectivity.

  6. Fe-Catalyzed Olefin Hydroamination with Diazo Compounds for Hydrazone Synthesis. (United States)

    Zheng, Jing; Qi, Jifeng; Cui, Sunliang


    A novel Fe-catalyzed olefin hydroamination with diazo compounds for accessing hydrazones has been developed. Diazo compounds are used as radical acceptors and can be trapped by the in situ generated alkyl radical toward C-N bond formation. The reaction conditions are mild, and the substrate scope is broad. Additionally, this hydroamination protocol is applicable for intramolecular reactions to construct diverse heterocycles.

  7. The role of backbone hydrogen bonds in the transition state for protein folding of a PDZ domain

    DEFF Research Database (Denmark)

    Pedersen, Søren W; Hultqvist, Greta; Strømgaard, Kristian;


    Backbone hydrogen bonds are important for the structure and stability of proteins. However, since conventional site-directed mutagenesis cannot be applied to perturb the backbone, the contribution of these hydrogen bonds in protein folding and stability has been assessed only for a very limited set...... of small proteins. We have here investigated effects of five amide-to-ester mutations in the backbone of a PDZ domain, a 90-residue globular protein domain, to probe the influence of hydrogen bonds in a β-sheet for folding and stability. The amide-to-ester mutation removes NH-mediated hydrogen bonds...

  8. Ester Tuiksoo. Proua Suhkru kibedad päevad / Ester Tuiksoo ; interv. Piret Tali

    Index Scriptorium Estoniae

    Tuiksoo, Ester, 1965-


    Põllumajandusminister Ester Tuiksoo, kellel peagi täitub ministri ametis aasta Euroopa Liidu suhkrutrahvist, maaettevõtlusest, põllumajandusest, Euroopa Liidu toetustest, ministri elu- ja teenistuskäigust. Lisa: Ester Tuiksoo

  9. 21 CFR 172.859 - Sucrose fatty acid esters. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sucrose fatty acid esters. 172.859 Section 172.859... CONSUMPTION Multipurpose Additives § 172.859 Sucrose fatty acid esters. Sucrose fatty acid esters identified...) Sucrose fatty acid esters are the mono-, di-, and tri-esters of sucrose with fatty acids and are...

  10. Synthesis and Structural Characterization of 1- and 2-Substituted Indazoles: Ester and Carboxylic Acid Derivatives

    Directory of Open Access Journals (Sweden)

    Isabel Bento


    Full Text Available A series of indazoles substituted at the N-1 and N-2 positions with ester-containing side chains -(CH2nCO2R of different lengths (n = 0-6, 9, 10 are described.Nucleophilic substitution reactions on halo esters (X(CH2nCO2R by 1H-indazole inalkaline solution lead to mixtures of N-1 and N-2 isomers, in which the N-1 isomerpredominates. Basic hydrolysis of the ester derivatives allowed the synthesis of thecorresponding indazole carboxylic acids. All compounds were fully characterised bymultinuclear NMR and IR spectroscopies, MS spectrometry and elemental analysis; theNMR spectroscopic data were used for structural assignment of the N-1 and N-2 isomers.The molecular structure of indazol-2-yl-acetic acid (5b was determined by X-raydiffraction, which shows a supramolecular architecture involving O2-H...N1intermolecular hydrogen bonds.

  11. Pinosylvin-Based Polymers: Biodegradable Poly(Anhydride-Esters) for Extended Release of Antibacterial Pinosylvin. (United States)

    Bien-Aime, Stephan; Yu, Weiling; Uhrich, Kathryn E


    Pinosylvin is a natural stilbenoid known to exhibit antibacterial bioactivity against foodborne bacteria. In this work, pinosylvin is chemically incorporated into a poly(anhydride-ester) (PAE) backbone via melt-condensation polymerization, and characterized with respect to its physicochemical and thermal properties. In vitro release studies demonstrate that pinosylvin-based PAEs hydrolytically degrade over 40 d to release pinosylvin. Pseudo-first order kinetic experiments on model compounds, butyric anhydride and 3-butylstilbene ester, indicate that the anhydride linkages hydrolyze first, followed by the ester bonds to ultimately release pinosylvin. An antibacterial assay shows that the released pinosylvin exhibit bioactivity, while in vitro cytocompatibility studies demonstrate that the polymer is noncytotoxic toward fibroblasts. These preliminary findings suggest that the pinosylvin-based PAEs can serve as food preservatives in food packaging materials by safely providing antibacterial bioactivity over extended time periods. PMID:27071713

  12. Ruthenium-Catalyzed meta-Selective C—H Bromination (United States)

    Teskey, Christopher J; Lui, Andrew Y W; Greaney, Michael F


    The first example of a transition-metal-catalyzed, meta-selective C–H bromination procedure is reported. In the presence of catalytic [{Ru(p-cymene)Cl2}2], tetrabutylammonium tribromide can be used to functionalize the meta C–H bond of 2-phenylpyridine derivatives, thus affording difficult to access products which are highly predisposed to further derivatization. We demonstrate this utility with one-pot bromination/arylation and bromination/alkenylation procedures to deliver meta-arylated and meta-alkenylated products, respectively, in a single step. PMID:26288217

  13. Ruthenium-Catalyzed meta-Selective C—H Bromination


    Teskey, Christopher J; Lui, Andrew Y W; Greaney, Michael F.


    The first example of a transition-metal-catalyzed, meta-selective C–H bromination procedure is reported. In the presence of catalytic [{Ru(p-cymene)Cl2}2], tetrabutylammonium tribromide can be used to functionalize the meta C–H bond of 2-phenylpyridine derivatives, thus affording difficult to access products which are highly predisposed to further derivatization. We demonstrate this utility with one-pot bromination/arylation and bromination/alkenylation procedures to deliver meta-arylated and...

  14. Iron-Catalyzed C-H Functionalization Processes. (United States)

    Cera, Gianpiero; Ackermann, Lutz


    Iron-catalyzed C-H activation has recently emerged as an increasingly powerful tool for the step-economical transformation of unreactive C-H bonds. Particularly, the recent development of low-valent iron catalysis has set the stage for novel C-H activation strategies via chelation assistance. The low-cost, natural abundance, and low toxicity of iron prompted its very recent application in organometallic C-H activation catalysis. An overview of the use of iron catalysis in C-H activation processes is summarized herein up to May 2016. PMID:27573499

  15. Iron-Catalyzed Hydroboration: Unlocking Reactivity through Ligand Modulation. (United States)

    Espinal-Viguri, Maialen; Woof, Callum R; Webster, Ruth L


    Iron-catalyzed hydroboration (HB) of alkenes and alkynes is reported. A simple change in ligand structure leads to an extensive change in catalyst activity. Reactions proceed efficiently over a wide range of challenging substrates including activated, unactivated and sterically encumbered motifs. Conditions are mild and do not require the use of reducing agents or other additives. Large excesses of borating reagent are not required, allowing control of chemo- and regioselectivity in the presence of multiple double bonds. Mechanistic insight reveals that the reaction is likely to proceed via a highly reactive iron hydride intermediate. PMID:27321704

  16. Cleavable ester linked magnetic nanoparticles for labeling of solvent exposed primary amine groups of peptides/proteins

    Directory of Open Access Journals (Sweden)

    Ujwal S. Patil


    Full Text Available Covalent labeling of solvent exposed amino acid residues using chemical reagents/crosslinkers followed by mass spectrometric analysis can be used to determine the solvent accessible amino acids of a protein. A variety of chemical reagents containing cleavable bonds were developed to label abundantly found lysine residues on the surface of protein. To achieve efficient separation of labeled peptides prior to mass spectrometric analysis, magnetic nanoparticles can be decorated with amino acid reactive functional groups and utilized for quick recovery of labeled peptides. [1] In this work, iron oxide magnetic nanoparticles (Fe3O4 MNPs were synthesized by thermal decomposition method and coated with silica (SiO2@Fe3O4 MNPs by reverse micro emulsion approach. The Fe3O4 MNPs and SiO2@Fe3O4 MNPs were characterized by TEM and XRD. The SiO2@Fe3O4 MNPs were further coated with amine groups and conjugated to N-hydroxysuccinimidyl (NHS ester groups via a cleavable ester bond. Fluorescence based qualitative analysis of ester linked NHS ester modified SiO2@Fe3O4 MNPs was performed to confirm the presence of NHS ester group. The active NHS ester sites on the surface of SiO2@Fe3O4 MNPs were determined by depletion approach and found to be 694 active sites per 1 mg of SiO2@Fe3O4 MNPs. Free amine groups of a small peptide, ACTH (4–11 were labeled by ester linked, NHS ester modified SiO2@Fe3O4 MNPs under physiological conditions. Superparamagnetic nature of SiO2@Fe3O4 MNPs allowed quick and efficient magnetic separation of labeled peptides from the solution. The ester bond was further cleaved to separate labeled peptides followed by mass spectrometric analysis. The ester linked, NHS ester modified SiO2@Fe3O4 MNPs introduced a mass shift of 115.09 Da on amine groups of ACTH (4–11, which was confirmed by mass spectrometry.

  17. Synthesis and characterization of functional elastomeric poly(ester amide) co-polymers. (United States)

    Jokhadze, G; Machaidze, M; Panosyan, H; Chu, C C; Katsarava, R


    A new family of random co-poly(ester amides)s (co-PEAs) having reactive pendant functional carboxylic acid groups were synthesized by co-polycondensation of di-p-toluenesulfonic acid salts of bis-(L-alpha-amino acid (L-leucine and/or L-phenylalanine)) alpha,omega-alkylene diesters with active diesters of dicarboxylic acids using di-p-toluenesulfonic acid salt of L-lysine benzyl ester as a co-monomer. The lateral benzyl ester groups in the L-lysine segment of co-PEAs were subsequently transformed into free COOH groups by catalytic hydrogenolysis using Pd black as a catalyst. The co-PEA-based polyacids obtained, as well as the original co-PEA having lateral benzyl ester groups were characterized by standard methods. In vitro biodegradation studies in the presence of hydrolases like alpha-chymotrypsin and lipase showed significant enzymatic-catalyzed biodegradation of these co-PEAs. These co-PEA-based polyacids were used for covalent attachment of iminoxyl radicals (4-amino-TEMPO) and in vitro biodegradation of 4-aminoTEMPO attached polymer was studied along with releasing kinetic of iminoxyl radical. PMID:17540117

  18. Regulation of ferulate-5-hydroxylase expression in Arabidopsis in the context of sinapate ester biosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Ruegger, M.; Meyer, K.; Cusumano, J.C.; Chapple, C. [Purdue Univ., West Lafayette, IN (United States). Dept. of Biochemistry


    Sinapic acid is an intermediate in syringyl lignin biosynthesis in angiosperms, and in some taxa serves as a precursor for soluble secondary metabolites. The biosynthesis and accumulation of the sinapate esters sinapoylglucose, sinapolymalate, and sinapolycholine are developmentally regulated in Arabidopsis and other members of the Brassicaceae. The FAH1 locus of Arabidopsis encodes the enzyme ferulate-5-hydroxylase (F5H), which catalyzes the rate-limiting step in syringyl lignin biosynthesis and is required for the production of sinapate esters. Here the authors show that F5H expression parallels sinapate ester accumulation in developing siliques and seedlings, but is not rate limiting for their biosynthesis. RNA gel-blot analysis indicated that the tissue-specific and developmentally regulated expression of F5H mRNA is distinct from that of other phenylpropanoid genes. Efforts to identify constructs capable of complementing the sinapate ester-deficient phenotype of fah1 mutants demonstrated that F5H expression in leaves is dependent on sequences 3{prime} of the F5H coding region. In contrast, the positive regulatory function of the downstream region is not required for F5H transcript or sinapolycholine accumulation in embryos.

  19. Ionic liquids as novel solvents for the synthesis of sugar fatty acid ester. (United States)

    Mai, Ngoc Lan; Ahn, Kihun; Bae, Sang Woo; Shin, Dong Woo; Morya, Vivek Kumar; Koo, Yoon-Mo


    Sugar fatty acid esters are bio-surfactants known for their non-toxic, non-ionic, and high biodegradability . With great emulsifying and conditioning effects, sugar fatty acids are widely used in the food, pharmaceutical, and cosmetic industries. Biosynthesis of sugar fatty acid esters has attracted growing attention in recent decades. In this study, the enzymatic synthesis of sugar fatty acid esters in ionic liquids was developed, optimized, and scaled up. Reaction parameters affecting the conversion yield of lipase-catalyzed synthesis of glucose laurate from glucose and vinyl laurate (i.e. temperature, vinyl laurate/glucose molar ratio, and enzyme loads) were optimized by response surface methodology (RSM). In addition, production was scaled up to 2.5 L, and recycling of enzyme and ionic liquids was investigated. The results showed that under optimal reaction conditions (66.86 °C, vinyl laurate/glucose molar ratio of 7.63, enzyme load of 73.33 g/L), an experimental conversion yield of 96.4% was obtained which is close to the optimal value predicted by RSM (97.16%). A similar conversion yield was maintained when the reaction was carried out at 2.5 L. Moreover, the enzymes and ionic liquids could be recycled and reused effectively for up to 10 cycles. The results indicate the feasibility of ionic liquids as novel solvents for the biosynthesis of sugar fatty acid esters.


    Directory of Open Access Journals (Sweden)

    N. Sampaio Neta


    Full Text Available Lipases are biocatalysts of great importance in different areas, being able to catalyze reactions in aqueous or organic media. Furthermore, these enzymes are capable of using several substrates being stable in a wide range of pH and temperatures. Lipases promote the esterification between fatty acids and ethanol producing oleate esters. The aim of this work is to produce ethyl oleate ester by enzymatic esterification of oleic acid with ethanol. A lipase from Candida antarctica type B was used at a temperature of 55 °C. The reaction was conducted using oleic acid, sodium sulfate anhydrous, lipase and ethanol, with a ratio of oleic acid (0.03 mol or 10 ml, lipase (0.1 mol or 0.01 g, sodium sulfate anhydrous (5 g and ethanol 99 % (100 ml. Several reaction times were studied, namely 48, 72, 96 and 120 hours. Nuclear Magnetic Resonance (1H and 13C and Infrared spectra confirmed the production of ethyl oleate ester for the studied conditions. The highest ethyl oleate production yield was obtained for 96 hours reaction time. Ethyl oleate esters have been reported to possess interesting applications in several industrial fields, such as food, aromatics, cosmetics, detergents, flavors and pharmaceuticals.

  1. Two-Step biocatalytic conversion of an ester to an aldehyde in reverse micelles. (United States)

    Yang, F; Russell, A J


    Lipases from Candida cyclindracea (L-1754) and wheat germ (L-3001) have been used to hydrolyze esters to their corresponding alcohols and acids in reverse micelles. Alcohol dehydrogenase from baker's yeast (YADH) was subsequently used to reduce the alcohol products to aldehydes. Cofactor recycling in the redox reaction was achieved using a sacrificial cosubstrate, as described previously. Four surfactants (sodium dioctylsulfosuccinate, Nonidet P-40 with Triton X-35, polyoxyethylene, 10-cetyl-ether, polyoxyethylene sorbitan trioleate) were employed to determine the effect of amphiphile on ester hydrolysis and redox reaction rates separately. The effect of type of organic solvent, W(0) [(water]/[surfactant)], and substrate concentration on separte enzyme activity were also investigated. A brief investigation of a single phase, two-step reaction catalyzed by the combination of lipase and YADH in reverse micelles is also reported. The activities of the enzymes are significantly different when used together instead of independently. (c) 1994 John Wiley & Sons, Inc.

  2. Development of Enantiospecific Coupling of Secondary and Tertiary Boronic Esters with Aromatic Compounds. (United States)

    Odachowski, Marcin; Bonet, Amadeu; Essafi, Stephanie; Conti-Ramsden, Philip; Harvey, Jeremy N; Leonori, Daniele; Aggarwal, Varinder K


    The stereospecific cross-coupling of secondary boronic esters with sp(2) electrophiles (Suzuki-Miyaura reaction) is a long-standing problem in synthesis, but progress has been achieved in specific cases using palladium catalysis. However, related couplings with tertiary boronic esters are not currently achievable. To address this general problem, we have focused on an alternative method exploiting the reactivity of a boronate complex formed between an aryl lithium and a boronic ester. We reasoned that subsequent addition of an oxidant or an electrophile would remove an electron from the aromatic ring or react in a Friedel-Crafts-type manner, respectively, generating a cationic species, which would trigger 1,2-migration of the boron substituent, creating the new C-C bond. Elimination (preceded by further oxidation in the former case) would result in rearomatization giving the coupled product stereospecifically. Initial work was examined with 2-furyllithium. Although the oxidants tested were unsuccessful, electrophiles, particularly NBS, enabled the coupling reaction to occur in good yield with a broad range of secondary and tertiary boronic esters, bearing different steric demands and functional groups (esters, azides, nitriles, alcohols, and ethers). The reaction also worked well with other electron-rich heteroaromatics and 6-membered ring aromatics provided they had donor groups in the meta position. Conditions were also found under which the B(pin)- moiety could be retained in the product, ortho to the boron substituent. This protocol, which created a new C(sp(2))-C(sp(3)) and an adjacent C-B bond, was again applicable to a range of secondary and tertiary boronic esters. In all cases, the coupling reaction occurred with complete stereospecificity. Computational studies verified the competing processes involved and were in close agreement with the experimental observations. PMID:27384259

  3. Development of Enantiospecific Coupling of Secondary and Tertiary Boronic Esters with Aromatic Compounds (United States)


    The stereospecific cross-coupling of secondary boronic esters with sp2 electrophiles (Suzuki–Miyaura reaction) is a long-standing problem in synthesis, but progress has been achieved in specific cases using palladium catalysis. However, related couplings with tertiary boronic esters are not currently achievable. To address this general problem, we have focused on an alternative method exploiting the reactivity of a boronate complex formed between an aryl lithium and a boronic ester. We reasoned that subsequent addition of an oxidant or an electrophile would remove an electron from the aromatic ring or react in a Friedel–Crafts-type manner, respectively, generating a cationic species, which would trigger 1,2-migration of the boron substituent, creating the new C–C bond. Elimination (preceded by further oxidation in the former case) would result in rearomatization giving the coupled product stereospecifically. Initial work was examined with 2-furyllithium. Although the oxidants tested were unsuccessful, electrophiles, particularly NBS, enabled the coupling reaction to occur in good yield with a broad range of secondary and tertiary boronic esters, bearing different steric demands and functional groups (esters, azides, nitriles, alcohols, and ethers). The reaction also worked well with other electron-rich heteroaromatics and 6-membered ring aromatics provided they had donor groups in the meta position. Conditions were also found under which the B(pin)- moiety could be retained in the product, ortho to the boron substituent. This protocol, which created a new C(sp2)–C(sp3) and an adjacent C–B bond, was again applicable to a range of secondary and tertiary boronic esters. In all cases, the coupling reaction occurred with complete stereospecificity. Computational studies verified the competing processes involved and were in close agreement with the experimental observations. PMID:27384259

  4. Ruthenium-Catalyzed Hydroalkynylative Cyclization of 1,6-Enynes Induced by Substituent Effects. (United States)

    Liu, Rui; Ni, Zhenjie; Giordano, Laurent; Tenaglia, Alphonse


    The ruthenium-catalyzed 1,6-enyne cyclization in the presence of bulky substituted terminal alkyne proceeds smoothly at room temperature to afford highly substituted five-membered cyclic compounds featuring a 1,5-enyne motif. Deuterium-labeling experiments showed that the key ruthenacyclopentene intermediate undergoes cleavage of metal-carbon bonds through the metal-assisted σ-bond metathesis reaction, thus leading to the formation of C(sp(2))-H and C(sp(3))-C(sp) bonds. PMID:27504966

  5. Synthesis of insecticidal sucrose esters

    Institute of Scientific and Technical Information of China (English)

    Song Zi-juan; Li Shu-jun; Chen Xi; Liu Li-mei; Song Zhan-qian


    Some synthetic sucrose esters (SE) are a relatively new class of insecticidal compounds produced by reacting sugars with fatty acids, which are safe for the environment. Especially, sucrose esters composed of C6-C12 fatty acids have desirable insecticidal properties against many soft-bodied arthropod pests. In our study, sucrose octanoate which has the highest activity against a range of arthropod species was synthesized by a trans-esterification method and proved its insecticidal property. Under the condition of a homogeneous liquid, sucrose octanoate was prepared by reacting ethyl octanoate with sucrose at reduced pressure; the yield was 79.11%. Sucrose octanoate synthesized was identified and its property analyzed by IR, TLC and spectrophotometric analysis. It was shown that the ratio of monoester to polyester in sucrose octanoate was 1.48:1. The insecticidal activity of the synthetic sucrose octanoate was evaluated at a concentration of 4 and 8 mg·mL-1. The mortality of first-instar larvae ofLymantria dispar from its contact toxicity was 72.5% after 36 hours, the revision insect reduced rate of Aphis glycines reached above 80% at 4 and 8 mg·mL-1 after being treated for 5 days. Since the SE products are nontoxic to humans and higher animals, fully biodegradable and hydrolyzed to readily metabolizable sucrose and fatty acid, they are not harmful to crops and appear to be good insecticide candidates.

  6. Sorption of organophosphate esters by carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Wei; Yan, Li [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Duan, Jinming [School of Environmental and Municipal Engineering, Xi’an University of Architecture and Technology, Xi’an 710055 (China); Jing, Chuanyong, E-mail: [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China)


    Graphical abstract: The interfacial interactions between the OPE molecules and CNTs. - Highlights: • Oxygen-containing groups on CNTs change the sorption property for OPEs. • Molecular configuration of OPEs has insignificant impact on their sorption. • Hydrophobic, π–π EDA and Brønsted acid–base interaction occurred between the CNTs and OPEs. - Abstract: Insights from the molecular-level mechanism of sorption of organophosphate esters (OPEs) on carbon nanotubes (CNTs) can further our understanding of the fate and transport of OPEs in the environment. The motivation for our study was to explore the sorption process of OPEs on multi-walled CNTs (MWCNTs), single-walled CNTs (SWCNTs) and their oxidized counterparts (O-MWCNTs and O-SWCNTs), and its molecular mechanism over a wide concentration range. The sorption isotherm results revealed that the hydrophobicity of OPEs dominated their affinities on a given CNT and the π–π electron donor–acceptor (EDA) interaction also played an important role in the sorption of aromatic OPEs. This π–π EDA interaction, verified with Raman and FT-IR spectroscopy, could restrict the radial vibration of SWCNTs and affect the deformation vibration γ(CH) bands of OPE molecules. The OPE surface coverage on CNTs, estimated using the nonlinear Dubinin–Ashtakhov model, indicated that the oxygen-containing functional groups on CNTs could interact with water molecules by H-bonding, resulting in a decrease in effective sorption sites. In addition, FTIR analysis also confirmed the occurrence of Brønsted acid–base interactions between OPEs and surface OH groups of SWCNTs. Our results should provide mechanistic insights into the sorption mechanism of OPE contaminants on CNTs.

  7. Synthesis and Biological Evaluation of a Valinomycin Analog Bearing a Pentafluorophenyl Active Ester Moiety. (United States)

    D'Accolti, Lucia; Denora, Nunzio; La Piana, Gianluigi; Marzulli, Domenico; Siwy, Zuzanna S; Fusco, Caterina; Annese, Cosimo


    A valuable analog of the K(+)-ionophore valinomycin (1), bearing a pentafluorophenyl ester moiety, has been obtained by selective reaction between the tertiary hydroxyl moiety of analog 2 (available from valinomycin hydroxylation) and the isocyanate group of pentafluorophenyl N-carbonyl glycinate (3) catalyzed by bis(N,N-dimethylformamide)dichlorodioxomolybdenum(VI). LC-HRMS studies show that analog 4 undergoes easy derivatization under mild conditions by reaction with OH- and NH2-containing compounds. Mitochondrial depolarization assays suggest that 4 acts as a K(+)-ionophore, provided that the glycine carboxyl group is appropriately masked. PMID:26566090

  8. Physio-pathological roles of transglutaminase-catalyzed reactions

    Institute of Scientific and Technical Information of China (English)

    Mariangela; Ricotta; Maura; Iannuzzi; Giulia; De; Vivo; Vittorio; Gentile


    Transglutaminases(TGs) are a large family of related and ubiquitous enzymes that catalyze post-translational modifications of proteins.The main activity of these enzymes is the cross-linking of a glutaminyl residue of a protein/peptide substrate to a lysyl residue of a protein/peptide co-substrate.In addition to lysyl residues,other second nucleophilic co-substrates may include monoamines or polyamines(to form mono-or bi-substituted/crosslinked adducts) or-OH groups(to form ester linkages) .In the absence of co-substrates,the nucleophile may be water,resulting in the net deamidation of the glutaminyl residue.The TG enzymes are also capable of catalyzing other reactions important for cell viability.The distribution and the physiological roles of TG enzymes have been widely studied in numerous cell types and tissues and their roles in several diseases have begun to be identified."Tissue" TG(TG2) ,a member of the TG family of enzymes,has definitely been shown to be involved in the molecular mechanisms responsible for a very widespread human pathology:i.e.celiac disease(CD) .TG activity has alsobeen hypothesized to be directly involved in the pathogenetic mechanisms responsible for several other human diseases,including neurodegenerative diseases,which are often associated with CD.Neurodegenerative diseases,such as Alzheimer’s disease,Parkinson’s disease,supranuclear palsy,Huntington’s disease and other recently identified polyglutamine diseases,are characterized,in part,by aberrant cerebral TG activity and by increased cross-linked proteins in affected brains.In this review,we discuss the physio-pathological role of TG-catalyzed reactions,with particular interest in the molecular mechanisms that could involve these enzymes in the physio-pathological processes responsible for human neurodegenerative diseases.

  9. Novel and highly efficient regioselective route to helicid esters by lipozyme TLL.

    Directory of Open Access Journals (Sweden)

    Rongling Yang

    Full Text Available Highly regioselective acylation of helicid with fatty acid vinyl esters catalyzed by the lipase from Thermomyces lanuginosus has been successfully performed for the first time. For the enzymatic caproylation of helicid, under the optimal conditions, initial reaction rate was 33.2 mM/h, and substrate conversion and regioselectivity were greater than 99%. In addition, the acyl recognition of the enzyme in the regioselective acylation of helicid was investigated. The results showed that although 6'-O-acyl derivatives of helicid were exclusively obtained with all the tested acyl donors, the enzymatic reaction rate varied widely with different acyl donors, presumably owing to their different interactions with the active site of the lipase. It is also interesting that the different configuration of only one hydroxyl group at C-3 in helicid couldn't affect the lipase-catalyzed esterification and helicid has the same regioselectivity as that of D-glucose and arbutin.

  10. Esteróles en esponjas marinas

    Directory of Open Access Journals (Sweden)

    Carmenza Duque


    Full Text Available Esta revisión bibliográfica comprende la mayona del trabajo publicado hasta el momento sobre esteróles aislados de esponjas marinas. Estos esteróles comprenden compuestos desde Cig hasta C31 con estructuras convencionales y con estructuras novedosas (núcleo y/o cadena lateral no convencional.

  11. Ligand-Promoted Borylation of C(sp(3))-H Bonds with Palladium(II) Catalysts. (United States)

    He, Jian; Jiang, Heng; Takise, Ryosuke; Zhu, Ru-Yi; Chen, Gang; Dai, Hui-Xiong; Dhar, T G Murali; Shi, Jun; Zhang, Hao; Cheng, Peter T W; Yu, Jin-Quan


    A quinoline-based ligand effectively promotes the palladium-catalyzed borylation of C(sp(3))-H bonds. Primary β-C(sp(3))-H bonds in carboxylic acid derivatives as well as secondary C(sp(3))-H bonds in a variety of carbocyclic rings, including cyclopropanes, cyclobutanes, cyclopentanes, cyclohexanes, and cycloheptanes, can thus be borylated. This directed borylation method complements existing iridium(I)- and rhodium(I)-catalyzed C-H borylation reactions in terms of scope and operational conditions. PMID:26611496

  12. Acid-catalyzed conversion of mono- and poly-sugars into platform chemicals: effects of molecular structure of sugar substrate. (United States)

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


    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

  13. Synthesis and intrinsic blue fluorescence study of hyperbranched poly(ester-amide-ether)

    Institute of Scientific and Technical Information of China (English)


    A series of hyperbranched poly(ester-amide-ether)s (H-PEAEs) were synthesized via the A2+CB3 approach by the self-transesterification of ethyl ester-amide-ethers end-capped with three hydroxyl groups and ethyl ester group at two terminals.The molecular structures were characterized with 1H NMR and FT-IR spectroscopy.The number average molecular weights were estimated by GPC analysis to possess bimodal wide distribution from 1.57 to 2.09.The strong inherent blue fluorescence was observed at 330 nm for excitation and 390 nm for emission.Moreover,the emission intensity and fluorescence quantum yield increased along with the incorporated ether chain length,as well as almost linearly with the H-PEAE concentration in an aqueous solution.For comparing the fluorescence performance,the linear poly(ester-amide-ether) (L-PEAE) and hyperbranched poly(ester-amide) (H-PEA) were synthesized.The results showed that the coexistence of ether bond and carboxyl group in the molecular chain was essential for generating the strong fluorescence.However,the compact backbone of H-PEAE would be propitious to the enhancement of fluorescence properties.

  14. Plasma Cholesterol Ester Fatty Acids: A New Biochemical Abnormality in Obstructive Jaundice


    Scriven, M. W.; Horrobin, D. F.; Puntis, M. C. A.


    Changes in fatty acid patterns may explain many of the observed abnormalities found in obstructive jaundice. This study looked at fatty acids in plasma cholesterol esters, in a group of patients with obstructive jaundice and a matched group of controls. Significant abnormalities were demonstrated, most importantly a fall in essential fatty acids, in the jaundiced group. Overall the saturation of this fraction, as assessed by double bond index, rose. The essential fatty acids ar...

  15. Asymmetric Stetter reactions catalyzed by thiamine diphosphate-dependent enzymes. (United States)

    Kasparyan, Elena; Richter, Michael; Dresen, Carola; Walter, Lydia S; Fuchs, Georg; Leeper, Finian J; Wacker, Tobias; Andrade, Susana L A; Kolter, Geraldine; Pohl, Martina; Müller, Michael


    The intermolecular asymmetric Stetter reaction is an almost unexplored transformation for biocatalysts. Previously reported thiamine diphosphate (ThDP)-dependent PigD from Serratia marcescens is the first enzyme identified to catalyze the Stetter reaction of α,β-unsaturated ketones (Michael acceptor substrates) and α-keto acids. PigD is involved in the biosynthesis of the potent cytotoxic agent prodigiosin. Here, we describe the investigation of two new ThDP-dependent enzymes, SeAAS from Saccharopolyspora erythraea and HapD from Hahella chejuensis. Both show a high degree of homology to the amino acid sequence of PigD (39 and 51 %, respectively). The new enzymes were heterologously overproduced in Escherichia coli, and the yield of soluble protein was enhanced by co-expression of the chaperone genes groEL/ES. SeAAS and HapD catalyze intermolecular Stetter reactions in vitro with high enantioselectivity. The enzymes possess a characteristic substrate range with respect to Michael acceptor substrates. This provides support for a new type of ThDP-dependent enzymatic activity, which is abundant in various species and not restricted to prodigiosin biosynthesis in different strains. Moreover, PigD, SeAAS, and HapD are also able to catalyze asymmetric carbon-carbon bond formation reactions of aldehydes and α-keto acids, resulting in 2-hydroxy ketones.

  16. Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

    Directory of Open Access Journals (Sweden)

    Masato Ohashi


    Full Text Available In this review, we summarize our recent development of palladium(0-catalyzed cross-coupling reactions of perfluoro organic compounds with organometallic reagents. The oxidative addition of a C–F bond of tetrafluoroethylene (TFE to palladium(0 was promoted by the addition of lithium iodide, affording a trifluorovinyl palladium(II iodide. Based on this finding, the first palladium-catalyzed cross-coupling reaction of TFE with diarylzinc was developed in the presence of lithium iodide, affording α,β,β-trifluorostyrene derivatives in excellent yield. This coupling reaction was expanded to the novel Pd(0/PR3-catalyzed cross-coupling reaction of TFE with arylboronates. In this reaction, the trifluorovinyl palladium(II fluoride was a key reaction intermediate that required neither an extraneous base to enhance the reactivity of organoboronates nor a Lewis acid additive to promote the oxidative addition of a C–F bond. In addition, our strategy utilizing the synergetic effect of Pd(0 and lithium iodide could be applied to the C–F bond cleavage of unreactive hexafluorobenzene (C6F6, leading to the first Pd(0-catalyzed cross-coupling reaction of C6F6 with diarylzinc compounds.

  17. Cross Shear Roll Bonding

    DEFF Research Database (Denmark)

    Bay, Niels; Bjerregaard, Henrik; Petersen, Søren. B;


    The present paper describes an investigation of roll bonding an AlZn alloy to mild steel. Application of cross shear roll bonding, where the two equal sized rolls run with different peripheral speed, is shown to give better bond strength than conventional roll bonding. Improvements of up to 20......-23% in bond strength are found and full bond strength is obtained at a reduction of 50% whereas 65% is required in case of conventional roll bonding. Pseudo cross shear roll bonding, where the cross shear effect is obtained by running two equal sized rolls with different speed, gives the same results....

  18. Antifungal properties of halofumarate esters. (United States)

    Gershon, H; Shanks, L


    Alkyl esters (C1--C4) of the four halofumaric acids were tested for antifungal activity against Candida albicans, Aspergillus niger, Mucor mucedo, and Trichophyton mentagrophytes at pH 5.6 and 7.0 in the absence and presence of 10% beef serum in Sabouraud dextrose agar. The most toxic compound to each organism was: C. albicans, ethyl iodofumarate (0.054 mmole/liter); A. niger, methyl bromofumarate (0.090 mmole/liter); M. mucedo, methyl fluorofumarate (0.037 mmole/liter); and T. mentagrophytes, ethyl iodofumarate (0.020 mmole/liter). The order of overall activity of the six most toxic compounds was: ethyl iodofumarate greater than ethyl chlorofumarate greater than methyl iodofumarate = methyl bromofumarate greater than methyl chlorofumarate greater than bromofumarate.

  19. A New Paradigm for Carbon-Carbon Bond Formation: Aerobic, Copper-Templated Cross-Coupling


    Villalobos, Janette M.; Srogl, Jiri; Liebeskind, Lanny S.


    Thiol esters and boronic acids react to produce ketones under aerobic conditions in the presence of catalytic quantities of a CuI or CuII salt. The reaction occurs at reasonable rates between room temperature and 50 °C at neutral pH using thiol esters derived from bulky 2° amides of thiosalicylamides such as those based on N-tert-butyl-2-mercaptobenzamide. In this mechanistically unprecedented reaction system the carbon-carbon bond formation occurs through templating of the thiol ester and th...

  20. Characterization, quantitation and evolution of monoepoxy compounds formed in model systems of fatty acid methyl esters and monoacid triglycerides heated at high temperature

    Directory of Open Access Journals (Sweden)

    Berdeaux, O.


    Full Text Available Monoepoxy compounds formed after heating methyl oleate and linoleate, triolein and trilinolein at 180°C for 5, 10 and 15 hours, were characterized and quantitated after derivatization to fatty acid methyl esters by using two base-catalyzed procedures. Structures were identified by GC-MS before and after hydrogénation. A complete recovery of the epoxy compounds was obtained by comparing results from methyl oleate and linoleate before and after transesterification, and good repeatability was also attained. Similar amounts of epoxides were found for methyl esters and triglycerides of the same degree of unsaturation, although formation was considerably greater for the less unsaturated substrates, methyl oleate and triolein, possibly due to the absence of remaining double bonds in the molecule which would involve a lower tendency to participate in further reactions. On other hand, independently of the degree of unsaturation of the model systems and of the period of heating, significantly higher amounts of trans isomers were formed. Finally from comparison between the amounts of epoxides and the level of polar fatty acids in samples, it was deduced that monoepoxy compounds were one of the major groups formed under the conditions used.

    En este estudio se identifican y cuantifican los compuestos epoxidados formados a partir de sistemas modelo de oleato y linoleato de metilo, trioleína y trilinoleína, calentados a 180°C durante 5,10 y 15 horas. La identificación se lleva a cabo mediante CG-EM en las muestras de esteres metílicos antes y después de someter a hidrogenación y para su cuantificación se utilizan dos procedimientos de transesterificación en medio alcalino. La comparación de las cantidades obtenidas, antes y después de la derivatización de los sistemas modelo de esteres metílicos, permitió deducir que la recuperación fue completa, obteniéndose también una excelente repetibilidad. Las cantidades de ep

  1. Synthesis of benzofuranyl and indolyl methyl azides by tandem silver-catalyzed cyclization and azidation. (United States)

    Ranjith Kumar, Gadi; Kiran Kumar, Yalla; Kant, Ruchir; Sridhar Reddy, Maddi


    Ag(i)-catalyzed synthesis of 2-azidomethyl benzofurans/indoles from linear and readily available hydroxyl/amino-phenyl propargyl alcohols is described via a highly regioselective C-O and C-N bond formation. Control experiments reveal that the reaction involves the sequential Ag(i)-catalyzed 5-exo-dig cyclization and a catalyst free γ-allylic azidation. The synthetic utility of this method has been demonstrated by using the azidomethyl unit of the above synthesized heterocycles as the base for a variety of other functionalizations, such as triazole-, tetrazole-, amide-, amine-, and pyrido-derivatives. PMID:27064507

  2. Wire bonding in microelectronics

    CERN Document Server

    Harman, George G


    Wire Bonding in Microelectronics, Third Edition, has been thoroughly revised to help you meet the challenges of today's small-scale and fine-pitch microelectronics. This authoritative guide covers every aspect of designing, manufacturing, and evaluating wire bonds engineered with cutting-edge techniques. In addition to gaining a full grasp of bonding technology, you'll learn how to create reliable bonds at exceedingly high yields, test wire bonds, solve common bonding problems, implement molecular cleaning methods, and much more. Coverage includes: Ultrasonic bonding systems and technologies, including high-frequency systems Bonding wire metallurgy and characteristics, including copper wire Wire bond testing Gold-aluminum intermetallic compounds and other interface reactions Gold and nickel-based bond pad plating materials and problems Cleaning to improve bondability and reliability Mechanical problems in wire bonding High-yield, fine-pitch, specialized-looping, soft-substrate, and extreme-temperature wire bo...

  3. Bioreversible Derivatives of Phenol. 2. Reactivity of Carbonate Esters with Fatty Acid-like Structures Towards Hydrolysis in Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Claus Larsen


    Full Text Available A series of model phenol carbonate ester prodrugs encompassing derivatives with fatty acid-like structures were synthesized and their stability as a function of pH (range 0.4 – 12.5 at 37°C in aqueous buffer solutions investigated. The hydrolysis rates in aqueous solutions differed widely, depending on the selected pro-moieties (alkyl and aryl substituents. The observed reactivity differences could be rationalized by the inductive and steric properties of the substituent groups when taking into account that the mechanism of hydrolysis may change when the type of pro-moiety is altered, e.g. n-alkyl vs. t-butyl. Hydrolysis of the phenolic carbonate ester 2-(phenoxycarbonyloxy-acetic acid was increased due to intramolecular catalysis, as compared to the derivatives synthesized from ω-hydroxy carboxylic acids with longer alkyl chains. The carbonate esters appear to be less reactive towards specific acid and base catalyzed hydrolysis than phenyl acetate. The results underline that it is unrealistic to expect that phenolic carbonate ester prodrugs can be utilized in ready to use aqueous formulations. The stability of the carbonate ester derivatives with fatty acid-like structures, expected to interact with the plasma protein human serum albumin, proved sufficient for further in vitro and in vivo evaluation of the potential of utilizing HSA binding in combination with the prodrug approach for optimization of drug pharmacokinetics.

  4. Kinetics of the Esterification Reaction between Pentanoic Acid and Methanol Catalyzed by Noncorrosive Cation Exchange Resin


    Sharma, M.; Toor, A. P.; R. K. Wanchoo


    Methyl pentanoate, commonly known as methyl valerate, is the methyl ester of pentanoic acid (valeric acid) with a fruity odour. Methyl pentanoate is commonly used in fragrances, beauty care, soap, laundry detergents at levels of 0.1 – 1 %. In its very pure form (purity 99.5 %) it is used as a plasticizer in the manufacture of plastics. In the present investigation, kinetics of esterification of pentanoic acid with methanol catalyzed by heterogeneous catalyst in a batch-type reactor is reporte...

  5. Enzyme-Catalyzed Modifications of Polysaccharides and Poly(ethylene glycol

    Directory of Open Access Journals (Sweden)

    H. N. Cheng


    Full Text Available Polysaccharides are used extensively in various industrial applications, such as food, adhesives, coatings, construction, paper, pharmaceuticals, and personal care. Many polysaccharide structures need to be modified in order to improve their end-use properties; this is mostly done through chemical reactions. In the past 20 years many enzyme-catalyzed modifications have been developed to supplement chemical derivatization methods. Typical reactions include enzymatic oxidation, ester formation, amidation, glycosylation, and molecular weight reduction. These reactions are reviewed in this paper, with emphasis placed on the work done by the authors. The polymers covered in this review include cellulosic derivatives, starch, guar, pectin, and poly(ethylene glycol.

  6. [Development of novel methods for synthesis of heterocyclic compounds catalyzed by transition metals in fluorinated alcohols]. (United States)

    Saito, Akio


    New possibilities for catalytic syntheses of lactone derivatives and nitrogen-containing heterocyclic compounds in fluorinated alcohols are described. The cationic Rh(I) catalyst in fluorinated alcohol solvents (hexafluoroisopropanol: HFIP, trifluoroethanol: TFE) brought about not only mild cycloaddition reactions of ester-tethered compounds but also a facile formation of indole derivatives by the aromatic amino-Claisen rearrangement of N-propargyl aniline derivatives. The use of HFIP as an additive exerted a remarkable effect on the Pictet-Spengler reaction catalyzed by the fluorinated surfactant-combined Brønsted acid catalyst in water.

  7. Mechanistic Study of the sPLA2 Mediated Hydrolysis of a Thio-ester Pro Anticancer Ether Lipid

    DEFF Research Database (Denmark)

    Linderoth, Lars; Fristrup, Peter; Hansen, Martin;


    ether lipids, which become cytotoxic upon sPLA2-catalyzed hydrolysis has previously been established. To optimize the hydrolysis rate of the lipids and thereby optimizing the release profile of the drugs from the liposomes, we have synthesized a thio-ester pro anticancer ether lipid. Liposomes...... constituted of this lipid showed an altered rate of hydrolysis by sPLA2. We have tested the cytotoxicity of the thio-ester pro anticancer ether lipids toward cancer cells, and the results showed that the cytotoxicity is indeed maintained upon sPLA2 exposure. To further understand the origin for the observed...

  8. Carbon dioxide as a carbon source in organic transformation: carbon-carbon bond forming reactions by transition-metal catalysts.


    Tsuji, Yasushi; Fujihara, Tetsuaki


    Recent carbon-carbon bond forming reactions of carbon dioxide with alkenes, alkynes, dienes, aryl zinc compounds, aryl boronic esters, aryl halides, and arenes having acidic C-H bonds are reviewed in which transition-metal catalysts play an important role.

  9. Cold Flow Properties of Fatty Esters

    Directory of Open Access Journals (Sweden)

    Andrea Kleinová


    Full Text Available The article is devoted to the study of cold fl ow properties of neat esters of branched chain alcohols with fatty acids and blends of these esters with fossil diesel fuel. According to the determined CFPP values, the influence of alcohol branching on the fuel filterability is negligible and was detected only in the case of 2-ethyl hexanol. Fossil fuel blending with fatty esters up to 10 % vol. does not substantially change the cold flow properties of fossil fuel. DSC cooling scan parameters should be employed to predict CFPP of blended diesel fuel.

  10. Biofuel-Promoted Polychlorinated Dibenzodioxin/furan Formation in an Iron-Catalyzed Diesel Particle Filter. (United States)

    Heeb, Norbert V; Rey, Maria Dolores; Zennegg, Markus; Haag, Regula; Wichser, Adrian; Schmid, Peter; Seiler, Cornelia; Honegger, Peter; Zeyer, Kerstin; Mohn, Joachim; Bürki, Samuel; Zimmerli, Yan; Czerwinski, Jan; Mayer, Andreas


    Iron-catalyzed diesel particle filters (DPFs) are widely used for particle abatement. Active catalyst particles, so-called fuel-borne catalysts (FBCs), are formed in situ, in the engine, when combusting precursors, which were premixed with the fuel. The obtained iron oxide particles catalyze soot oxidation in filters. Iron-catalyzed DPFs are considered as safe with respect to their potential to form polychlorinated dibenzodioxins/furans (PCDD/Fs). We reported that a bimetallic potassium/iron FBC supported an intense PCDD/F formation in a DPF. Here, we discuss the impact of fatty acid methyl ester (FAME) biofuel on PCDD/F emissions. The iron-catalyzed DPF indeed supported a PCDD/F formation with biofuel but remained inactive with petroleum-derived diesel fuel. PCDD/F emissions (I-TEQ) increased 23-fold when comparing biofuel and diesel data. Emissions of 2,3,7,8-TCDD, the most toxic congener [toxicity equivalence factor (TEF) = 1.0], increased 90-fold, and those of 2,3,7,8-TCDF (TEF = 0.1) increased 170-fold. Congener patterns also changed, indicating a preferential formation of tetra- and penta-chlorodibenzofurans. Thus, an inactive iron-catalyzed DPF becomes active, supporting a PCDD/F formation, when operated with biofuel containing impurities of potassium. Alkali metals are inherent constituents of biofuels. According to the current European Union (EU) legislation, levels of 5 μg/g are accepted. We conclude that risks for a secondary PCDD/F formation in iron-catalyzed DPFs increase when combusting potassium-containing biofuels.

  11. On Bond Portfolio Management


    Vladislav Kargin


    This paper describes a new method of bond portfolio optimization based on stochastic string models of correlation structure in bond returns. The paper shows how to approximate correlation function of bond returns, compute the optimal portfolio allocation using Wiener-Hopf factorization, and check whether a collection of bonds presents arbitrage opportunities.

  12. Astaxanthin preparation by fermentation of esters from Haematococcus pluvialis algal extracts with Stenotrophomonas species. (United States)

    Dong, Hao; Li, Xuemin; Xue, Changhu; Mao, Xiangzhao


    Natural astaxanthin (Ax) is an additive that is widely used because of its beneficial biochemical functions. However, the methods used to produce free Ax have drawbacks. Chemical saponification methods produce several by-products, and lipase-catalyzed hydrolysis methods are not cost effective. In this study, a bacterial strain of Stenotrophomonas sp. was selected to enzymatically catalyze the saponification of Ax esters to produce free all-trans-Ax. Through single-factor experiments and a Box-Behnken design, the optimal fermentation conditions were determined as follows: a seed culture age of 37.79 h, an inoculum concentration of 5.92%, and an initial broth pH of 6.80. Under these conditions, a fermentation curve was drawn, and the optimal fermentation time was shown to be 60 h. At 60 h, the degradation rate of the Ax esters was 98.08%, and the yield of free all-trans-Ax was 50.130 μg/mL. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:649-656, 2016.

  13. Thermodynamics of Enzyme-Catalyzed Reactions Database (United States)

    SRD 74 Thermodynamics of Enzyme-Catalyzed Reactions Database (Web, free access)   The Thermodynamics of Enzyme-Catalyzed Reactions Database contains thermodynamic data on enzyme-catalyzed reactions that have been recently published in the Journal of Physical and Chemical Reference Data (JPCRD). For each reaction the following information is provided: the reference for the data, the reaction studied, the name of the enzyme used and its Enzyme Commission number, the method of measurement, the data and an evaluation thereof.

  14. Stau-catalyzed Nuclear Fusion


    Hamaguchi, K.; Hatsuda, T.(Theoretical Research Division, Nishina Center, RIKEN, Saitama, 351-0198, Japan); Yanagida, T. T.


    We point out that the stau may play a role of a catalyst for nuclear fusions if the stau is a long-lived particle as in the scenario of gravitino dark matter. In this letter, we consider d d fusion under the influence of stau where the fusion is enhanced because of a short distance between the two deuterons. We find that one chain of the d d fusion may release an energy of O(10) GeV per stau. We discuss problems of making the stau-catalyzed nuclear fusion of practical use with the present tec...

  15. Gold-catalyzed naphthalene functionalization


    Iván Rivilla; M. Mar Díaz-Requejo; Pedro J. Pérez


    The complexes IPrMCl (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene, M = Cu, 1a; M = Au, 1b), in the presence of one equiv of NaBAr'4 (Ar' = 3,5-bis(trifluoromethyl)phenyl), catalyze the transfer of carbene groups: C(R)CO2Et (R = H, Me) from N2C(R)CO2Et to afford products that depend on the nature of the metal center. The copper-based catalyst yields exclusively a cycloheptatriene derivative from the Buchner reaction, whereas the gold analog affords a mixture of products derived either f...

  16. Space-Qualifiable Cyanate Ester Elastomer Project (United States)

    National Aeronautics and Space Administration — Cornerstone Research Group, Inc. (CRG) proposes to design and develop a space-qualifiable cyanate ester elastomer for application in self-deployable space...

  17. Space-Qualifiable Cyanate Ester Elastomer Project (United States)

    National Aeronautics and Space Administration — In Phase 1, CRG demonstrated the feasibility of a novel approach to prepare cyanate ester based elastomers. This approach polymerizes in-situ siloxane within a...

  18. Synthesis of a new energetic nitrate ester

    Energy Technology Data Exchange (ETDEWEB)

    Chavez, David E [Los Alamos National Laboratory


    Nitrate esters have been known as useful energetic materials since the discovery of nitroglycerin by Ascanio Sobrero in 1846. The development of methods to increase the safety and utility of nitroglycerin by Alfred Nobel led to the revolutionary improvement in the utility of nitroglycerin in explosive applications in the form of dynamite. Since then, many nitrate esters have been prepared and incorporated into military applications such as double-based propellants, detonators and as energetic plasticizers. Nitrate esters have also been shown to have vasodilatory effects in humans and thus have been studied and used for treatments of ailments such as angina. The mechanism of the biological response towards nitrate esters has been elucidated recently. Interestingly, many of the nitrate esters used for military purposes are liquids (ethylene glycol dinitrate, propylene glycol dinitrate, etc). Pentaerythritol tetranitrate (PETN) is one of the only solid nitrate esters, besides nitrocellulose, that is used in any application. Unfortunately, PETN melting point is above 100 {sup o}C, and thus must be pressed as a solid for detonator applications. A more practical material would be a melt-castable explosive, for potential simplification of manufacturing processes. Herein we describe the synthesis of a new energetic nitrate ester (1) that is a solid at ambient temperatures, has a melting point of 85-86 {sup o}C and has the highest density of any known nitrate ester composed only of carbon, hydrogen, nitrogen and oxygen. We also describe the chemical, thermal and sensitivity properties of 1 as well as some preliminary explosive performance data.

  19. Rapid Output Growth of Special Acrylic Esters

    Institute of Scientific and Technical Information of China (English)

    Wang Lianzhi


    @@ Acrylic esters are usually classified into general-purpose varieties and special varieties. The production and application of general-purpose varieties is already quite matured in the world and their output growth tends to be flat. Owing to the development of coatings, electronics, automobiles,textiles, printing and construction sectors, especially the application of radiation curing technology in various sectors, special acrylic esters have developed rapidly.

  20. The general base in the thymidylate synthase catalyzed proton abstraction. (United States)

    Ghosh, Ananda K; Islam, Zahidul; Krueger, Jonathan; Abeysinghe, Thelma; Kohen, Amnon


    The enzyme thymidylate synthase (TSase), an important chemotherapeutic drug target, catalyzes the formation of 2'-deoxythymidine-5'-monophosphate (dTMP), a precursor of one of the DNA building blocks. TSase catalyzes a multi-step mechanism that includes the abstraction of a proton from the C5 of the substrate 2'-deoxyuridine-5'-monophosphate (dUMP). Previous studies on ecTSase proposed that an active-site residue, Y94 serves the role of the general base abstracting this proton. However, since Y94 is neither very basic, nor connected to basic residues, nor located close enough to the pyrimidine proton to be abstracted, the actual identity of this base remains enigmatic. Based on crystal structures, an alternative hypothesis is that the nearest potential proton-acceptor of C5 of dUMP is a water molecule that is part of a hydrogen bond (H-bond) network comprised of several water molecules and several protein residues including H147, E58, N177, and Y94. Here, we examine the role of the residue Y94 in the proton abstraction step by removing its hydroxyl group (Y94F mutant). We investigated the effect of the mutation on the temperature dependence of intrinsic kinetic isotope effects (KIEs) and found that these KIEs are more temperature dependent than those of the wild-type enzyme (WT). These results suggest that the phenolic -OH of Y94 is a component of the transition state for the proton abstraction step. The findings further support the hypothesis that no single functional group is the general base, but a network of bases and hydroxyls (from water molecules and tyrosine) sharing H-bonds across the active site can serve the role of the general base to remove the pyrimidine proton.

  1. Transesterification of mustard (Brassica nigra) seed oil with ethanol: Purification of the crude ethyl ester with activated carbon produced from de-oiled cake

    International Nuclear Information System (INIS)

    Highlights: • Biodiesel ethyl ester has been developed from mustard seed oil. • Variables affect the transesterification were investigated. • Dry washing using the activated carbon produced from the extraction remaining was applied to purify the ethyl esters. • Properties of the produced fuels were measured. • Blending of the produced ethyl ester with petro diesel was also investigated. - Abstract: The present study reports the production of mustard seed oil ethyl esters (MSOEE) through alkali-catalyzed transesterification with ethanol using potassium hydroxide as a catalyst. The influence of the process parameters such as catalyst concentration, ethanol to oil molar ratio, reaction temperature, reaction duration and the catalyst type was investigated so as to find out the optimal conditions for the transesterification process. As a result, optimum conditions for production of MSOEE were found to be: 0.90% KOH wt/wt of oil, 8:1 ethanol to oil molar ratio, a reaction temperature of 60 °C, and a reaction time of 60 min. Dry washing method with (2.50% wt.) of the activated carbon that was produced from the de-oiled cake was used to purify the crude ethyl ester from the residual catalyst and glycerol. The transesterification process provided a yield of 94% w/w of ethyl esters with an ester content of 98.22% wt. under the optimum conditions. Properties of the produced ethyl esters satisfied the specifications prescribed by the ASTM standards. Blending MSOEE with petro diesel was also investigated. The results showed that the ethyl esters had a slight influence on the properties of petro diesel

  2. Expression levels of the yeast alcohol acetyltransferase genes ATF1, Lg-ATF1, and ATF2 control the formation of a broad range of volatile esters. (United States)

    Verstrepen, Kevin J; Van Laere, Stijn D M; Vanderhaegen, Bart M P; Derdelinckx, Guy; Dufour, Jean-Pierre; Pretorius, Isak S; Winderickx, Joris; Thevelein, Johan M; Delvaux, Freddy R


    Volatile aroma-active esters are responsible for the fruity character of fermented alcoholic beverages such as beer and wine. Esters are produced by fermenting yeast cells in an enzyme-catalyzed intracellular reaction. In order to investigate and compare the roles of the known Saccharomyces cerevisiae alcohol acetyltransferases, Atf1p, Atf2p and Lg-Atf1p, in volatile ester production, the respective genes were either deleted or overexpressed in a laboratory strain and a commercial brewing strain. Subsequently, the ester formation of the transformants was monitored by headspace gas chromatography and gas chromatography combined with mass spectroscopy (GC-MS). Analysis of the fermentation products confirmed that the expression levels of ATF1 and ATF2 greatly affect the production of ethyl acetate and isoamyl acetate. GC-MS analysis revealed that Atf1p and Atf2p are also responsible for the formation of a broad range of less volatile esters, such as propyl acetate, isobutyl acetate, pentyl acetate, hexyl acetate, heptyl acetate, octyl acetate, and phenyl ethyl acetate. With respect to the esters analyzed in this study, Atf2p seemed to play only a minor role compared to Atf1p. The atf1Delta atf2Delta double deletion strain did not form any isoamyl acetate, showing that together, Atf1p and Atf2p are responsible for the total cellular isoamyl alcohol acetyltransferase activity. However, the double deletion strain still produced considerable amounts of certain other esters, such as ethyl acetate (50% of the wild-type strain), propyl acetate (50%), and isobutyl acetate (40%), which provides evidence for the existence of additional, as-yet-unknown ester synthases in the yeast proteome. Interestingly, overexpression of different alleles of ATF1 and ATF2 led to different ester production rates, indicating that differences in the aroma profiles of yeast strains may be partially due to mutations in their ATF genes. PMID:12957907

  3. The effect of disulfide bond introduction and related Cys/Ser mutations on the stability of a cyclohexanone monooxygenase. (United States)

    Schmidt, Sandy; Genz, Maika; Balke, Kathleen; Bornscheuer, Uwe T


    Baeyer-Villiger monooxygenases (BVMO) belong to the class B of flavin-dependent monooxygenases (type I BVMOs) and catalyze the oxidation of (cyclic) ketones into esters and lactones. The prototype BVMO is the cyclohexanone monooxygenase (CHMO) from Acinetobacter sp. NCIMB 9871. This enzyme shows an impressive substrate scope with a high chemo-, regio- and/or enantioselectivity. BVMO reactions are often difficult, if not impossible to achieve by chemical approaches and this makes these enzymes thus highly desired candidates for industrial applications. Unfortunately, the industrial use is hampered by several factors related to the lack of stability of these biocatalysts. Thus, the aim of this study was to improve the CHMO's long-term stability, one of the most relevant parameter for biocatalytic processes, and additionally its stability against oxidation. We used an easy computational method for the prediction of stabilizing disulfide bonds in the CHMO-scaffold. The three most promising predicted disulfide pairs were created and biochemically characterized. The most oxidatively stable variant (Y411C-A463C) retained nearly 60% activity after incubation with 25 mM H2O2 whereas the wild type retained only 16%. In addition, one extra disulfide pair (T415C-A463C) was created and tested for increased stability. The melting temperature (Tm) of this variant was increased by 5°C with simultaneous improved long-term stability. After verification by ABD-F labeling that this mutant does not form a disulfide bond, single and double Cys/Ser mutants were prepared and investigated. Subsequent analysis revealed that the T415C single point variant is the most stable variant with a 30-fold increased long-term stability (33% residual activity after 24h incubation at 25°C) showcasing a great achievement for practical applications.

  4. Phenylalanine and tyrosine methyl ester intramolecular interactions and conformational analysis by (1)H NMR and infrared spectroscopies and theoretical calculations. (United States)

    Cormanich, Rodrigo A; Ducati, Lucas C; Tormena, Cláudio F; Rittner, Roberto


    Amino acid conformational analysis in solution are scarce, since these compounds present a bipolar zwitterionic structure ((+)H3NCHRCOO(-)) in these media. Also, intramolecular hydrogen bonds have been classified as the sole interactions governing amino acid conformational behavior in the literature. In the present work we propose phenylalanine and tyrosine methyl ester conformational studies in different solvents by (1)H NMR and infrared spectroscopies and theoretical calculations. Both experimental and theoretical results are in agreement and suggest that the conformational behavior of the phenylalanine and tyrosine methyl esters are similar and are dictated by the interplay between steric and hyperconjugative interactions.

  5. Iron-Catalyzed C-C Cross-Couplings Using Organometallics. (United States)

    Guérinot, Amandine; Cossy, Janine


    Over the last decades, iron-catalyzed cross-couplings have emerged as an important tool for the formation of C-C bonds. A wide variety of alkenyl, aryl, and alkyl (pseudo)halides have been coupled to organometallic reagents, the most currently used being Grignard reagents. Particular attention has been devoted to the development of iron catalysts for the functionalization of alkyl halides that are generally challenging substrates in classical cross-couplings. The high functional group tolerance of iron-catalyzed cross-couplings has encouraged organic chemists to use them in the synthesis of bioactive compounds. Even if some points remain obscure, numerous studies have been carried out to investigate the mechanism of iron-catalyzed cross-coupling and several hypotheses have been proposed. PMID:27573401

  6. Advances in nickel-catalyzed cycloaddition reactions to construct carbocycles and heterocycles. (United States)

    Thakur, Ashish; Louie, Janis


    Transition-metal catalysis has revolutionized the field of organic synthesis by facilitating the construction of complex organic molecules in a highly efficient manner. Although these catalysts are typically based on precious metals, researchers have made great strides in discovering new base metal catalysts over the past decade. This Account describes our efforts in this area and details the development of versatile Ni complexes that catalyze a variety of cycloaddition reactions to afford interesting carbocycles and heterocycles. First, we describe our early work in investigating the efficacy of N-heterocyclic carbene (NHC) ligands in Ni-catalyzed cycloaddition reactions with carbon dioxide and isocyanate. The use of sterically hindered, electron donating NHC ligands in these reactions significantly improved the substrate scope as well as reaction conditions in the syntheses of a variety of pyrones and pyridones. The high reactivity and versatility of these unique Ni(NHC) catalytic systems allowed us to develop unprecedented Ni-catalyzed cycloadditions that were unexplored due to the inefficacy of early Ni catalysts to promote hetero-oxidative coupling steps. We describe the development and mechanistic analysis of Ni/NHC catalysts that couple diynes and nitriles to form pyridines. Kinetic studies and stoichiometric reactions confirmed a hetero-oxidative coupling pathway associated with this Ni-catalyzed cycloaddition. We then describe a series of new substrates for Ni-catalyzed cycloaddition reactions such as vinylcyclopropanes, aldehydes, ketones, tropones, 3-azetidinones, and 3-oxetanones. In reactions with vinycyclopropanes and tropones, DFT calculations reveal noteworthy mechanistic steps such as a C-C σ-bond activation and an 8π-insertion of vinylcyclopropane and tropone, respectively. Similarly, the cycloaddition of 3-azetidinones and 3-oxetanones also requires Ni-catalyzed C-C σ-bond activation to form N- and O-containing heterocycles. PMID:26200651

  7. Synthesis of alkyl esters by cutinase in miniemulsion and organic solvent media. (United States)

    de Barros, Dragana P C; Fonseca, Luís P; Cabral, Joaquim M S; Weiss, Clemens K; Landfester, Katharina


    The main objective of this work was studying and testing the nature and influence of reaction media (organic solvent vs. miniemulsion system) on the synthesis of alkyl esters catalyzed by Fusarium solani pisi cutinase. Ester synthesis and cutinase selectivity for different chain length of acids and alcohols (ethyl and hexyl) were evaluated. In iso-octane, after 1 h of reaction, cutinase exhibits rates of esterification between 0.24 micromol x mg(-)1 x min(-1) for ethyl oleate and 1.15 micromol x mg(-)1 x min(-1) for ethyl butyrate, while in a miniemulsion system the rates were from 0.05 for ethyl heptanoate to 0.76 micromol x mg(-1) x min(-1) for ethyl decanoate. The reaction rate for the synthesis of hexyl esters in a miniemulsion system was from 0.19 for hexyl heptanoate to 1.07 micromol x mg(-)1 x min(-1) for hexyl decanoate. High conversion yields of 95% at equilibrium after 8 h of reaction in iso-octane for pentanoic acid (C(5)) with ethanol at equimolar concentration (0.1 M) was achieved. Additionally, this work showed that a significant and unexpected shift in cutinase selectivity occurred towards longer chain length carboxylic acids (C(8)-C(10)) in miniemulsion system as compared to organic solvent (iso-octane) and previous studies in reverse micellar systems. The possibility of working with higher concentration of substrates, without inhibitory effect on the enzyme, was another advantage of the miniemulsion system.

  8. Synthesis of thermoplastic poly(ester-siloxanes in the melt and in solution

    Directory of Open Access Journals (Sweden)



    Full Text Available Two series of thermoplastic elastomers, based on poly(dimethylsiloxane, PDMS, as the soft segment and poly(butylene terephthalate, PBT, as the hard segment, were synthesized by catalyzed transesterification, from dimethyl terephthalate, DMT, silanol-terminated poly(dimethylsiloxane, PDMS-OH, Mn = 1750 g/mol, and 1,4-butanediol, BD. The mole ratio of the starting comonomers was selected to result in a constant hard to soft weight ratio of 55:45. The first series was synthesized in order to determine the optimal mole ratio of BD and DMT for the synthesis of high molecular weight thermoplastic poly(ester-siloxanes, TPESs. The second series was performed in the presence of the high-boiling solvent, 1,2,4-trichlorbenzene in order to increase the mixing between the extremely non-polar siloxane prepolymer and the polar reactants, DMT and BD, and, therefore, avoid phase separation during synthesis. The structure and composition of the synthesized poly(ester- siloxanes were verified by 1H-NMR spectroscopy, while the melting temperatures and degree of crystallinity were determined by differential scanning calorimetry (DSC. The effectiveness of the incorporation of the silanol-terminated poly( dimethylsiloxane into the polyester chains was verified by chloroform extraction. The rheological properties of the poly(ester-siloxanes were investigated by dynamic mechanical spectroscopy (DMA.

  9. The Role of Backbone Hydrogen Bonds in the Transition State for Protein Folding of a PDZ Domain.

    Directory of Open Access Journals (Sweden)

    Søren W. Pedersen

    Full Text Available Backbone hydrogen bonds are important for the structure and stability of proteins. However, since conventional site-directed mutagenesis cannot be applied to perturb the backbone, the contribution of these hydrogen bonds in protein folding and stability has been assessed only for a very limited set of small proteins. We have here investigated effects of five amide-to-ester mutations in the backbone of a PDZ domain, a 90-residue globular protein domain, to probe the influence of hydrogen bonds in a β-sheet for folding and stability. The amide-to-ester mutation removes NH-mediated hydrogen bonds and destabilizes hydrogen bonds formed by the carbonyl oxygen. The overall stability of the PDZ domain generally decreased for all amide-to-ester mutants due to an increase in the unfolding rate constant. For this particular region of the PDZ domain, it is therefore clear that native hydrogen bonds are formed after crossing of the rate-limiting barrier for folding. Moreover, three of the five amide-to-ester mutants displayed an increase in the folding rate constant suggesting that the hydrogen bonds are involved in non-native interactions in the transition state for folding.

  10. Hydrogen bonded supramolecular structures

    CERN Document Server

    Li, Zhanting


    This book covers the advances in the studies of hydrogen-bonding-driven supramolecular systems  made over the past decade. It is divided into four parts, with the first introducing the basics of hydrogen bonding and important hydrogen bonding patterns in solution as well as in the solid state. The second part covers molecular recognition and supramolecular structures driven by hydrogen bonding. The third part introduces the formation of hollow and giant macrocycles directed by hydrogen bonding, while the last part summarizes hydrogen bonded supramolecular polymers. This book is designed to b

  11. Palladium-catalyzed regioselective intramolecular coupling of o-carborane with aromatics via direct cage B-H activation. (United States)

    Quan, Yangjian; Xie, Zuowei


    Palladium-catalyzed intramolecular coupling of o-carborane with aromatics via direct cage B-H bond activation has been achieved, leading to the synthesis of a series of o-carborane-functionalized aromatics in high yields with excellent regioselectivity. In addition, the site selectivity can also be tuned by the substituents on cage carbon atom. PMID:25747772

  12. Amidines for Versatile Cobalt(III)-Catalyzed Synthesis of Isoquinolines through C-H Functionalization with Diazo Compounds. (United States)

    Li, Jie; Tang, Mengyao; Zang, Lei; Zhang, Xiaolei; Zhang, Zhao; Ackermann, Lutz


    A cobalt(III)-catalyzed C-H/N-H bond functionalization for the synthesis of 1-aminoisoquinolines from aryl amidines and diazo compounds has been developed. The reaction proceeds under mild reaction conditions, obviates the need for oxidants, produces only N2 and H2O as the byproducts, and features a broad substrate scope. PMID:27219713

  13. Selective Synthesis of Isoquinolines by Rhodium(III)-Catalyzed C-H/N-H Functionalization with α-Substituted Ketones. (United States)

    Li, Jie; Zhang, Zhao; Tang, Mengyao; Zhang, Xiaolei; Jin, Jian


    A rhodium(III)-catalyzed C-H/N-H bond functionalization for the synthesis of 1-aminoisoquinolines from aryl amidines and α-MsO/TsO/Cl ketones was achieved under mild reaction conditions. Thus, this approach provides a practical method for the site-selective synthesis of various synthetically valuable isoquinolines with wide functional group tolerance. PMID:27441726

  14. Palladium-catalyzed regioselective intramolecular coupling of o-carborane with aromatics via direct cage B-H activation. (United States)

    Quan, Yangjian; Xie, Zuowei


    Palladium-catalyzed intramolecular coupling of o-carborane with aromatics via direct cage B-H bond activation has been achieved, leading to the synthesis of a series of o-carborane-functionalized aromatics in high yields with excellent regioselectivity. In addition, the site selectivity can also be tuned by the substituents on cage carbon atom.

  15. Hydroformylation of methyl oleate catalyzed by rhodium complexes; Hidroformilacao do oleato de metila catalisada por complexos de rodio

    Energy Technology Data Exchange (ETDEWEB)

    Mendes, Ana Nery Furlan [Universidade Federal do Espirito Santo (UFES), Sao Mateus, ES (Brazil). Centro Universitario Norte do Espirito Santo. Dept. de Ciencias Naturais; Rosa, Ricardo Gomes da; Gregorio, Jose Ribeiro, E-mail: [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica


    In this work, we describe the hydroformylation of methyl oleate catalyzed by several rhodium complexes. Parameters including total pressure, phosphorous/rhodium and CO/H{sub 2} ratio, temperature and phosphorous ligands were scanned. Total conversion of the starting double bonds was achieved while maintaining excellent selectivity in aldehydes. (author)


    Previous studies have shown that beta -carotene 15,15'-monooxygenase (CMO1) catalyzes the cleavage of beta -carotene at the central carbon 15, 15’-double bond, but cleaves lycopene with much lower activity. However, expressing the mouse carotene-9’,10’-monooxygenase (CMO2) in beta-carotene/lycopene...

  17. Aminophenols as Efficient Ligand for Copper-Catalyzed Ullmann-type Synthesis of Diaryl Ethers

    International Nuclear Information System (INIS)

    An efficient Cu-catalyzed synthesis of diaryl ethers from various aromatic iodides (bromides) and phenols was developed by using L2(2-((o-toluidino)methyl)phenol) as the ligand. The present protocol is applicable to a variety of phenols and aryl iodides (bromides) containing electron-withdrawing, electron-donating, and sterically demanding substrate combinations under mild conditions. The further study on design and application of new ligands in copper based Ullmann-type coupling reaction is currently ongoing. Carbon-oxygen bonds extensively exist in all kinds of biologically active natural products, important pharmaceutical compounds and polymers. The palladium-catalyzed formation of carbon-oxygen bonds is one of the two major methods available for aryl ether synthesis. However, palladium-based protocols, although successful, have some inherent limitations such as moisture sensitivity, costly metal catalysts, and environmental toxicity

  18. Hydrolyzable polyureas bearing hindered urea bonds. (United States)

    Ying, Hanze; Cheng, Jianjun


    Hydrolyzable polymers are widely used materials that have found numerous applications in biomedical, agricultural, plastic, and packaging industrials. They usually contain ester and other hydrolyzable bonds, such as anhydride, acetal, ketal, or imine, in their backbone structures. Here, we report the first design of hydrolyzable polyureas bearing dynamic hindered urea bonds (HUBs) that can reversibly dissociate to bulky amines and isocyanates, the latter of which can be further hydrolyzed by water, driving the equilibrium to facilitate the degradation of polyureas. Polyureas bearing 1-tert-butyl-1-ethylurea bonds that show high dynamicity (high bond dissociation rate), in the form of either linear polymers or cross-linked gels, can be completely degraded by water under mild conditions. Given the simplicity and low cost for the production of polyureas by simply mixing multifunctional bulky amines and isocyanates, the versatility of the structures, and the tunability of the degradation profiles of HUB-bearing polyureas, these materials are potentially of very broad applications. PMID:25406025

  19. Detection of testosterone esters in blood. (United States)

    Forsdahl, Guro; Erceg, Damir; Geisendorfer, Thomas; Turkalj, Mirjana; Plavec, Davor; Thevis, Mario; Tretzel, Laura; Gmeiner, Günter


    Injections of synthetic esters of testosterone are among the most common forms of testosterone application. In doping control, the detection of an intact ester of testosterone in blood gives unequivocal proof of the administration of exogenous testosterone. The aim of the current project was to investigate the detection window for injected testosterone esters as a mixed substance preparation and as a single substance preparation in serum and plasma. Furthermore, the suitability of different types of blood collection devices was evaluated. Collection tubes with stabilizing additives, as well as non-stabilized serum separation tubes, were tested. A clinical study with six participants was carried out, comprising a single intramuscular injection of either 1000 mg testosterone undecanoate (Nebido(®)) or a mixture of 30 mg testosterone propionate, 60 mg testosterone phenylpropionate, 60 mg testosterone isocaproate, and 100 mg testosterone decanoate (Sustanon(®)). Blood was collected throughout a testing period of 60 days. The applied analytical method for blood analysis included liquid-liquid extraction and preparation of oxime derivatives, prior to TLX-sample clean-up and liquid chromatography-tandem mass spectrometry (LC-MS/MS) detection. All investigated testosterone esters could be detected in post-administration blood samples. The detection time depended on the type of ester administered. Furthermore, results from the study show that measured blood concentrations of especially short-chained testosterone esters are influenced by the type of blood collection device applied. The testosterone ester detection window, however, was comparable. PMID:26695486

  20. Mono- and tri-ester hydrogenolysis using tandem catalysis. Scope and mechanism.

    Energy Technology Data Exchange (ETDEWEB)

    Lohr, Tracy L.; Li, Zhi; Assary, Rajeev S.; Curtiss, Larry A.; Marks, Tobin J.


    The scope and mechanism of thermodynamically leveraged ester RC(O)O-R' bond hydrogenolysis by tandem metal triflate + supported Pd catalysts are investigated both experimentally and theoretically by DFT and energy span analysis. This catalytic system has a broad scope, with relative cleavage rates scaling as, tertiary 4 secondary 4 primary ester at 1 bar H-2, yielding alkanes and carboxylic acids with high conversion and selectivity. Benzylic and allylic esters display the highest activity. The rate law is nu = k[M(OTf )(n)](1)[ester](0)[H-2](0) with an H/D kinetic isotope effect = 6.5 +/- 0.5, implying turnover-limiting C-H scission following C-O cleavage, in agreement with theory. Intermediate alkene products are then rapidly hydrogenated. Applying this approach with the very active Hf(OTf)(4) catalyst to bio-derived triglycerides affords near-quantitative yields of C-3 hydrocarbons rather than glycerol. From model substrates, it is found that RC(O)O-R' cleavage rates are very sensitive to steric congestion and metal triflate identity. For triglycerides, primary/external glyceryl CH2-O cleavage predominates over secondary/internal CH-O cleavage, with the latter favored by less acidic or smaller ionic radius metal triflates, raising the diester selectivity to as high as 48% with Ce(OTf)(3).

  1. Base catalyzed transesterification of acid treated vegetable oil blend for biodiesel production

    Energy Technology Data Exchange (ETDEWEB)

    Yusup, Suzana; Khan, Modhar Ali [Chemical Engineering Department, Universiti Teknologi PETRONAS, Seri Iskandar, Tronoh, Perak 31750 (Malaysia)


    Biodiesel can be produced from low cost non-edible oils and fats. However, most of these sources are of high free fatty acid content which requires two stage transesterification to reduce the acid value and produce biodiesel. The acid treatment step is usually followed by base transesterification since the latter can yield higher conversions of methyl esters at shorter reaction time when compared with acid catalyzed reaction. In the current study, base transesterification in the second stage of biodiesel synthesis is studied for a blend of crude palm/crude rubber seed oil that had been characterized and treated with acid esterification. Optimum conditions for the reaction were established and effect of each variable was investigated. The base catalyzed transesterification favored a temperature of 55 C with methanol/oil molar ratio of 8/1 and potassium hydroxide at 2% (ww{sup -1}) (oil basis). The conversion of methyl esters exceeded 98% after 5 h and the product quality was verified to match that for biodiesel with international standards. (author)

  2. Cobalt-Catalyzed Vinylation of Organozinc Reagents with Aldehydes

    Institute of Scientific and Technical Information of China (English)

    WANG; JinXian


    Transtion metal catalyzed vinylation of organic halides are known to be a very convenient method for forming carbon-carbon bonds at unsubstituted vinylic position. The versatility of stilbenes is well known because of its various biological active components, the variety of its reactions in organic syntheses, and its ability to function as a bonding partner for metals in complexes.  Many methods have been described for the synthesis of stilbenes. The reduction, dehydrogenation, and elimination reactions leading to stilbenes without formation of new carbon-carbon bonds are known to be a very convenient methods. Synthetically more important are the dimerization reactions: oxidative or eleminative dimerization of a suitable methylarene often constitutes the method of choice for the preparation of a symmetric stilbene. Meerwein arylation and Heck reaction are prominent examples for the synthesis of stilbenes from arenes and styrenes. Moreover, condensation reactions of a nucleophilic with an electrophilic arylmethyl compound include Knoevenagel type reactions and the very general Wittig and Wittig-Horner reactions are also known methods.  ……

  3. Iridium-catalyzed intermolecular dehydrogenative silylation of polycyclic aromatic compounds without directing groups. (United States)

    Murai, Masahito; Takami, Keishi; Takai, Kazuhiko


    This study describes the iridium-catalyzed intermolecular dehydrogenative silylation of C(sp(2))-H bonds of polycyclic aromatic compounds without directing groups. The reaction produced various arylsilanes through both Si-H and C-H bond activation, with hydrogen as the sole byproduct. Reactivity was affected by the electronic nature of the aromatic compounds, and silylation of electron-deficient and polycyclic aromatic compounds proceeded efficiently. Site-selectivity was controlled predominantly by steric factors. Therefore, the current functionalization proceeded with opposite chemo- and site-selectivity compared to that observed for general electrophilic functionalization of aromatic compounds.

  4. Catalyzed electrolytic plutonium oxide dissolution

    International Nuclear Information System (INIS)

    Catalyzed electrolytic plutonium oxide dissolution (CEPOD) was first demonstrated at Pacific Northwest Laboratory (PNL) in early 1974 in work funded by the Exxon Corporation. The work, aimed at dissolution of Pu-containing residues remaining after the dissolution of spent mixed-oxide reactor fuels, was first publicly disclosed in 1981. The process dissolves PuO2 in an anolyte containing small (catalytic) amounts of elements that form kinetically fast, strongly oxidizing ions. These are continuously regenerated at the anode. Catalysts used, in their oxidized form, include Ag2+, Ce4+, Co3+, and AmO22+. This paper reviews the chemistry involved in CEPOD and the results of its application to the dissolution of the Pu content of a variety of PuO2-containing materials such as off-standard oxide, fuels dissolution residues, incinerator ash, contaminated soils, and other scraps or wastes. Results are presented for both laboratory-scale and plant-scale dissolves

  5. The catalytic mechanism of benzoxazine to the polymerization of cyanate ester

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiaodan, E-mail: [Chongqing Key Laboratory of Catalysis and Functional Organic Molecules, College of Environment and Biological Engineering, Chongqing Technology and Business University, Chongqing 400067 (China); Luo, Xiaoyong; Liu, Ming [State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Sichuan, Chengdu 610065 (China); Ran, Qichao, E-mail: [State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Sichuan, Chengdu 610065 (China); Gu, Yi, E-mail: [State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Sichuan, Chengdu 610065 (China)


    Two model compounds, 3-Phenyl-3,4-dihydro-2H-1,3-benzoxazine (PA) and 6,8-dimethyl-3-(2,4,6-trimethyl-phenyl)-3,4-dihydro-2H-1,3-benzoxazine (s-PA), were successfully synthesized and purificated. Compared with PA, s-PA also catalyzed the polymerization of BADCy even though there was no phenolic hydroxyl in its final ring-opened structures. It was confirmed that the real mechanism of benzoxazine catalyzing the polymerization of cyanate ester is the nucleophilic addition reaction of the oxygen anion on ring-opened benzoxazine to the positively charged carbon atom on cyano group. The catalytic effect also contains the contribution from the phenolic hydroxyl, but it is a secondary factor. - Highlights: • Two model compounds, PA and s-PA, were successfully synthesized and purificated. • There is no phenolic hydroxyl in the final ring-opened structures of s-PA. • Compared with PA, s-PA also can catalyze the polymerization of BADCy. • The main catalytic process is caused by the oxygen anion. • The catalytic effect from the phenolic hydroxyl is a secondary factor.

  6. Hydrogen evolution catalyzed by cobaloximes. (United States)

    Dempsey, Jillian L; Brunschwig, Bruce S; Winkler, Jay R; Gray, Harry B


    Natural photosynthesis uses sunlight to drive the conversion of energy-poor molecules (H(2)O, CO(2)) to energy-rich ones (O(2), (CH(2)O)(n)). Scientists are working hard to develop efficient artificial photosynthetic systems toward the "Holy Grail" of solar-driven water splitting. High on the list of challenges is the discovery of molecules that efficiently catalyze the reduction of protons to H(2). In this Account, we report on one promising class of molecules: cobalt complexes with diglyoxime ligands (cobaloximes). Chemical, electrochemical, and photochemical methods all have been utilized to explore proton reduction catalysis by cobaloxime complexes. Reduction of a Co(II)-diglyoxime generates a Co(I) species that reacts with a proton source to produce a Co(III)-hydride. Then, in a homolytic pathway, two Co(III)-hydrides react in a bimolecular step to eliminate H(2). Alternatively, in a heterolytic pathway, protonation of the Co(III)-hydride produces H(2) and Co(III). A thermodynamic analysis of H(2) evolution pathways sheds new light on the barriers and driving forces of the elementary reaction steps involved in proton reduction by Co(I)-diglyoximes. In combination with experimental results, this analysis shows that the barriers to H(2) evolution along the heterolytic pathway are, in most cases, substantially greater than those of the homolytic route. In particular, a formidable barrier is associated with Co(III)-diglyoxime formation along the heterolytic pathway. Our investigations of cobaloxime-catalyzed H(2) evolution, coupled with the thermodynamic preference for a homolytic route, suggest that the rate-limiting step is associated with formation of the hydride. An efficient water splitting device may require the tethering of catalysts to an electrode surface in a fashion that does not inhibit association of Co(III)-hydrides. PMID:19928840

  7. Australia's Bond Home Bias


    Mishra, Anil V; Umaru B. Conteh


    This paper constructs the float adjusted measure of home bias and explores the determinants of bond home bias by employing the International Monetary Fund's high quality dataset (2001 to 2009) on cross-border bond investment. The paper finds that Australian investors' prefer investing in countries with higher economic development and more developed bond markets. Exchange rate volatility appears to be an impediment for cross-border bond investment. Investors prefer investing in countries with ...

  8. Catalysis of protein disulfide bond isomerization in a homogeneous substrate. (United States)

    Kersteen, Elizabeth A; Barrows, Seth R; Raines, Ronald T


    Protein disulfide isomerase (PDI) catalyzes the rearrangement of nonnative disulfide bonds in the endoplasmic reticulum of eukaryotic cells, a process that often limits the rate at which polypeptide chains fold into a native protein conformation. The mechanism of the reaction catalyzed by PDI is unclear. In assays involving protein substrates, the reaction appears to involve the complete reduction of some or all of its nonnative disulfide bonds followed by oxidation of the resulting dithiols. The substrates in these assays are, however, heterogeneous, which complicates mechanistic analyses. Here, we report the first analysis of disulfide bond isomerization in a homogeneous substrate. Our substrate is based on tachyplesin I, a 17-mer peptide that folds into a beta hairpin stabilized by two disulfide bonds. We describe the chemical synthesis of a variant of tachyplesin I in which its two disulfide bonds are in a nonnative state and side chains near its N and C terminus contain a fluorescence donor (tryptophan) and acceptor (N(epsilon)-dansyllysine). Fluorescence resonance energy transfer from 280 to 465 nm increases by 28-fold upon isomerization of the disulfide bonds into their native state (which has a lower E(o') = -0.313 V than does PDI). We use this continuous assay to analyze catalysis by wild-type human PDI and a variant in which the C-terminal cysteine residue within each Cys-Gly-His-Cys active site is replaced with alanine. We find that wild-type PDI catalyzes the isomerization of the substrate with kcat/K(M) = 1.7 x 10(5) M(-1) s(-1), which is the largest value yet reported for catalysis of disulfide bond isomerization. The variant, which is a poor catalyst of disulfide bond reduction and dithiol oxidation, retains virtually all of the activity of wild-type PDI in catalysis of disulfide bond isomerization. Thus, the C-terminal cysteine residues play an insignificant role in the isomerization of the disulfide bonds in nonnative tachyplesin I. We conclude

  9. Bond percolation in films (United States)

    Korneta, W.; Pytel, Z.


    Bond percolation in films with simple cubic structure is considered. It is assumed that the probability of a bond being present between nearest-neighbor sites depends on the distances to surfaces. Based on the relation between the Potts model and the bond percolation model, and using the mean-field approximation, the phase diagram and profiles of the percolation probability have been obtained.

  10. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael


    to think in alternative ways such as issuing corporate bonds. A market for corporate bonds exists in countries such as Norway, Germany, France, the United Kingdom and the United States, while Denmark is still behind in this trend. Some large Danish corporations have instead used foreign corporate bonds...

  11. Chemical bond fundamental aspects of chemical bonding

    CERN Document Server

    Frenking, Gernot


    This is the perfect complement to ""Chemical Bonding - Across the Periodic Table"" by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community. The resulting book is a unique overview of the different approaches used for describing a chemical bond, including molecular-orbital based, valence-bond based, ELF, AIM and density-functional based methods. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemica

  12. Synthesis of isoquinolines via Rh-catalyzed C-H activation/C-N cyclization with diazodiesters or diazoketoesters as a C2 source. (United States)

    Wang, Jie; Zha, Shanke; Chen, Kehao; Zhang, Feifei; Zhu, Jin


    Synthesis of isoquinolines based on efficient C-C and C-N bond formation through Rh(iii)-catalyzed C-H activation and subsequent intramolecular cyclization is reported. Diazodiesters serving as a C2 source in the newly formed heterocycles are first demonstrated. Additionally, the Rh(iii)-catalyzed direct C-H activation/cyclization of benzimidates with diazoketoesters is also described. PMID:27146107

  13. Production and Characterization of Ethyl Ester from Crude Jatropha curcas Oil having High Free Fatty Acid Content (United States)

    Kumar, Rajneesh; Dixit, Anoop; Singh, Shashi Kumar; Singh, Gursahib; Sachdeva, Monica


    The two step process was carried out to produce biodiesel from crude Jatropha curcas oil. The pretreatment process was carried out to reduce the free fatty acid content by (≤2 %) acid catalyzed esterification. The optimum reaction conditions for esterification were reported to be 5 % H2SO4, 20 % ethanol and 1 h reaction time at temperature of 65 °C. The pretreatment process reduced the free fatty acid of oil from 7 to 1.85 %. In second process, alkali catalysed transesterification of pretreated oil was carried and the effects of the varying concentrations of KOH and ethanol: oil ratios on percent ester recovery were investigated. The optimum reaction conditions for transesterification were reported to be 3 % KOH (w/v of oil) and 30 % (v/v) ethanol: oil ratio and reaction time 2 h at 65 °C. The maximum percent recovery of ethyl ester was reported to be 60.33 %.

  14. Protease-catalyzed Synthesis of Bz-Arg-Gly-Asp-OMe in Full Aqueous Medium

    Institute of Scientific and Technical Information of China (English)

    HOU Rui-zhen; LI Hong-mei; LIU Yun-jia; ZHANG Long; XU Li; ZHANG Xue-zhong


    Synthesis of N-benzoyl-argininylglycylasparagine methyl ester(Bz-Arg-Gly-Asp-OMe), a precursor tripeptide of Arg-Gly-Asp) was catalyzed by papain under kinetic control, at alkaline pH, in a full aqueous medium. The substrates were N-benzoyl-argininylglycine ethyl ester and asparagine dimethyl ester. An aqueous solution of 0. 1 mol/L KCl/NaOH containing 8 mmol/L EDTA and 2 mmol/L DTT was selected as the reaction medium. The synthesized hydrophilic tripeptide was soluble in the reaction medium during the reaction process, however, the secondary hydrolysis of the tripeptide product was not considerable. The effects of different factors, including water content, temperature, reaction time, and molar ratio of the substrates, on the yield of Bz-Arg-Gly-Asp-OMe were examined. The optimal reaction conditions were 0.05 mol/L Bz-Arg-Gly-OEt and 0.15 mol/L Asp(-OMe)2 · HCl in 0.1 mol/L KCl/NaOH solution(pH 8.5), at 40 ℃, and a reaction time of 60 min, with a maximum conversion yield of 62.4%.

  15. Enzyme-catalyzed organic syntheses: transesterification reactions of chlorophyl a, bacteriochlorophyll a, and derivatives with chlorophyllase

    Energy Technology Data Exchange (ETDEWEB)

    Michalski, T.J.; Hunt, J.E.; Bradshaw, C.; Wagner, A.M.; Norris, J.R.; Katz, J.J.


    The green plant enzyme chlorophyllase (EC, chlorophyll chlorophyllido-hydroase) has been used for the synthesis of a variety of primary alcohol and diol esters of chlorophyll a, bacteriochlorophyll a, and pyrobacteriochlorophyll a. Green plant chlorophyllase accepts a much larger range of alcohol and chlorophyll substrates than had previously been realized. Thus, chlorophyllide and bacteriochlorophyllide esters of primary alcohols such as retinol and the detergent Triton X-100 and of dihydric alcohols such as ethylene glycol, butanediol, or 2-hydroxyethyl disulfide can readily be obtained by enzyme-assisted transesterification. The diol chlorophyllide esters are valuable intermediates for the synthesis of reaction center special pair models. Chlorophyllase-assisted reactions can be carried out in media containing up to 95% of organic solvents without the concomitant side reactions that important chlorophyll functional groups readily undergo even under mild conditions in conventional chemical synthetic procedures. In competitive chlorophyllase-catalyzed transesterification reactions, long-chain alcohols such as farnesol and retinol vs simple aliphatic alcohols and diols, the enzyme shows a definite preference for the long-chain alcohol. 37 references, 1 figure, 2 tables.

  16. Bonding thermoplastic polymers (United States)

    Wallow, Thomas I.; Hunter, Marion C.; Krafcik, Karen Lee; Morales, Alfredo M.; Simmons, Blake A.; Domeier, Linda A.


    We demonstrate a new method for joining patterned thermoplastic parts into layered structures. The method takes advantage of case-II permeant diffusion to generate dimensionally controlled, activated bonding layers at the surfaces being joined. It is capable of producing bonds characterized by cohesive failure while preserving the fidelity of patterned features in the bonding surfaces. This approach is uniquely suited to production of microfluidic multilayer structures, as it allows the bond-forming interface between plastic parts to be precisely manipulated at micrometer length scales. The bond enhancing procedure is easily integrated in standard process flows and requires no specialized equipment.

  17. A highly regioselective route to arbutin esters by immobilized lipase from Penicillium expansum. (United States)

    Yang, Rong-Ling; Li, Ning; Li, Ri-Feng; Smith, Thomas J; Zong, Min-Hua


    Immobilized lipase from Penicillium expansum, a novel and inexpensive enzyme preparation that we immobilized in our laboratory, was an excellent catalyst for highly regioselective acylation of arbutin with fatty acid vinyl esters. For the enzymatic butanoylation of arbutin, under the optimal conditions, initial reaction rate was 75.1 mM/h, and substrate conversion and regioselectivity were greater than 99%. In addition, a variety of 6'-esters of arbutin were prepared with high conversion (>99%) and excellent regioselectivity (>99%). It was found that the enzymatic reaction rate varied widely with different acyl donors, presumably owing to their different interactions with the active site of the lipase. The immobilized lipase from P. expansum displayed highest catalytic activity with medium-length straight-chain acyl donors. Acyl donors bearing a substituent or a conjugate double bond gave reduced reaction rates. PMID:19695875

  18. Synthesis and Crystal Structure of a Sodium Monosulfuron-ester (N-[2'-(4-Methyl)pyrimidinyl]-2-carbomethoxy Benzyl Sulfonylurea Sodium)

    Institute of Scientific and Technical Information of China (English)

    KOU Jun-Jie; LI Zheng-Ming; SONG Hai-Bin


    Monosulfuron-ester is a novel sulfonylurea herbicide with ultra-low dosage. Herein sodium monosulfuron-ester was synthesized and its crystal structure was determined by X-ray diffraction method. The title compound belongs to monoclinic, space group P21/c with a = 9.335(5), b = 20.632(12), c = 13.853(8) (A), β = 107.193(9)°, Mr = 487.46, Z = 4, Dc = 1.270 g/cm3, μ = 0.293 mm-1, F(000) = 1015, R = 0.0859 and wR = 0.2633. In the title compound, Na coordinates with N(1), O(1) and O(3) from one monosulfuron-ester molecule, N(4A) and O(5A) from the other monosulfuron-ester molecule and one oxygen atom from DMSO to give six coordination bonds.

  19. Investigation on the mechanism of aminosilane-mediated bonding of thermoplastics and poly(dimethylsiloxane). (United States)

    Sunkara, Vijaya; Cho, Yoon-Kyoung


    A possible mechanism for the aminosilane-mediated room-temperature (RT) bonding of thermoplastics and poly(dimethylsiloxane) (PDMS) is presented. The plasma-activated thermoplastic or PDMS substrates were modified with alkoxy silanes having different organo functional groups, and their bonding characteristics were studied. Manual peeling tests revealed that strong bonding was realized only when the silane had a free amino group and at least two alkoxy groups on the silicon. Silanization was carried out in both aqueous and anhydrous conditions; bonding occurred readily at RT in the former case, but a longer incubation time or a higher temperature was needed for the latter. The presence of the silane on the surface was confirmed by contact-angle measurements and UV spectrophotometric, attenuated total reflectance infrared spectroscopic (ATR-IR) and X-ray photoelectron spectroscopic (XPS) analyses. In the case where the aminosilane was deposited from aqueous solution, the amino functionality of the silane-catalyzed siloxane bond formation between the silanol on the modified thermoplastic surface and the silanol of the plasma-activated PDMS. In the case of anhydrous phase deposition, the aminosilane first catalyzed the hydrolysis of the ethoxy groups on the silicon, and then, catalyzed the condensation between the silanol groups of both materials. Shelf life tests of the modified thermoplastics showed that the aminosilane was stable over 2 weeks, and that bonding occurred at RT when the substrates were soaked in water before bonding.

  20. Enzyme-Catalyzed Regioselective Modification of Starch Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Chakraborty, Soma [Polytechnic Univ., Brooklyn, NY (United States). National Science Foundation (NSF) Center for Biocatalysis and Bioprocessing of Macromolecules, Othmer Dept. of Chemical and Biological Science and Engineering; Sahoo, Bishwabhusan [Polytechnic Univ., Brooklyn, NY (United States). National Science Foundation (NSF) Center for Biocatalysis and Bioprocessing of Macromolecules, Othmer Dept. of Chemical and Biological Science and Engineering; Teraoka, Iwao [Polytechnic Univ., Brooklyn, NY (United States). National Science Foundation (NSF) Center for Biocatalysis and Bioprocessing of Macromolecules, Othmer Dept. of Chemical and Biological Science and Engineering; Miller, Lisa M. [Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source (NSLS); Gross, Richard A. [Polytechnic Univ., Brooklyn, NY (United States). National Science Foundation (NSF) Center for Biocatalysis and Bioprocessing of Macromolecules, Othmer Dept. of Chemical and Biological Science and Engineering


    The selective esterification of starch nanoparticles was performed using as catalyst Candida antartica Lipase B (CAL-B) in its immobilized (Novozym 435) and free (SP-525) forms. The starch nanoparticles were made accessible for acylation reactions by formation of Aerosol-OT (AOT, bis(2-ethylhexyl)sodium sulfosuccinate) stabilized microemulsions. Starch nanoparticles in microemulsions were reacted with vinyl stearate, ε-caprolactone, and maleic anhydride at 40 °C for 48 h to give starch esters with degrees of substitution (DS) of 0.8, 0.6, and 0.4, respectively. Substitution occurred regioselectively at the C-6 position of the glucose repeat units. Infrared microspectroscopy (IRMS) revealed that AOT-coated starch nanoparticles diffuse into the outer 50 μm shell of catalyst beads. Thus, even though CAL-B is immobilized within a macroporous resin, CAL-B is sufficiently accessible to the starch nanoparticles. When free CAL-B was incorporated along with starch within AOT-coated reversed micelles, CAL-B was also active and catalyzed the acylation with vinyl stearate (24 h, 40 °C) to give DS = 0.5. After removal of surfactant from the modified starch nanoparticles, they were dispersed in DMSO or water and were shown to retain their nanodimensions.

  1. Application conditions for ester cured alkaline phenolic resin sand

    Directory of Open Access Journals (Sweden)

    Ren-he Huang


    Full Text Available Five organic esters with different curing speeds: propylene carbonate (i.e. high-speed ester A; 1, 4-butyrolactone; glycerol triacetate (i.e. medium-speed ester B; glycerol diacetate; dibasic ester (DBE (i.e. low-speed ester C, were chosen to react with alkaline phenolic resin to analyze the application conditions of ester cured alkaline phenolic resin. The relationships between the curing performances of the resin (including pH value, gel pH value, gel time of resin solution, heat release rate of the curing reaction and tensile strength of the resin sand and the amount of added organic ester and curing temperature were investigated. The results indicated the following: (1 The optimal added amount of organic ester should be 25wt.%-30wt.% of alkaline phenolic resin and it must be above 20wt.%-50 wt.% of the organic ester hydrolysis amount. (2 High-speed ester A (propylene carbonate has a higher curing speed than 1, 4-butyrolactone, and they were both used as high-speed esters. Glycerol diacetate is not a high-speed ester in alkaline phenolic resin although it was used as a high-speed ester in ester cured sodium silicate sand; glycerol diacetate and glycerol triacetate can be used as medium-speed esters in alkaline phenolic resin. (3 High-speed ester A, medium-speed ester B (glycerol triacetate and low-speed ester C (dibasic ester, i.e., DBE should be used below 15 ìC, 35 ìC and 50 ìC, respectively. High-speed ester A or low-speed ester C should not be used alone but mixed with medium-speed ester B to improve the strength of the resin sand. (4 There should be a suitable solid content (generally 45wt.%-65wt.% of resin, alkali content (generally 10wt.%-15wt.% of resin and viscosity of alkaline phenolic resin (generally 50-300 mPa≤s in the preparation of alkaline phenolic resin. Finally, the technique conditions of alkaline phenolic resin preparation and the application principles of organic ester were discussed.

  2. Efficient photolytic C-H bond functionalization of alkylbenzene with hypervalent iodine(iii) reagent. (United States)

    Sakamoto, Ryu; Inada, Tsubasa; Selvakumar, Sermadurai; Moteki, Shin A; Maruoka, Keiji


    A practical approach to radical C-H bond functionalization by the photolysis of a hypervalent iodine(iii) reagent is presented. The photolysis of [bis(trifluoroacetoxy)iodo]benzene (PIFA) leads to the generation of trifluoroacetoxy radicals, which allows the smooth transformation of various alkylbenzenes to the corresponding benzyl ester compounds under mild reaction conditions. PMID:26686276

  3. Efficient Synthesis of Chiral Trisubstituted 1,2-Allenyl Ketones by Catalytic Asymmetric Conjugate Addition of Malonic Esters to Enynes. (United States)

    Yao, Qian; Liao, Yuting; Lin, Lili; Lin, Xiaobin; Ji, Jie; Liu, Xiaohua; Feng, Xiaoming


    An N,N'-dioxide/scandium(III) complex catalyzed, highly efficient conjugate addition of malonic esters to enynes is described. A range of trisubstituted 1,2-allenyl ketones were obtained in high yields (up to 99 %) with good d.r. (up to 95/5) and excellent ee values (97 %-99 %). Moreover, the products could be easily transformed into chiral furan and 5-hydroxypyrazoline derivatives, both of which are important skeletons of many biologically active compounds and pharmacologicals. PMID:26694204

  4. Effect of Ozone Produced from Antibody-catalyzed Water Oxidation on Pathogenesis of Atherosclerosis

    Institute of Scientific and Technical Information of China (English)

    Ke-Jun PENG; Yu-Shan HUANG; Li-Na AN; Xiao-Qun HAN; Jing-Ge ZHANG; Qiu-Lin WANG; Jing SUN; Shu-Ren WANG


    Recent studies have suggested that antibodies can catalyze the generation of unknown oxidants including hydrogen peroxide (H2O2) and ozone (O3) from singlet oxygen (1O2) and water. This study is aimedto detect the effect of antibody-catalyzed water oxidation on atherosclerosis. Our results showed that both H2O2 and O3 were produced in human leukemia THP- 1 monocytes incubated with human immunoglobulin G and phorbol myristate acetate. In the THP-1 monocytes incubated with human immunoglobulin G, phorbol myristate acetate and low density lipoprotein, the intracellular total cholesterol, free cholesterol, cholesteryl ester and lipid peroxides clearly increased, and a larger number of foam cells were observed by oil red O staining. The accumulation of all intracellular lipids was significantly inhibited by vinylbenzoic acid, and only slightly affected by catalase. These findings suggested that the production of O3, rather than H2O2, might be involved in the pathogenesis of atherosclerosis through the antibody-catalyzed water oxidation pathway.

  5. Affinity labelling enzymes with esters of aromatic sulfonic acids (United States)

    Wong, Show-Chu; Shaw, Elliott


    Novel esters of aromatic sulfonic acids are disclosed. The specific esters are nitrophenyl p- and m-amidinophenylmethanesulfonate. Also disclosed is a method for specific inactivation of the enzyme, thrombin, employing nitrophenyl p-amidinophenylmethanesulfonate.

  6. Chiral extraction of ketoprofen enantiomers with chiral selector tartaric esters

    Institute of Scientific and Technical Information of China (English)

    ZHOU Dan; LIU Jia-jia; TANG Ke-wen; HUANG Ke-long


    Distribution behavior of ketoprofen enantiomers was examined in methanol aqueous and organic solvent mixture containing tartaric esters. The influence of length of alkyl chain of tartaric esters, concentration of L-tartaric esters and methanol aqueous, kind of organic solvent on partition ratio and separation factors was investigated. The results show that L-tartaric and D-tartaric esters have different chiral recognition abilities. S-ketoprofen is easily extracted by L-tartaric esters, and R-ketoprofen is easily extracted by D-tartaric esters. L-tartaric esters form more stable diastereomeric complexes with S-enantiomer than that with R-enantiomer. This distribution behavior is consistent with chiral recognition mechanism. With the increase of the concentration of tartaric ester from 0 to 0.3 mol/L, partition coefficient K and separation factor α increase. Also, the kind of organic solvent and the concentration of the methanol aqueous have significant influence on K and α.

  7. NF EN 14103. July 2003. Fatty compounds derived products. Fatty acids methylic esters (FAME). Determination of the ester and methylic ester content of linoleic acid; NF EN 14103. Juillet 2003. Produits derives des corps gras. Esters methyliques d'acides gras (EMAG). Determination de la teneur en ester et en ester methylique de l'acide linolenique

    Energy Technology Data Exchange (ETDEWEB)



    This European standard aims at determining the ester and methylic ester content of fatty acids methylic esters (FAME) used as pure bio-fuels or as constituent of a heating or diesel fuel. This method allows also to determine the methylic ester content of linoleic acid. It allows to verify that the ester content of FAMEs is greater than 90% (m/m) and that the linoleic acid content is comprised between 1% (m/m) and 15% (m/m). The method is applicable to FAMEs with methylic ester contents comprised between C14 and C24. (J.S.)

  8. Gold-Catalyzed Direct Arylation


    Ball, L. T.; Lloyd-jones, G. C.; Russell, C. A.


    Biaryls (two directly connected aromatic rings, Ar1-Ar2) are common motifs in pharmaceuticals, agrochemicals, and organic materials. Current methods for establishing the Ar1-Ar2 bond are dominated by the cross-coupling of aryl halides (Ar1-X) with aryl metallics (Ar2-M). We report that, in the presence of 1 to 2 mole percent of a gold catalyst and a mild oxidant, a wide range of arenes (Ar1-H) undergo site-selective arylation by arylsilanes (Ar2-SiMe3) to generate biaryls (Ar1-Ar2), with litt...

  9. Yarrowia lipolytica lipase Lip2: an efficient enzyme for the production of concentrates of docosahexaenoic acid ethyl ester. (United States)

    Casas-Godoy, Leticia; Meunchan, Muchalin; Cot, Marlène; Duquesne, Sophie; Bordes, Florence; Marty, Alain


    The production of Omega-3 (ω-3) polyunsaturated fatty acids (PUFAs) rich in cis-4,7,10,13,16,19-docosahexaenoic acid (DHA) was studied using lipase-catalysed hydrolysis of a mixture of ethyl esters from tuna oil. Lipases from Yarrowia lipolytica (YLL2), Thermomyces lanuginosus (TLL) and Candida rugosa (CRL1, CRL3 and CRL4) were tested. C. rugosa lipases discriminated esters on the basis of their chain length, with less affinity for γ-linolenate, 11-eicosenoate, arachidonate, EPA, DPA and DHA ethyl esters. However, YLL2 and TLL improved discrimination towards DHA, as enzyme selectivity was shown to be mainly based on the position of the double bond closest to the carboxylic group. From the point of view of kinetics, purity and yield, YLL2 was the most effective lipase for DHA purification. Using this enzyme in an open reactor process resulted in the highest concentrations of DHA ethyl ester (77%) and ω-3 esters (81%) with a recovery of 94% and 77% respectively. PMID:24657346

  10. Weak bond screening system (United States)

    Chuang, S. Y.; Chang, F. H.; Bell, J. R.

    Consideration is given to the development of a weak bond screening system which is based on the utilization of a high power ultrasonic (HPU) technique. The instrumentation of the prototype bond strength screening system is described, and the adhesively bonded specimens used in the system developmental effort are detailed. Test results obtained from these specimens are presented in terms of bond strength and level of high power ultrasound irradiation. The following observations were made: (1) for Al/Al specimens, 2.6 sec of HPU irradiation will screen weak bond conditions due to improper preparation of bonding surfaces; (2) for composite/composite specimens, 2.0 sec of HPU irradiation will disrupt weak bonds due to under-cured conditions; (3) for Al honeycomb core with composite skin structure, 3.5 sec of HPU irradiation will disrupt weak bonds due to bad adhesive or oils contamination of bonding surfaces; and (4) for Nomex honeycomb with Al skin structure, 1.3 sec of HPU irradiation will disrupt weak bonds due to bad adhesive.

  11. Long-lived testosterone esters in the rat.


    Borg, W; Shackleton, C. H.; Pahuja, S L; Hochberg, R B


    Over the past decade it has become increasingly clear that steroid hormones are enzymatically esterified with fatty acids. These steroidal esters are the natural analogs of synthetic esters that are used therapeutically. One such family of pharmacological steroids is the synthetic alkyl esters of testosterone, androgens with great hormonal potency. We have investigated whether testosterone esters exist naturally by using the rat as a model. Most tissues of male rats, including blood, have ver...



    DOS SANTOS, Marcel Silveira


    Phthalates are a group of diesters of phthalic acid (dialkyl or alkyl aryl esters of 1,2-benzenedicarboxylic acid) and they are primarily used as plasticizers (substances added to plastics to increase their flexibility). As the phthalates are not chemically bonded to the polymer, these compounds can migrate from the plastic material to the environment and, consequently, they are found in food, water, soil, air and in the human body. This article discusses the problem of using those compoun...

  13. Rapid Estimation of Enantioselectivity in Lipase-catalyzed Resolution of Glycidyl Butyrate Using pH Indicator

    Institute of Scientific and Technical Information of China (English)

    WANG Ping; WANG Lei; WANG Li-cheng; LI Chun-yuan; WANG Ren; MIAO Qing-hua; YANG Ming; WANG Zhi


    A simple method for rapid estimation of the enantioselectivity of lipase in resolution of chiral esters is described. The enantioselectivity of lipase can be estimated rapidly through comparing the dif-ference of hydrolysis rates for the racemic ester and its slow reacting enantiomer under the same condition because the difference mainly depends on the enantioselective ratio(E values). The higher the enantiose-lectivity of enzyme, the larger the difference of hydrolysis rate. The bromothymol blue(BTB) can be used as pH indicator for microplate reader to monitor the formation of acid in lipase-catalyzed hydrolysis ofesters. This method has been successfully used to rapidly estimate the enantioselectivity of several lipases in the resolution of glycidyl butyrate.

  14. Palladium-catalyzed Reppe carbonylation. (United States)

    Kiss, G


    PdX2L2/L/HA (A = weakly coordinating anion, L = phosphine) complexes are active catalysts in the hydroesterification of alkenes, alkynes, and conjugated dienes. Shell, the only major corporate player in the field, recently developed two very active catalyst systems tailored to the hydroesterification of either alkenes or alkynes. The hydroesterification of propyne with their Pd(OAc)2/PN/HA (PN = (2-pyridyl)diphenylphosphine, HA = strong acid with weakly coordinating anion, like methanesulfonic acid) catalyst has been declared commercially ready. However, despite the significant progress in the activity of Pd-hydroesterification catalysts, further improvements are warranted. Thus, for example, activity maintenance still seems to be an issue. Homogeneous Pd catalysts are prone to a number of deactivation reactions. Activity and stability promoters are often corrosive and add to the complexity of the system, making it less attractive. Nonetheless, the versatility of the process and its tolerance toward the functional groups of substrates should appeal especially to the makers of specialty products. Although hydroesterification yields esters from alkenes, alkynes, and dienes in fewer steps than hydroformylation does, the latter has some advantages at the current state of the art. (1) Hydroformylation catalysts, particularly some recently published phosphine-modified Rh systems, can achieve very high regioselectivity for the linear product that hydroesterification catalysts cannot match yet. By analogy with hydroformylation, bulkier ligands ought to be tested in hydroesterification to increase normal-ester selectivity. (2) Hydroformylation is proven, commercial. Hydroesterification can only replace it if it can provide significant economic incentives. Similar or just marginally better performance could not justify the cost of development of a new technology. (3) Hydroesterification requires pure CO while hydroformylation uses syngas, a mixture of CO and H2. The latter

  15. Acrylic Acid and Esters Will Be Oversupply

    Institute of Scientific and Technical Information of China (English)

    Zheng Chengwang


    @@ Drastic capacity growth The production capacity of acrylic acid in China has grown drastically in recent years. With the completion of the 80 thousand t/a acrylic acid and 130 thous and t/a acrylic ester project in Shenyang Paraffin Chemical Industrial Co., Ltd., (CCR2006,No. 31) the capacity of acrylic acid in China has reached 882 thousand t/a.

  16. Avocado and olive oil methyl esters (United States)

    Biodiesel, the mono-alkyl esters of vegetable oils, animal fats or other triacylglycerol-containing materials and an alternative to conventional petroleum-based diesel fuel, has been derived from a variety of feedstocks. Numerous feedstocks have been investigated as potential biodiesel sources, incl...

  17. Determination of Mass Spectrometric Sensitivity of Different Metalloporphyrin Esters Relative to Porphyrin Ester

    DEFF Research Database (Denmark)

    Larsen, Elfinn; Egsgaard, Helge; Møller, J.;


    Quantitative determination of metalloporphyrin contamination in preparations of biologically important porphyrins was achieved mass spectrometrically by application of the integrated ion current technique. For this purpose, the relative molecular ion sensitivities of the contaminating metal...... complexes were determined from the ratios of the integrated molecular ion currents of a series of calibration samples containing a porphyrin ester and one of its metal complexes in known molar ratio. Complexes formed with divalent ions of Cu, Zn, Fe, Co and Ni of copro- as well as uro......-prophyrin permethylester were all found to have the same molecular ion sensitivities as their metal-free porphyrin ester. The relative metalloporphyrin ester content in a sample of porphyrin ester was thus obtained directly as the integrated ion current ratios of the normalized molecular ions. The preparation of...

  18. Ester Tuiksoo - Eesti esimene naissoost põllumajandusminister / Ester Tuiksoo ; interv. Toomas Verrev

    Index Scriptorium Estoniae

    Tuiksoo, Ester, 1965-


    Ametist lahkuv põllumajandusminister Ester Tuiksoo räägib saadud juhtimiskogemusest, Euroopa Liidu ühise põllumajanduspoliitika juurutamisest, rahvuskala valimisest, Rahvaliidu käekäigust parlamendivalimistel

  19. 21 CFR 175.210 - Acrylate ester copolymer coating. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylate ester copolymer coating. 175.210 Section... COATINGS Substances for Use as Components of Coatings § 175.210 Acrylate ester copolymer coating. Acrylate ester copolymer coating may safely be used as a food-contact surface of articles intended for...

  20. Half esters and coating compositions comprising reactions products of half esters and polyepoxides


    Blaauw, R; Mulder, W J; Koelewijn, R.; Boswinkel, G.


    The present invention relates to half esters based on dicarboxylic acid derivatives and dimer fatty diols, wherein the dimer fatty dio ls are based on dimerised and/or trimerised and/or oligomerised unsaturated fatty acids. The present invention further relates to resin compositions based on the half ester and an polyepoxide. The resin composition can be used in high solids coatings, inks, adhesives, wall covering products, flooring products and plastic products

  1. Expanding the modular ester fermentative pathways for combinatorial biosynthesis of esters from volatile organic acids. (United States)

    Layton, Donovan S; Trinh, Cong T


    Volatile organic acids are byproducts of fermentative metabolism, for example, anaerobic digestion of lignocellulosic biomass or organic wastes, and are often times undesired inhibiting cell growth and reducing directed formation of the desired products. Here, we devised a general framework for upgrading these volatile organic acids to high-value esters that can be used as flavors, fragrances, solvents, and biofuels. This framework employs the acid-to-ester modules, consisting of an AAT (alcohol acyltransferase) plus ACT (acyl CoA transferase) submodule and an alcohol submodule, for co-fermentation of sugars and organic acids to acyl CoAs and alcohols to form a combinatorial library of esters. By assembling these modules with the engineered Escherichia coli modular chassis cell, we developed microbial manufacturing platforms to perform the following functions: (i) rapid in vivo screening of novel AATs for their catalytic activities; (ii) expanding combinatorial biosynthesis of unique fermentative esters; and (iii) upgrading volatile organic acids to esters using single or mixed cell cultures. To demonstrate this framework, we screened for a set of five unique and divergent AATs from multiple species, and were able to determine their novel activities as well as produce a library of 12 out of the 13 expected esters from co-fermentation of sugars and (C2-C6) volatile organic acids. We envision the developed framework to be valuable for in vivo characterization of a repertoire of not-well-characterized natural AATs, expanding the combinatorial biosynthesis of fermentative esters, and upgrading volatile organic acids to high-value esters. Biotechnol. Bioeng. 2016;113: 1764-1776. © 2016 Wiley Periodicals, Inc. PMID:26853081

  2. Synthesis of 11C labelled methyl esters: transesterification of enol esters versus BF3 catalysed esterification-a comparative study

    International Nuclear Information System (INIS)

    C-11 labelled methyl esters have been synthesized via the transesterification of enol esters in the presence of C-11 methanol and 1,3 dichlorodibutylstannoxane as catalyst. This method leaves functional groups intact and allows access to a wider variety of C-11 labelled methyl esters compared to the BF3 catalysed ester formation, which uses carboxylic acids and C-11 methanol as starting materials

  3. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G


    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  4. Equilibrium CO bond lengths (United States)

    Demaison, Jean; Császár, Attila G.


    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 Å within the full range of 1.10-1.43 Å, corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  5. The Bond Market's q


    Thomas Philippon


    I propose an implementation of the q-theory of investment using bond prices instead of equity prices. Credit risk makes corporate bond prices sensitive to future asset values, and q can be inferred from bond prices. The bond market's q performs much better than the usual measure in standard investment equations. With aggregate data, the fit is three times better, cash flows are driven out and the implied adjustment costs are reduced by more than an order of magnitude. The new measure also imp...

  6. NMR Studies of a New Binding Mode of the Amino Acid Esters by Porphyrinatozinc(Ⅱ)

    Institute of Scientific and Technical Information of China (English)


    The binding mode of the amino acid ethyl esters(guest) by 5-(2-carboxylphenyl)-10,15,20-triphenylporphyrinatozinc(Ⅱ)(host 1) was studied by means of 1H NMR spectra. The binding mode is the hydrogen-bonding between the amino group of the guest and the carboxyl group of host 1 plus the coordination between the zinc atom of porphyrinatozinc(Ⅱ) and the carbonyl group of the guest. This is a novel binding mode of the metalloporphyrin to amino acid derivatives.

  7. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, Guy [Univ. of California, San Diego, CA (United States)


    high temperatures and long reaction times. To address this issue, we have developed several new families of carbon- and boron-based ligands, which are even better donors. The corresponding metal complexes (particularly gold, rhodium, iridium, and ruthenium) of all these species will be tested in the Markovnikov and anti-Markovnikov hydroamination of alkynes, allenes, and also alkenes with ammonia and hydrazine. We will also develop metal-free catalytic processes for the functionalization of ammonia and hydrazine. By possessing both a lone pair of electrons and an accessible vacant orbital, singlet carbenes resemble and can mimic the chemical behavior of transition metals. Our preliminary results demonstrate that specially designed carbenes can split the N–H bond of ammonia by an initial nucleophilic activation that prevents the formation of Lewis acid-base adducts, which is the major hurdle for the transition metal catalyzed functionalization of NH3. The use of purely organic compounds as catalysts will eliminate the major drawbacks of transition-metal-catalysis technology, which are the excessive cost of metal complexes (metal + ligands) and in many cases the toxicity of the metal.

  8. Suzuki-Miyaura Cross-Coupling Reactions of Unactivated Alkyl Halides Catalyzed by a Nickel Pincer Complex


    Di Franco, Thomas; Boutin, Nicolas; Hu, Xile


    A nickel(II) pincer complex, [((N2N)-N-Me)Ni-Cl], was used to catalyze alkyl-alkyl and alkyl-aryl Suzuki-Miyaura coupling reactions of unactivated alkyl halides. The coupling of 9-alkyl-9-borabicyclo[3.3.1]nonane and 9-phenyl-9-borabicyclo[3.3.1]nonane reagents with alkyl halides was achieved in modest to good yields. The reactions tolerated a variety of useful functional groups including ester, ether, furan, thioether, acetal, and Boc groups.

  9. Rh-Catalyzed reductive Mannich-type reaction and its application towards the synthesis of (±)-ezetimibe (United States)

    Isoda, Motoyuki; Sato, Kazuyuki; Kunugi, Yurika; Tokonishi, Satsuki; Tarui, Atsushi; Minami, Hideki


    Summary An effective synthesis for syn-β-lactams was achieved using a Rh-catalyzed reductive Mannich-type reaction. A rhodium–hydride complex (Rh–H) derived from diethylzinc (Et2Zn) and a Rh catalyst was used for the 1,4-reduction of an α,β-unsaturated ester to give a Reformatsky-type reagent, which in turn, reacted with an imine to give the syn-β-lactam. Additionally, the reaction was applied to the synthesis of (±)-ezetimibe, a potent β-lactamic cholesterol absorption inhibitor. PMID:27559413

  10. End-labeled amino terminated monotelechelic glycopolymers generated by ROMP and Cu(I-catalyzed azide–alkyne cycloaddition

    Directory of Open Access Journals (Sweden)

    Ronald Okoth


    Full Text Available Functionalizable monotelechelic polymers are useful materials for chemical biology and materials science. We report here the synthesis of a capping agent that can be used to terminate polymers prepared by ring-opening metathesis polymerization of norbornenes bearing an activated ester. The terminating agent is a cis-butene derivative bearing a Teoc (2-trimethylsilylethyl carbamate protected primary amine. Post-polymerization modification of the polymer was accomplished by amidation with an azido-amine linker followed by Cu(I-catalyzed azide–alkyne cycloaddition with propargyl sugars. Subsequent Teoc deprotection and conjugation with pyrenyl isothiocyanates afforded well-defined end-labeled glycopolymers.

  11. Production of Structured Phosphatidylcholine with High Content of DHA/EPA by Immobilized Phospholipase A1-Catalyzed Transesterification


    Xiang Li; Jia-Feng Chen; Bo Yang; Dao-Ming Li; Yong-Hua Wang; Wei-Fei Wang


    This paper presents the synthesis of structured phosphatidylcholine (PC) enriched with docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA) by transesterification of DHA/EPA-rich ethyl esters with PC using immobilized phospholipsase A1 (PLA1) in solvent-free medium. Firstly, liquid PLA1 was immobilized on resin D380, and it was found that a pH of 5 and a support/PLA1 ratio (w/v) of 1:3 were the best conditions for the adsorption. Secondly, the immobilized PLA1 was used to catalyze trans...

  12. Synthesis and Triethylamine-catalyzed Cyclization Reaction of 4-Pentyne-1,3-dione System Having Various Substituents

    Institute of Scientific and Technical Information of China (English)

    KURODA,Hirofumi; IZAWA,Hironori


    4-Pentyne-1,3-dione system having various substituents was synthesized in two steps and the cyclization behavior of the obtained 1 ,3-dicarbonyl compounds was examined. y-Pyrones and 2-alkylidene-2,3-dihydro-3-fu-ranones were obtained by the triethylamine-catalyzed cyclization of the 4-pentyne-l,3-dione system having a dike-tone moiety. Furthermore, a phenol derivative was obtained in the case of 4-pentyne-1,3-dione system having an ester moiety. Thus, it was found that the kind of substituents in the 4-pentyne-1,3-dione system remarkably influenced the selectivity in the cyclization.

  13. Extraction of microalgal lipids and the influence of polar lipids on biodiesel production by lipase-catalyzed transesterification. (United States)

    Navarro López, Elvira; Robles Medina, Alfonso; González Moreno, Pedro Antonio; Esteban Cerdán, Luis; Molina Grima, Emilio


    In order to obtain microalgal saponifiable lipids (SLs) fractions containing different polar lipid (glycolipids and phospholipids) contents, SLs were extracted from wet Nannochloropsis gaditana microalgal biomass using seven extraction systems, and the polar lipid contents of some fractions were reduced by low temperature acetone crystallization. We observed that the polar lipid content in the extracted lipids depended on the polarity of the first solvent used in the extraction system. Lipid fractions with polar lipid contents between 75.1% and 15.3% were obtained. Some of these fractions were transformed into fatty acid methyl esters (FAMEs, biodiesel) by methanolysis, catalyzed by the lipases Novozym 435 and Rhizopus oryzae in tert-butanol medium. We observed that the reaction velocity was higher the lower the polar lipid content, and that the final FAME conversions achieved after using the same lipase batch to catalyze consecutive reactions decreased in relation to an increase in the polar lipid content. PMID:27323242

  14. Synthesis of pteroylglutamic acid-3',5'-2H2 by trifluoroacetic acid catalyzed exchange with deuterium oxide

    International Nuclear Information System (INIS)

    Pteroylglutamic acid (PGA) was deuterated by trifluoroacetic acid catalyzed exchange with deuterium oxide. The product, pteroylglutamic acid-3',5'-2H2, was specifically deuterated in the aromatic protons of the p-aminobenzoyl (PABA) moiety; the protons on C7 and C9 and in the glutamic acid residue were not exchanged. Deuterium incorporation was measured by chemical ionization mass spectrometry (CI-MS). Pteroylglutamates were cleaved by a base-catalyzed, oxidative hydrolysis to PABA, which was converted to the methyl ester, N-trifluoroacetate for analysis by gas chromatography-chemical ionization-mass spectrometry. Products from the exchange typically contained 1 percent 2H1 and 90 percent 2H2 species. The procedure may be used to label specifically various analogs of PGA with deuterium in the PABA portion of the molecule

  15. Palladium-catalyzed direct arylation and cyclization of o-iodobiaryls to a library of tetraphenylenes (United States)

    Zhu, Chendan; Zhao, Yue; Wang, Di; Sun, Wei-Yin; Shi, Zhuangzhi


    Aryl–aryl bond formation constitutes one of the most important subjects in organic synthesis. The recent developments in direct arylation reactions forming aryl–aryl bond have emerged as very attractive alternatives to traditional cross-coupling reactions. Here, we describe a general palladium-catalyzed direct arylation and cyclization of o-iodobiaryls to build a library of tetraphenylenes. This transformation represents one of the very few examples of C-H activation process that involves simultaneous formation of two aryl–aryl bonds. Oxygen plays a vital role by ensuring high reactivity, with air as the promoter furnished the best results. We anticipate this ligand-free and aerobic catalytic system will simplify the synthesis of tetraphenylenes as many of the reported methods involve use of preformed organometallic reagents and will lead to the discovery of highly efficient new direct arylation process.

  16. Catalytic effect of carbon nanotubes on polymerization of cyanate ester resins

    Directory of Open Access Journals (Sweden)


    Full Text Available Kinetic peculiarities of polycyclotrimerization process of dicyanate ester of bisphenol A (DCBA in the presence of multi-walled carbon nanotubes (MWCNTs have been investigated using Fourier Transform Infrared Spectroscopy (FTIR spectroscopy technique. It has been found that even very small amounts of MWCNTs (0.01–0.1 wt% catalyze the reaction of polycyclotrimerization of DCBA leading to formation of polycyanurate network (PCN/MWCNTs nanocomposite. However, some decrease in final degree of conversion for nanocomposites compared to the neat PCN within the temperature/time schedule used was observed. The kinetic rate constants increased with addition of MWCNTs and energies of activation were found to be significantly decreased even at low contents of MWCNTs.

  17. Preparation and characterization of carbosilane denddmer-bonded silica gel and its use in LC

    Institute of Scientific and Technical Information of China (English)

    Chen Guowen; Zhao Shigui; Feng Shengyu


    Divergently synthesized carbosilane dendrimers generations 1(G1) and 2 (G2) with allyl end groups were bonded onto silica gel.Reactions between the dendrimers and acid-processed silica gel took place,with toluene reflux and organic base as catalyst.Chemically bonded silica gel was characterized by transmission electron microscopy (TEM),infrared (IR),and other methods.The chemically modified silica gels were packed into high-pressure liquid chromatography (HPLC) column and their separation characters were evaluated.G2-bonded silica gel was effective in separating homologous compounds of alcohol, alkyl-substituted benzene,N-substituted benzene,metacrylic acid ester and phthalate.

  18. Comparison of Gold Bonding with Mercury Bonding

    NARCIS (Netherlands)

    Kraka, Elfi; Filatov, Michael; Cremer, Dieter


    Nine AuX molecules (X = H, O, S, Se, Te, F, Cl, Br, I), their isoelectronic HgX(+) analogues, and the corresponding neutral HgX diatomics have been investigated using NESC (Normalized Elimination of the Small Component) and B3LYP theory to determine relativistic effects for bond dissociation energie

  19. Real-Time monitoring of intracellular wax ester metabolism

    Directory of Open Access Journals (Sweden)

    Karp Matti


    Full Text Available Abstract Background Wax esters are industrially relevant molecules exploited in several applications of oleochemistry and food industry. At the moment, the production processes mostly rely on chemical synthesis from rather expensive starting materials, and therefore solutions are sought from biotechnology. Bacterial wax esters are attractive alternatives, and especially the wax ester metabolism of Acinetobacter sp. has been extensively studied. However, the lack of suitable tools for rapid and simple monitoring of wax ester metabolism in vivo has partly restricted the screening and analyses of potential hosts and optimal conditions. Results Based on sensitive and specific detection of intracellular long-chain aldehydes, specific intermediates of wax ester synthesis, bacterial luciferase (LuxAB was exploited in studying the wax ester metabolism in Acinetobacter baylyi ADP1. Luminescence was detected in the cultivation of the strain producing wax esters, and the changes in signal levels could be linked to corresponding cell growth and wax ester synthesis phases. Conclusions The monitoring system showed correlation between wax ester synthesis pattern and luminescent signal. The system shows potential for real-time screening purposes and studies on bacterial wax esters, revealing new aspects to dynamics and role of wax ester metabolism in bacteria.

  20. Curing mechanism of alkaline phenolic resin with organic ester

    Institute of Scientific and Technical Information of China (English)

    Huang Renhe; Wang Yanmin; Zhang Baoping


    To study the curing mechanism of alkaline phenolic resin with organic ester, three esters were chosen to react with three systems - alkaline phenolic resin, potassium hydroxide aqueous solution containing phenol, and potassium hydroxide aqueous solution. The variations of pH, heat release and gel pH during the reactions were monitored and measured. Infrared spectroscopy (IR) and thermal gravity analysis (TG) techniques were used to characterize the curing reaction. It was found that organic ester is only partial y hydrolyzed and resin can be cured through organic ester hydrolysis process as wel as the reaction with redundant organic ester. The sequential curing mechanism of alkaline phenolic resin cured by organic ester was identified as fol ows: a portion of organic ester is firstly hydrolyzed owing to the effect of the strong alkaline; the gel is then formed after the pH decreases to about 10.8-10.88, meanwhile, the redundant organic ester (i.e. non-hydrolysis ester) starts the curing reaction with the resin. It has also been found that the curing rate depends on the hydrolysis velocity of organic ester. The faster the hydrolysis speed of the ester, the faster the curing rate of the resin.

  1. Effects of ultraviolet irradiation on bonding strength between Co-Cr alloy and citric acid-crosslinked gelatin matrix. (United States)

    Inoue, Motoki; Sasaki, Makoto; Katada, Yasuyuki; Taguchi, Tetsushi


    Novel techniques for creating a strong bond between polymeric matrices and biometals are required. We immobilized polymeric matrices on the surface of biometal for drug-eluting stents through covalent bond. We performed to improve the bonding strength between a cobalt-chromium alloy and a citric acid-crosslinked gelatin matrix by ultraviolet irradiation on the surface of cobalt-chromium alloy. The ultraviolet irradiation effectively generated hydroxyl groups on the surface of the alloy. The bonding strength between the gelatin matrix and the alloy before ultraviolet irradiation was 0.38 ± 0.02 MPa, whereas it increased to 0.48 ± 0.02 MPa after ultraviolet irradiation. Surface analysis showed that the citric acid derivatives occurred on the surface of the cobalt-chromium alloy through ester bond. Therefore, ester bond formation between the citric acid derivatives active esters and the hydroxyl groups on the cobalt-chromium alloy contributed to the enhanced bonding strength. Ultraviolet irradiation and subsequent immobilization of a gelatin matrix using citric acid derivatives is thus an effective way to functionalize biometal surfaces.

  2. Fullerene-catalyzed reduction of azo derivatives in water under UV irradiation

    KAUST Repository

    Guo, Yong


    Metal-free fullerene (C60) was found to be an effective catalyst for the reduction of azo groups in basic aqueous solution under UV irradiation in the presence of NaBH4. Use of NaBH4 by itself is not sufficient to reduce the azo dyes without the assistance of a metal catalyst such as Pd and Ag. Experimental and theoretical results suggest that C 60 catalyzes this reaction by using its vacant orbital to accept the electron in the bonding orbital of azo dyes, which leads to the activation of the N=N bond. UV irradiation increases the ability of C60 to interact with electron-donor moieties in azo dyes. Filling a vacancy: Experimental and theoretical methods have been combined to show that C60-catalyzed reductions of azo compounds form aromatic amines under UV irradiation (see scheme). The obtained results show that C60 acts as an electron acceptor to catalyze the reduction of azo compounds, and the role of UV irradiation is to increase the ability of C60 to interact with electron-donor moieties in azo compounds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Coupled valence bond theory

    NARCIS (Netherlands)

    Havenith, R.W.A.


    In this Letter, the formulation and implementation of a parallel response property code for non-orthogonal, valence bond wave-functions are described. Test calculations on benzene and cyclobutadiene show that the polarisability and magnetisability tensors obtained using valence bond theory are compa

  4. Bonded labour in Pakistan


    Ercelawn, Aly; Nauman, Muhammad


    Examines the continuing prevalence of debt bondage in the 1990s despite the introduction of national legislation banning the practice. Makes recommendations to the Government and the international community for actions to be taken to eliminate bonded labour and provide rehabilitation for freed workers. Includes texts of Land Reforms Regulations, 1972, the Sindh Tenancy Act, 1950 and the Bonded Labour System (Abolition) Act, 1992.

  5. Hydrogen bonding in polyanilines

    Energy Technology Data Exchange (ETDEWEB)

    Bahceci, S. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey)); Toppare, L. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey)); Yurtsever, E. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey))


    Hydrogen bonding between poly(bisphenol A carbonate) (PC) and polyaniline (PAn) is analyzed using semi-empirical quantum methodology. Fully optimized AM1 molecular orbital calculations are reported for various aniline structures (monomer, dimer and trimer), the monomer of the PC and the hydrogen-bonded model of PAn-PC oligomer. ((orig.))

  6. The dissociative bond. (United States)

    Gordon, Nirit


    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other.

  7. The samurai bond market


    Frank Packer; Elizabeth Reynolds


    Issuance in the samurai bond market has more than tripled over the past several years. Some observers have attributed this growth to a systematic underestimation of credit risk in the market. A detailed review of credit quality, ratings differences, and initial issue pricing in the samurai bond market, however, turns up little evidence to support this concern.

  8. Dry chemical pretreatment of titanium and polymers for adhesive bonding. Trockenchemische Vorbehandlung von Titan und Kunststoffen fuer das Kleben

    Energy Technology Data Exchange (ETDEWEB)

    Krueger, G.; Hennemann, O.D. (Fraunhofer-Institut fuer Angewandte Materialforschung, Bremen (Germany))


    Titan alloys have to be pretreated to increase the adhesive bonding strength. Because of environmental reasons dry chemical pretreatment methods are preferred compared to wet chemical techniques. One successful method is a silicatisation referring to the Saco-technique. Layers generated by this method on titanium or polymer substrates lead to highly water-resistant adhesive bondings. Also adhesive joints of Ti with polymer show high bond strength when polymer and Ti are Saco treated. With a suitable optimization of the technological parameters it is possible to adhesively bond polymers also with anaerobic acrylic esters. (orig.).

  9. Horseradish peroxidase-catalyzed polymerization of cardanol in the presence of redox mediators. (United States)

    Won, Keehoon; Kim, Yong Hwan; An, Eun Suk; Lee, Yeon Soo; Song, Bong Keun


    Horseradish peroxidase-catalyzed polymerization of cardanol in aqueous organic solvent was investigated in the presence of a redox mediator. Cardanol is a phenol derivative from a renewable resource mainly having a C15 unsaturated hydrocarbon chain with mostly 1-3 double bonds at a meta position. Unlike soybean peroxidase (SBP), it has been shown that horseradish peroxidase (HRP) is not able to perform oxidative polymerization of phenol derivatives having a bulky meta substituent such as cardanol. For the first time, redox mediators have been applied to enable horseradish peroxidase to polymerize cardanol. Veratryl alcohol, N-ethyl phenothiazine, and phenothiazine-10-propionic acid were tested as a mediator. It is surprising that the horseradish peroxidase-catalyzed polymerization of cardanol took place in the presence of N-ethyl phenothiazine or phenothiazine-10-propionic acid. However, veratryl alcohol showed no effect. FT-IR and GPC analysis of the product revealed that the structure and properties of polycardanol formed by HRP with a mediator were similar to those by SBP. This is the first work to apply a redox mediator to enzyme-catalyzed oxidative polymerization. Our new finding that oxidative polymerization of a poor substrate, which the enzyme is not active with, can take place in the presence of an appropriate mediator will present more opportunities for the application of enzyme-catalyzed polymerization. PMID:14715000

  10. Enzyme-Catalyzed Henry Reaction in Choline Chloride-Based Deep Eutectic Solvents. (United States)

    Tian, Xuemei; Zhang, Suoqin; Zheng, Liangyu


    The enzyme-catalyzed Henry reaction was realized using deep eutectic solvents (DESs) as a reaction medium. The lipase from Aspergillus niger (lipase AS) showed excellent catalytic activity toward the substrates aromatic aldehydes and nitromethane in choline chloride:glycerol at a molar ratio of 1:2. Addition of 30 vol% water to DES further improved the lipase activity and inhibited DES-catalyzed transformation. A final yield of 92.2% for the lipase AS-catalyzed Henry reaction was achieved under optimized reaction conditions in only 4 h. In addition, the lipase AS activity was improved by approximately 3-fold in a DES-water mixture compared with that in pure water, which produced a final yield of only 33.4%. Structural studies with fluorescence spectroscopy showed that the established strong hydrogen bonds between DES and water may be the main driving force that affects the spatial conformation of the enzyme, leading to a change in lipase activity. The methodology was also extended to the aza-Henry reaction, which easily occurred in contrast to that in pure water. The enantioselectivity of both Henry and aza-Henry reactions was not found. However, the results are still remarkable, as we report the first use of DES as a reaction medium in a lipase-catalyzed Henry reaction. PMID:26437947

  11. Wood Bond Testing (United States)


    A joint development program between Hartford Steam Boiler Inspection Technologies and The Weyerhaeuser Company resulted in an internal bond analyzer (IBA), a device which combines ultrasonics with acoustic emission testing techniques. It is actually a spinoff from a spinoff, stemming from a NASA Lewis invented acousto-ultrasonic technique that became a system for testing bond strength of composite materials. Hartford's parent company, Acoustic Emission Technology Corporation (AET) refined and commercialized the technology. The IBA builds on the original system and incorporates on-line process control systems. The IBA determines bond strength by measuring changes in pulsar ultrasonic waves injected into a board. Analysis of the wave determines the average internal bond strength for the panel. Results are displayed immediately. Using the system, a mill operator can adjust resin/wood proportion, reduce setup time and waste, produce internal bonds of a consistent quality and automatically mark deficient products.

  12. Water's Hydrogen Bond Strength

    CERN Document Server

    Chaplin, Martin


    Water is necessary both for the evolution of life and its continuance. It possesses particular properties that cannot be found in other materials and that are required for life-giving processes. These properties are brought about by the hydrogen bonded environment particularly evident in liquid water. Each liquid water molecule is involved in about four hydrogen bonds with strengths considerably less than covalent bonds but considerably greater than the natural thermal energy. These hydrogen bonds are roughly tetrahedrally arranged such that when strongly formed the local clustering expands, decreasing the density. Such low density structuring naturally occurs at low and supercooled temperatures and gives rise to many physical and chemical properties that evidence the particular uniqueness of liquid water. If aqueous hydrogen bonds were actually somewhat stronger then water would behave similar to a glass, whereas if they were weaker then water would be a gas and only exist as a liquid at sub-zero temperature...

  13. Synthesis of calixarenes and their extraction performance for ester catechins

    Institute of Scientific and Technical Information of China (English)


    A series of extractants (tert-butylcalix[6]arene, tert-butylcalix[8]arene and octeacetate of tert-butylcalix[8]arene) were synthesized, and their structures were identified by IR and 1H-NMR. The distribution behavior of ester catechins monomer in the aqueous and chloroform two-phase system containing one of calixarene was studied. The influences of different extractants,concentration of tert-butylcalix[8]arene and extraction temperature on the partition coefficients and the separation factors were investigated. The experiment results show that tert-butylcalix[8]arene is the best extractant that forms a more stable supramolecular compound with gallocatechin gallate (GCG) than with epigallocathechin gallate (EGCG) or epicatechin gallate (ECG). When the concentration ofp-tert-butylcalix[8]arene is 3.79 mmol/L, the extraction temperature is 4 ℃C, the partition coefficients of KGG cG, KECG,KEGG cG are 0.987, 0.629, 0.449, the separation factors ofα1 and α2 are 1.450 and 1.596, respectively. The important factors influencing the extraction properties of calixarene are discovered to be its cavity size and hydrogen bonding.

  14. Highly Efficient Cascade Reaction for Selective Formation of Spirocyclobutenes from Dienallenes via Palladium-Catalyzed Oxidative Double Carbocyclization–Carbonylation–Alkynylation (United States)


    A highly selective cascade reaction that allows the direct transformation of dienallenes to spirocyclobutenes (spiro[3.4]octenes) as single diastereoisomers has been developed. The reaction involves formation of overall four C–C bonds and proceeds via a palladium-catalyzed oxidative transformation with insertion of olefin, olefin, and carbon monoxide. Under slightly different reaction conditions, an additional CO insertion takes place to give spiro[4.4]nonenes with formation of overall five C–C bonds. PMID:27704805

  15. Effects of gamma-ray irradiation on a cyanate ester/epoxy resin

    International Nuclear Information System (INIS)

    Effects of γ-ray irradiation on a cyanate ester/epoxy resin composed of dicyanate ester of bisphenol A (DCBA) and diglycidyl ether of bisphenol A (DGEBA) were investigated by changes in physicochemical and mechanical properties after the γ-ray irradiation with dose of 100 MGy as maximum at around 40 °C under vacuum. After the irradiation, gases of hydrogen, carbon monoxide and carbon dioxide were evolved, glass transition temperature decreased, and flexural strength also decreased. It was concluded that ether linkages bonded to cyanurate, isocyanurate and oxazolidinone structures are mainly decomposed by the irradiation. After 100 MGy irradiation, the flexural strength of DCBA/DGEBA was maintained more than 170 MPa which is 90% of initial value of 195 MPa. Flexural modulus and density slightly increased to the values of 3.9 GPa and 1.211 g/cm3 from initial values of 3.4 GPa and 1.199 g/cm3, respectively. - Highlights: • A cyanate ester/epoxy resin was irradiated by γ-rays with dose of 100 MGy in vacuum. • Viscoelastic property, structural change and gas evolution were investigated. • Ether linkages in the network structure were mainly decomposed by the irradiation. • The flexural strength of resin was maintained >170 MPa which is 90% of initial value

  16. Adsorption of surfactants onto acrylic ester resins with different pore size distribution

    Institute of Scientific and Technical Information of China (English)

    YANG Weiben; LI Aimin; CAI Jianguo; MENG Guanhua; ZHANG Quanxing


    In this study, a series of acrylic ester resins with different pore size distribution were prepared successfully by varying the type and the amount of pore-forming agents. In order to investigate the adsorption behavior and mechanism of surfactants on acrylic ester resins, three kinds of surfactants were utilized as adsorbates that were sodium 6-dodecyl benzenesulfonate (6-NaDBS),sodium 1-dodecyl benzene sulfonate (1-NaDBS) and sodium 1-dodecyl sulfonate, respectively. It was observed that the surface area was available in a particular pore size and an appropriate pore size of resins appeared to be more important for the adsorption of surfactants. As compared to commercial acrylic ester resins XAD-7 and HP2MG, 50# and 38# resins exhibited more excellent adsorption properties toward 1-NaDBS and 6-NaDBS. The experimental equilibrium data were fitted to the Langmuir, and double-Langmuir models. Two models provided very good fittings for all resins over the temperature range studied. The investigation dicated that electrostatic attraction and hydrogen bond between resins and surfactants were the main forces and had an obvious effect on adsorption process.

  17. Atmospheric oxidation of selected alcohols and esters

    Energy Technology Data Exchange (ETDEWEB)

    Becker, K.H.; Cavalli, F.


    The decision whether it is appropriate and beneficial for the environment to deploy specific oxygenated organic compounds as replacements for traditional solvent types requires a quantitative assessment of their potential atmospheric impacts including tropospheric ozone and other photooxidant formation. This involves developing chemical mechanisms for the gasphase atmospheric oxidation of the compounds which can be reliably used in models to predict their atmospheric reactivity under a variety of environmental conditions. Until this study, there was very little information available concerning the atmospheric fate of alcohols and esters. The objectives of this study were to measure the atmospheric reaction rates and to define atmospheric reaction mechanisms for the following selected oxygenated volatile organic compounds: the alcohols, 1-butanol and 1-pentanol, and the esters, methyl propionate and dimethyl succinate. The study has successfully addressed these objectives. (orig.)

  18. Naturally occurring antifungal aromatic esters and amides

    International Nuclear Information System (INIS)

    During the search of antifungal natural products from terrestrial plants, a new long chained aromatic ester named grandiflorate along with spatazoate from Portulaca grandiflora and N-[2-methoxy-2-(4-methoxyphenyl) ethyl]-trans-cinnamide and aegeline from Solanum erianthum of Nigeria were isolated and tested against six fungal species. The known constituents have not been reported so far from mentioned investigated plants. Structures of the isolated compounds were elucidated with the aid of spectroscopic techniques including two dimensional NMR experiments. Among the compounds, the esters found more potent than amides against Candida albicans and Aspergillus flavus. The new compound grandiflorate gave response against all tested fungal species while aegeline was found to give lowest inhibition during this study. (author)

  19. Cobalt-catalyzed redox-neutral synthesis of isoquinolines:C-H activation assisted by an oxidizing N-S bond%三价钴催化下N-S键辅助的非氧化条件下经碳氢活化合成异喹啉

    Institute of Scientific and Technical Information of China (English)

    王芬; 王强; 包明; 李兴伟


    反应中以氮–氧键断裂作为内部氧化剂。但是在钴催化条件下氧化性的氮–硫键作为内部氧化剂辅助碳氢键活化的反应尚无报道。本课题组最近报道了芳基酮的N-亚磺酰亚胺与烯烃和胺化试剂的偶联反应,经N–S键断裂,高效合成了喹唑啉。本文利用三价钴催化剂在无外加氧化剂条件下实现了芳基酮N-亚磺酰亚胺与炔烃的偶联,反应经历了碳氢键活化和氮硫键断裂得到异喹啉。此反应对端炔和内炔底物均适用。为了初步了解反应机理,我们利用分子内竞争的方法进行了动力学同位素效应测定,结果表明碳氢键断裂过程可能是反应的决速步骤。结合文献结果,提出了可能的反应机理。%A redox‐neutral avenue to access isoquinolines has been realized by a Co(III)‐catalyzed C–H activa‐tion process. Starting from readily available N‐sulfinyl imine substrates and alkynes, the reaction occurred via N–S cleavage with broad substrate scope and functional group compatibility in the presence of cost‐effective cobalt catalysts.

  20. Withanolides and Sucrose Esters from Physalis neomexicana. (United States)

    Cao, Cong-Mei; Wu, Xiaoqing; Kindscher, Kelly; Xu, Liang; Timmermann, Barbara N


    Four withanolides (1-4) and two sucrose esters (5, 6) were isolated from the aerial parts of Physalis neomexicana. The structures of 1-6 were elucidated through a variety of spectroscopic techniques. Cytotoxicity studies of the isolates revealed that 2 inhibited human breast cancer cell lines (MDA-MB-231 and MCF-7) with IC50 values of 1.7 and 6.3 μM, respectively.

  1. Ultrasound assisted synthesis of isopropyl esters from palm fatty acid distillate. (United States)

    Deshmane, Vishwanath G; Gogate, Parag R; Pandit, Aniruddha B


    Esterification is one of the most preferred synthesis routes for organic esters which are most frequently used as plasticizers, solvents and perfumery and flavour chemicals. The present work deals with acid catalyzed synthesis of isopropyl esters from palm fatty acid distillate (PFAD) in the presence of ultrasonic irradiations operating at 25kHz frequency and 1kW of supplied power. Effect of different operating parameters such as molar ratio of reactants, catalyst quantity and operating temperature has been studied with an aim of optimization. It has been observed that ultrasound enhances the rate of reaction and the extent of equilibrium conversion. The optimum parameters for this process have been found to be 1:5 molar ratio of PFAD to isopropanol, catalyst concentration of 5% of PFAD and 60 degrees C reaction temperature. Maximum conversion levels of about 80% have been obtained in 6h of reaction time under these optimized conditions. Analysis of the kinetic data indicates that the reaction follows first order reversible path. PMID:18977682

  2. Orthogonal Fatty Acid Biosynthetic Pathway Improves Fatty Acid Ethyl Ester Production in Saccharomyces cerevisiae. (United States)

    Eriksen, Dawn T; HamediRad, Mohammad; Yuan, Yongbo; Zhao, Huimin


    Fatty acid ethyl esters (FAEEs) are a form of biodiesel that can be microbially produced via a transesterification reaction of fatty acids with ethanol. The titer of microbially produced FAEEs can be greatly reduced by unbalanced metabolism and an insufficient supply of fatty acids, resulting in a commercially inviable process. Here, we report on a pathway engineering strategy in Saccharomyces cerevisiae for enhancing the titer of microbially produced FAEEs by providing the cells with an orthogonal route for fatty acid synthesis. The fatty acids generated from this heterologous pathway would supply the FAEE production, safeguarding endogenous fatty acids for cellular metabolism and growth. We investigated the heterologous expression of a Type-I fatty acid synthase (FAS) from Brevibacterium ammoniagenes coupled with WS/DGAT, the wax ester synthase/acyl-coenzyme that catalyzes the transesterification reaction with ethanol. Strains harboring the orthologous fatty acid synthesis yielded a 6.3-fold increase in FAEE titer compared to strains without the heterologous FAS. Variations in fatty acid chain length and degree of saturation can affect the quality of the biodiesel; therefore, we also investigated the diversity of the fatty acid production profile of FAS enzymes from other Actinomyces organisms. PMID:25594225

  3. A monolithic lipase reactor for biodiesel production by transesterification of triacylglycerides into fatty acid methyl esters

    KAUST Repository

    Urban, Jiří T.


    An enzymatic reactor with lipase immobilized on a monolithic polymer support has been prepared and used to catalyze the transesterification of triacylglycerides into the fatty acid methyl esters commonly used for biodiesel. A design of experiments procedure was used to optimize the monolithic reactor with variables including control of the surface polarity of the monolith via variations in the length of the hydrocarbon chain in alkyl methacrylate monomer, time of grafting of 1-vinyl-4,4-dimethylazlactone used to activate the monolith, and time used for the immobilization of porcine lipase. Optimal conditions involved the use of a poly(stearyl methacrylate-co-ethylene dimethacrylate) monolith, grafted first with vinylazlactone, then treated with lipase for 2h to carry out the immobilization of the enzyme. Best conditions for the transesterification of glyceryl tributyrate included a temperature of 37°C and a 10min residence time of the substrate in the bioreactor. The reactor did not lose its activity even after pumping through it a solution of substrate equaling 1,000 reactor volumes. This enzymatic reactor was also used for the transesterification of triacylglycerides from soybean oil to fatty acid methyl esters thus demonstrating the ability of the reactor to produce biodiesel. © 2011 Wiley Periodicals, Inc.

  4. Ethyl ester production from (RBD palm oil

    Directory of Open Access Journals (Sweden)

    Oscar Mauricio Martínez Ávila


    Full Text Available This work develops a methodology for obtaining ethyl esters from RBD (refined, bleached and deodorised palm oil by evaluating the oil’s transesterification and separation. Two catalysts were first tested (KOH and NaOH by studying the effect of water presence on the reaction. The separation process was then evaluated by using water and water-salt and water-acid mixtures, establishing the agent offering the best results and carrying out the purification stage. Raw materials and products were characterised for comparing the latter with those obtained by traditional means and verifying the quality of the esters so produced; minimum differences were found bet-ween both. The proposed methodology thus allows esters to be used as raw material in petrochemical industry applications. A more profitable process can be obtained compared to those used today, given the amounts of separation agent so established (1% H3PO4 solution, in water. The overall process achieved 74.4% yield, based on the oil being used.

  5. An efficient and scalable one-pot double Michael addition-Dieckmann condensation for the synthesis of 4,4-disubstituted cyclohexane beta-keto esters. (United States)

    DeGraffenreid, Michael R; Bennett, Sarah; Caille, Sebastien; Gonzalez-Lopez de Turiso, Felix; Hungate, Randall W; Julian, Lisa D; Kaizerman, Jacob A; McMinn, Dustin L; Rew, Yosup; Sun, Daqing; Yan, Xuelei; Powers, Jay P


    A simple, scalable, and efficient one-pot methodology for the synthesis of 4,4-disubstituted cyclohexane beta-keto esters from benzylic nitriles or esters and methyl acrylate promoted by potassium tert-butoxide is described. The process relies on a tandem double Michael addition-Dieckmann condensation reaction, which results in the formation of three discrete carbon-carbon bonds in a single pot, including a quaternary center. The method allows for the convenient and rapid synthesis of a variety of 4-aryl-4-cyano-2-carbomethoxycyclohexanone and 4-aryl-2,4-biscarbomethoxycyclohexanone building blocks for use in natural products synthesis and medicinal chemistry. PMID:17696402

  6. Synthesis of phenanthridines via palladium-catalyzed picolinamide-directed sequential C–H functionalization

    Directory of Open Access Journals (Sweden)

    Ryan Pearson


    Full Text Available We report a new synthesis of phenanthridines based on palladium-catalyzed picolinamide-directed sequential C–H functionalization reactions starting from readily available benzylamine and aryl iodide precursors. Under the catalysis of Pd(OAc2, the ortho-C–H bond of benzylpicolinamides is first arylated with an aryl iodide. The resulting biaryl compound is then subjected to palladium-catalyzed picolinamide-directed intramolecular dehydrogenative C–H amination with PhI(OAc2 oxidant to form the corresponding cyclized dihydrophenanthridines. The benzylic position of these dihydrophenanthridines could be further oxidized with Cu(OAc2, removing the picolinamide group and providing phenathridine products. The cyclization and oxidation could be carried out in a single step and afford phenathridines in moderate to good yields.

  7. Pengaruh Katalis H2SO4 pada Reaksi Epoksidasi Metil Ester PFAD (Palm Fatty Acid Distillate)


    Sinaga, Mersi Suriani


    Ester epoksi selain sebagai pelunak juga dapat memperbaiki ketahanan komponen polivinil klorida (PVC) terhadap panas dan cahaya. Penelitian ini dilakukan untuk merumuskan kondisi katalis yang sesuai bagi pembuatan senyawa epoksi metil ester PFAD dari senyawa metil ester PFAD. Metil ester PFAD terdiri dari ester lemak jenuh dan tidak jenuh., metode pemisahan kristalisasi dengan pelarut metanol untuk memisahkan ester lemak jenuh dari ester lemak tak jenuh, yang bertujuan meningkatkan kemamp...

  8. Transversely Compressed Bonded Joints

    DEFF Research Database (Denmark)

    Hansen, Christian Skodborg; Schmidt, Jacob Wittrup; Stang, Henrik


    The load capacity of bonded joints can be increased if transverse pressure is applied at the interface. The transverse pressure is assumed to introduce a Coulomb-friction contribution to the cohesive law for the interface. Response and load capacity for a bonded single-lap joint was derived using...... non-linear fracture mechanics. The results indicated a good correlation between theory and tests. Furthermore, the model is suggested as theoretical base for determining load capacity of bonded anchorages with transverse pressure, in externally reinforced concrete structures....

  9. Chemo-enzymatic epoxidation of olefins by carboxylic acid esters and hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Ruesch gen. Klaas, M.; Warwel, S. [Inst. for Biochemistry and Technology of Lipids, H.P. Kaufmanm-Inst., Federal Centre for Cereal, Potato and Lipid Research, Muenster (Germany)


    Ethylen and, recently, butadiene can be epoxidized directly with oxygen and for the epoxidation of propylene, the use of heterogeneous transition metals and organic peroxides (Halcon-Process) is the major player. But, beside from those notable exceptions, all other epoxidations, including large ones like the epoxidation of plant oils as PVC-stabilizers (about 200.000 t/year), are carried out with peroxy acids. Because mcpba is far to expensive for most applications, short chain peracids like peracetic acid are used. Being much less stable than mcpba and thus risky handled in large amounts and high concentrations, these peroxy acids were preferably prepared in-situ. However, conventional in-situ formation of peracids has the serious drawback, that a strong acid is necessary to catalyze peroxy acid formation from the carboxylic acid and hydrogen peroxide. The presence of a strong acid in the reaction mixture often results in decreased selectivity because of the formation of undesired by-products by opening of the oxirane ring. Therefore, we propose a new method for epoxidation based on the in-situ preparation of percarboxylic acids from carboxylic acid esters and hydrogen peroxide catalyzed by a commercial, immobilized lipase. (orig.)

  10. Production of fatty acid butyl esters using the low cost naturally immobilized Carica papaya lipase. (United States)

    Su, Erzheng; Wei, Dongzhi


    In this work, the low cost naturally immobilized Carica papaya lipase (CPL) was investigated for production of fatty acid butyl esters (FABE) to fulfill the aim of reducing the lipase cost in the enzymatic butyl-biodiesel process. The CPL showed specificities to different alcohol acyl acceptors. Alcohols with more than three carbon atoms did not have negative effects on the CPL activity. The CPL catalyzed butanolysis for FABE production was systematically investigated. The reaction solvent, alcohol/oil molar ratio, enzyme amount, reaction temperature, and water activity all affected the butanolysis process. Under the optimized conditions, the highest conversion of 96% could be attained in 24 h. These optimal conditions were further applied to CPL catalyzed butanolysis of other vegetable oils. All of them showed very high conversion. The CPL packed-bed reactor was further developed, and could be operated continuously for more than 150 h. All of these results showed that the low cost Carica papaya lipase can be used as a promising lipase for biodiesel production.

  11. Studies on PNPP Hydrolysis Catalyzed by Schiff Base Cobalt(Ⅱ) Complexes

    Institute of Scientific and Technical Information of China (English)

    HU Wei; LI Jian-Zhang; WANG Ying; LI Ci; DU Juana; MENG Xiang-Guang; HU Chang-Wei; ZENG Xian-Cheng


    Two cobalt(Ⅱ) complexes of the Schiff base with morpholino or aza-crown ether pendants, CoL1 and CoL2, as mimic hydrolytic metalloenzyme, were used in catalytic hydrolysis of carboxylic ester (PNPP). The analysis of specific absorption spectra of the hydrolytic reaction systems indicates that key intermediates, made up of PNPP and Co(Ⅱ)complexes, have been formed in reaction processes of the PNPP catalytic hydrolysis. The mechanism of PNPP catalytic hydrolysis has been proposed based on the analytic result of specific absorption spectrum. A kinetic mathematical model, applied to the calculation of the kinetic parameter of PNPP catalytic hydrolysis, has been established based on the mechanism proposed. The acid effect of buffer solution, structural effect of the complexes,and effect of temperature on the rate of PNPP hydrolysis catalyzed by the complexes have been also discussed.

  12. Empirical modeling the ultrasound-assisted base-catalyzed sunflower oil methanolysis kinetics

    Directory of Open Access Journals (Sweden)

    Avramović Jelena M.


    Full Text Available The ultrasound-assisted sunflower oil methanolysis catalyzed by KOH was studied to define a simple empirical kinetic model useful for reactor design without complex computation. It was assumed that the neutralization of free fatty acids and the saponification reaction were negligible. The methanolysis process rate was observed to be controlled by the mass transfer limitation in the initial heterogeneous regime and by the chemical reaction in the later pseudo-homogeneous regime. The model involving the irreversible second-order kinetics was established and used for simulation of the triacylglycerol conversion and the fatty acid methyl esters formation in the latter regime. A good agreement between the proposed model and the experimental data in the chemically controlled regime was found.

  13. Lipase-Catalyzed Kinetic Resolution of Novel Antifungal N-Substituted Benzimidazole Derivatives. (United States)

    Łukowska-Chojnacka, Edyta; Staniszewska, Monika; Bondaryk, Małgorzata; Maurin, Jan K; Bretner, Maria


    A series of new N-substituted benzimidazole derivatives was synthesized and their antifungal activity against Candida albicans was evaluated. The chemical step included synthesis of appropriate ketones containing benzimidazole ring, reduction of ketones to the racemic alcohols, and acetylation of alcohols to the esters. All benzimidazole derivatives were obtained with satisfactory yields and in relatively short times. All synthesized compounds exhibit significant antifungal activity against Candida albicans 900028 ATCC (% cell inhibition at 0.25 μg concentration > 98%). Additionally, racemic mixtures of alcohols were separated by lipase-catalyzed kinetic resolution. In the enzymatic step a transesterification reaction was applied and the influence of a lipase type and solvent on the enantioselectivity of the reaction was studied. The most selective enzymes were Novozyme SP 435 and lipase Amano AK from Pseudomonas fluorescens (E > 100). PMID:26922853

  14. Mechanism of maltal hydration catalyzed by β-amylase: Role of protein structure in controlling the steric outcome of reactions catalyzed by a glycosylase

    International Nuclear Information System (INIS)

    Crystalline (monomeric) soybean and (tetrameric) sweet potato β-amylase were shown to catalyze the cis hydration of maltal (α-D-glucopyranosyl-2-deoxy-D-arabino-hex-1-enitol) to form β-2-deoxymaltose. As reported earlier with the sweet potato enzyme, maltal hydration in D2O by soybean β-amylase was found to exhibit an unusually large solvent deuterium kinetic isotope effect (VH/VD=6.5), a reaction rate linearly dependent on the mole fraction of deuterium, and 2-deoxy-[2(a)-2H]maltose as product. These results indicate (for each β-amylase) that protonation is the rate-limiting step in a reaction involving a nearly symmetric one-proton transition state and that maltal is specifically protonated from above the double bond. That maltal undergoes cis hydration provides evidence in support of a general-acid-catalyzed, carbonium ion mediated reaction. Of fundamental significance is that β-amylase protonates maltal from a direction opposite that assumed for protonating strach, yet creates products of the same anomeric configuration from both. Such stereochemical dichotomy argues for the overriding role of protein structures is dictating the steric outcome of reactions catalyzed by a glycosylase, by limiting the approach and orientation of water or other acceptors to the reaction center

  15. Palladium-Catalyzed Amination of Bromoanthancene

    Institute of Scientific and Technical Information of China (English)

    YU Ming-Xin; CHEN Xiao-Hang; CHENG Chien-Hong


    @@ Triarylamines are an important class of compounds, because they have been used as the hole-transport layer in electroluminescent devices. [1] New palladium catalyzed methods to form arylamines have emerged recently from Hartwing and Bucchwald . [2,3] Our group have investigated unusual diboration of allenes catalyzed by palladium complex and organic iodides. [4] Here we will report that arylamines react with bromoanthrancene (or dibromoanthancene) to afford triarylamines in the presence of Ligand-palladium complex. The structures of products were de termined by 1H NMR, 13C NMR, 13C (DEPT), IR and MS (HREI and EI) spectra.

  16. Attractor Explosions and Catalyzed Vacuum Decay

    Energy Technology Data Exchange (ETDEWEB)

    Green, Daniel; Silverstein, Eva; Starr, David


    We present a mechanism for catalyzed vacuum bubble production obtained by combining moduli stabilization with a generalized attractor phenomenon in which moduli are sourced by compact objects. This leads straightforwardly to a class of examples in which the Hawking decay process for black holes unveils a bubble of a different vacuum from the ambient one, generalizing the new endpoint for Hawking evaporation discovered recently by Horowitz. Catalyzed vacuum bubble production can occur for both charged and uncharged bodies, including Schwarzschild black holes for which massive particles produced in the Hawking process can trigger vacuum decay. We briefly discuss applications of this process to the population and stability of metastable vacua.

  17. A review on biodiesel production using catalyzed transesterification

    Energy Technology Data Exchange (ETDEWEB)

    Leung, Dennis Y.C.; Wu, Xuan; Leung, M.K.H. [Department of Mechanical Engineering, The University of Hong Kong, Pokfulam Road, Hong Kong (China)


    Biodiesel is a low-emissions diesel substitute fuel made from renewable resources and waste lipid. The most common way to produce biodiesel is through transesterification, especially alkali-catalyzed transesterification. When the raw materials (oils or fats) have a high percentage of free fatty acids or water, the alkali catalyst will react with the free fatty acids to form soaps. The water can hydrolyze the triglycerides into diglycerides and form more free fatty acids. Both of the above reactions are undesirable and reduce the yield of the biodiesel product. In this situation, the acidic materials should be pre-treated to inhibit the saponification reaction. This paper reviews the different approaches of reducing free fatty acids in the raw oil and refinement of crude biodiesel that are adopted in the industry. The main factors affecting the yield of biodiesel, i.e. alcohol quantity, reaction time, reaction temperature and catalyst concentration, are discussed. This paper also described other new processes of biodiesel production. For instance, the Biox co-solvent process converts triglycerides to esters through the selection of inert co-solvents that generates a one-phase oil-rich system. The non-catalytic supercritical methanol process is advantageous in terms of shorter reaction time and lesser purification steps but requires high temperature and pressure. For the in situ biodiesel process, the oilseeds are treated directly with methanol in which the catalyst has been preciously dissolved at ambient temperatures and pressure to perform the transesterification of oils in the oilseeds. This process, however, cannot handle waste cooking oils and animal fats. (author)

  18. Chiral N-1-adamantyl-N-trans-cinnamylaniline type ligands: synthesis and application to palladium-catalyzed asymmetric allylic alkylation of indoles. (United States)

    Mino, Takashi; Nishikawa, Kenji; Asano, Moeko; Shima, Yamato; Ebisawa, Toshibumi; Yoshida, Yasushi; Sakamoto, Masami


    Such chiral phosphine-internal olefin hybrid type ligands as N-1-adamantyl-N-cinnamylaniline derivatives 1 with C(aryl)-N(amine) bond axial chirality were synthesized and utilized for the palladium-catalyzed asymmetric allylic alkylation of indoles to afford the desired products in high enantioselectivities (up to 98% ee). PMID:27425209

  19. Evidence for the Formation of an Enamine Species during Aldol and Michael-type Addition Reactions Promiscuously Catalyzed by 4-Oxalocrotonate Tautomerase

    NARCIS (Netherlands)

    Poddar, Harshwardhan; Rahimi, Mehran; Geertsema, Edzard; Thunnissen, Andy; Poelarends, Gerrit


    The enzyme 4-oxalocrotonate tautomerase (4-OT), which has a catalytic N-terminal proline residue (Pro1), can promiscuously catalyze various carbon–carbon bond-forming reactions, including aldol condensation of acetaldehyde with benzaldehyde to yield cinnamaldehyde, and Michael-type addition of aceta

  20. Cp*Co(III)-Catalyzed Dehydrative C-H Allylation of 6-Arylpurines and Aromatic Amides Using Allyl Alcohols in Fluorinated Alcohols. (United States)

    Bunno, Youka; Murakami, Nanami; Suzuki, Yudai; Kanai, Motomu; Yoshino, Tatsuhiko; Matsunaga, Shigeki


    Cp*Co(III)-catalyzed C-H allylation of various aromatic C-H bonds using allyl alcohols as allylating reagents is described. Improved reaction conditions using fluorinated alcohol solvents afforded efficient directed C-H allylation of 6-arylpurines, benzamides, and a synthetically useful Weinreb amide with good functional group compatibility.

  1. Ferric chloride-catalyzed reaction of [60]fullerene with tert-butyl N-substituted carbamates: synthesis of oxazolidino[4,5:1,2][60]fullerenes. (United States)

    You, Xun; Wang, Guan-Wu


    The rare oxazolidinofullerenes have been prepared by the ferric chloride-catalyzed reaction of [60]fullerene with various tert-butyl N-substituted carbamates via t-Bu-O bond cleavage and heteroannulation under mild conditions. A possible mechanism for the formation of oxazolidinofullerenes is proposed. PMID:24328055

  2. Remote C−H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling

    KAUST Repository

    Xu, Jun


    Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a formidable challenge in organic chemistry. Herein, we report a novel approach to activating remote C-H bonds at the C5 position of 8-aminoquinoline through copper-catalyzed sulfonylation under mild conditions. Our strategy shows high conversion efficiency, a broad substrate scope, and good toleration with different functional groups. Furthermore, our mechanistic investigations suggest that a single-electron-transfer process plays a vital role in generating sulfonyl radicals and subsequently initiating C-S cross-coupling. Importantly, our copper-catalyzed remote functionalization protocol can be expanded for the construction of a variety of chemical bonds, including C-O, C-Br, C-N, C-C, and C-I. These findings provide a fundamental insight into the activation of remote C-H bonds, while offering new possibilities for rational design of drug molecules and optoelectronic materials requiring specific modification of functional groups. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Synthesis and emulsifying properties of carbohydrate fatty acid esters produced from Agave tequilana fructans by enzymatic acylation. (United States)

    Casas-Godoy, Leticia; Arrizon, Javier; Arrieta-Baez, Daniel; Plou, Francisco J; Sandoval, Georgina


    Carbohydrate fatty acid esters are non-ionic surfactants with a broad spectrum of applications. These molecules are generally synthesized using short carbohydrates or linear fructans; however in this research carbohydrate fatty acid esters were produced for the first time with branched fructans from Agave tequilana. Using immobilized lipases we successfully acylated A. tequilana fructans with vinyl laurate, obtaining products with different degrees of polymerization (DP). Lipozyme 435 was the most efficient lipase to catalyze the transesterification reaction. HPLC and ESI-MS analysis proved the presence of a mixture of acylated products as a result of the chemical complexity of fructans in the A. tequilana. The ESI-MS spectra showed a molecular mass shift between 183 and 366g/mol for fructooligosaccharides with a DP lower than 6, which indicated the presence of Agave fructans that had been mono- and diacylated with lauric acid. The carbohydrate fatty acid esters (CFAE) obtained showed good emulsifying properties in W/O emulsions. PMID:26988522

  4. Handbook of wafer bonding

    CERN Document Server

    Ramm, Peter; Taklo, Maaike M V


    Written by an author and editor team from microsystems companies and industry-near research organizations, this handbook and reference presents dependable, first-hand information on bonding technologies.In the first part, researchers from companies and institutions around the world discuss the most reliable and reproducible technologies for the production of bonded wafers. The second part is devoted to current and emerging applications, including microresonators, biosensors and precise measuring devices.

  5. Modification of Purine and Pyrimidine Nucleosides by Direct C-H Bond Activation

    Directory of Open Access Journals (Sweden)

    Yong Liang


    Full Text Available Transition metal-catalyzed modifications of the activated heterocyclic bases of nucleosides as well as DNA or RNA fragments employing traditional cross-coupling methods have been well-established in nucleic acid chemistry. This review covers advances in the area of cross-coupling reactions in which nucleosides are functionalized via direct activation of the C8-H bond in purine and the C5-H or C6-H bond in uracil bases. The review focuses on Pd/Cu-catalyzed couplings between unactivated nucleoside bases with aryl halides. It also discusses cross-dehydrogenative arylations and alkenylations as well as other reactions used for modification of nucleoside bases that avoid the use of organometallic precursors and involve direct C-H bond activation in at least one substrate. The scope and efficiency of these coupling reactions along with some mechanistic considerations are discussed.

  6. Environmentally friendly properties of vegetable oil methyl esters

    Directory of Open Access Journals (Sweden)

    Gateau Paul


    Full Text Available Measurements were carried out on Vegetable Oil Methyl Esters (VOME or FAME answering the most recent specifications. The products tested are RME (Rapeseed oil Methyl Ester, ERME (Erucic Rapeseed oil Methyl Esters, SME (Sunflower oil Methyl Esters, and HOSME (High Oleic Sunflower oil Methyl Esters. They contain more than 99.5% of fatty acid mono esters. The compositions are given. VOME are not volatile and they are not easily flammable. They are not soluble in water and they are biodegradable. According to the methods implemented for the determination of the German classification of substances hazardous to waters WGK, they are not toxic on mammals and unlike diesel fuel they are not toxic on fish, daphnia, algae and bacteria. The RME is not either toxic for shrimps. According to tests on rabbits, RME and SME are not irritating for the skin and the eyes. VOME display particularly attractive environmental properties.

  7. An Umpolung Strategy for the Synthesis of β-Aminoketones via Copper-Catalyzed Electrophilic Amination of Cyclopropanols. (United States)

    Ye, Zhishi; Dai, Mingji


    A novel copper-catalyzed electrophilic amination of cyclopropanols with O-benzoyl-N,N-dialkylhydroxylamines to synthesize various β-aminoketones via a sequence that includes C-C bond cleavage and Csp(3)-N bond formation is reported. The reaction conditions are mild and tolerate a wide range of functional groups including benzoate, tosylate, expoxide, and α,β-unsaturated carbonyls, which are incompatible in the traditional amine nucleophilic conjugate addition and the Mannich reaction conditions. Preliminary mechanistic studies and a proposed catalytic cycle of this umpolung β-aminoketone synthesis process have been described as well. PMID:25885943

  8. Synthesis of Substituted 2-Aminoimidazoles via Pd-Catalyzed Alkyne Carboamination Reactions. Application to the Synthesis of Preclathridine Natural Products


    Zavesky, Blane P.; Babij, Nicholas R.; Wolfe, John P.


    A new method for the synthesis of 2-aminoimidazole products is described. The heterocyclic products are generated in good yields via Pd-catalyzed carboamination reactions of N-propargyl guanidines and aryl triflates. This methodology generates both a C–N and C–C bond during the annulation step and facilitates the rapid construction of 2-aminoimidazole products with different aryl groups. The utility of this methodology was demonstrated in the total synthesis of preclathridine A, preclathridin...

  9. Palladium-Catalyzed Dearomative Allylic Alkylation of Indoles with Alkynes To Synthesize Indolenines with C3-Quarternary Centers. (United States)

    Gao, Shang; Wu, Zijun; Fang, Xinxin; Lin, Aijun; Yao, Hequan


    A palladium-catalyzed dearomative allylic alkylation of indoles with alkynes to construct indolenines with C3-quarternary centers was reported. The in situ formed arylallene intermediate omitted the need to install leaving groups on the allylic compounds and employ extra oxidants to oxidize the allylic C-H bonds. The reaction exhibited good functional group tolerance and high atom economy. Moreover, the reaction was further expanded to synthesize pyrroloindolines and furanoindolines. PMID:27442021

  10. Cleavage of an amide bond by a ribozyme (United States)

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


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

  11. Isolation and identification of an ester from a crude oil (United States)

    Phillips, H.F.; Breger, I.A.


    A dioctylphthalate has been isolated from a crude oil by means of adsorption column chromatography. The ester was identified by means of elemental analysis, refractive index, and its infra-red absorption spectrum. Saponification of the isolate and examination of the resultant alcohol by means of infrared absorption spectra led to the conclusion that the ester is a branched chain dioctylphthalate. This is the first reported occurrence of an ester in crude petroleum. ?? 1958.

  12. Palladium catalyzed hydrogenation of bio-oils and organic compounds (United States)

    Elliott, Douglas C.; Hu, Jianli; Hart, Todd R.; Neuenschwander, Gary G.


    The invention provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Experimental results have shown unexpected and superior results for palladium-catalyzed hydrogenations of organic compounds typically found in bio-oils.

  13. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert


    Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

  14. Mechanochemical ruthenium-catalyzed olefin metathesis. (United States)

    Do, Jean-Louis; Mottillo, Cristina; Tan, Davin; Štrukil, Vjekoslav; Friščić, Tomislav


    We describe the development of a mechanochemical approach for Ru-catalyzed olefin metathesis, including cross-metathesis and ring-closing metathesis. The method uses commercially available catalysts to achieve high-yielding, rapid, room-temperature metathesis of solid or liquid olefins on a multigram scale using either no or only a catalytic amount of a liquid.

  15. Data, Leadership, and Catalyzing Culture Change (United States)

    Benson, R. Todd; Trower, Cathy A.


    It is crucial to understand today's tenure-track workers so that colleges and universities can continue to attract and retain a large subset of them by understanding and supporting their satisfaction and success at work. In this article, the authors talk about data, leadership, and catalyzing culture change. They discuss data use in the academy…

  16. Pinacol Coupling Reactions Catalyzed by Active Zinc

    Institute of Scientific and Technical Information of China (English)

    Hui ZHAO; Wei DENG; Qing Xiang GUO


    Pinacol coupling reactions catalyzed by active zinc revealed high activity and extensive suitability. The efficiency of the reaction was improved apparently owing to decreasing reductive potential of zinc. In addition, the results indicated that the zinc activity has a direct relation to the coupling reactivity compared to untreated zinc or other general active zinc.

  17. Mechanochemical ruthenium-catalyzed olefin metathesis. (United States)

    Do, Jean-Louis; Mottillo, Cristina; Tan, Davin; Štrukil, Vjekoslav; Friščić, Tomislav


    We describe the development of a mechanochemical approach for Ru-catalyzed olefin metathesis, including cross-metathesis and ring-closing metathesis. The method uses commercially available catalysts to achieve high-yielding, rapid, room-temperature metathesis of solid or liquid olefins on a multigram scale using either no or only a catalytic amount of a liquid. PMID:25668586

  18. Zeolite 5A Catalyzed Etherification of Diphenylmethanol (United States)

    Cooke, Jason; Henderson, Eric J.; Lightbody, Owen C.


    An experiment for the synthetic undergraduate laboratory is described in which zeolite 5A catalyzes the room temperature dehydration of diphenylmethanol, (C[subscript 6]H[subscript 5])[subscript 2]CHOH, producing 1,1,1',1'-tetraphenyldimethyl ether, (C[subscript 6]H[subscript 5])[subscript 2]CHOCH(C[subscript 6]H[subscript 5])[subscript 2]. The…

  19. A novel thermooxidatively stable poly(ester-imide-benzoxazole)

    Energy Technology Data Exchange (ETDEWEB)

    Sundar, R.A.; Mathias, L.J. [Univ. of Sothern Mississippi, Hattiesburg, MS (United States)


    A poly(ester-amide-imide) was synthesized by the low temperature solution polycondensation of 4-amino-5-hydroxy-N,4{prime}-hydroxyphenyl phthalimide with isophthaloyl chloride. Subsequent thermal cyclodehydration of the poly(ester-amide-imide) at 320{degrees}C in vacuum afforded the poly(ester-imide-benzoxazole). This polymer was only soluble in sulfuric acid. FTIR and NMR spectra confirmed structure. The poly(ester-imide-benzoxazole) had no detectable thermal transitions up to 500{degrees}C in nitrogen, and was reasonably stable in air and nitrogen, with weight retentions of 95% at 500{degrees}C.

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

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


    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