Sample records for efficient chemoselective synthesis

  1. Chemoselective synthesis of functional homocysteine residues in polypeptides and peptides.

    PubMed

    Gharakhanian, Eric G; Deming, Timothy J

    2016-04-18

    A methodology was developed for efficient, chemoselective transformation of methionine residues into stable, functional homocysteine derivatives. Methionine residues can undergo highly chemoselective alkylation reactions at low pH to yield stable sulfonium ions, which could then be selectively demethylated to give stable alkyl homocysteine residues. This mild, two-step process is chemoselective, efficient, tolerates many functional groups, and provides a means for creation of new functional biopolymers, site-specific peptide tagging, and synthesis of biomimetic and structural analogs of peptides.

  2. Chemoselective synthesis of ketones and ketimines by addition of organometallic reagents to secondary amides

    NASA Astrophysics Data System (ADS)

    Bechara, William S.; Pelletier, Guillaume; Charette, André B.

    2012-03-01

    The development of efficient and selective transformations is crucial in synthetic chemistry as it opens new possibilities in the total synthesis of complex molecules. Applying such reactions to the synthesis of ketones is of great importance, as this motif serves as a synthetic handle for the elaboration of numerous organic functionalities. In this context, we report a general and chemoselective method based on an activation/addition sequence on secondary amides allowing the controlled isolation of structurally diverse ketones and ketimines. The generation of a highly electrophilic imidoyl triflate intermediate was found to be pivotal in the observed exceptional functional group tolerance, allowing the facile addition of readily available Grignard and diorganozinc reagents to amides, and avoiding commonly observed over-addition or reduction side reactions. The methodology has been applied to the formal synthesis of analogues of the antineoplastic agent Bexarotene and to the rapid and efficient synthesis of unsymmetrical diketones in a one-pot procedure.

  3. Exploiting 1,2,3-Triazolium Ionic Liquids for Synthesis of Tryptanthrin and Chemoselective Extraction of Copper(II) Ions and Histidine-Containing Peptides.

    PubMed

    Li, Hsin-Yi; Chen, Chien-Yuan; Cheng, Hui-Ting; Chu, Yen-Ho

    2016-10-13

    Based on a common structural core of 4,5,6,7-tetrahydro[1,2,3]triazolo[1,5- a ]pyridine, a number of bicyclic triazolium ionic liquids 1 - 3 were designed and successfully prepared. In our hands, this optimized synthesis of ionic liquids 1 and 2 requires no chromatographic separation. Also in this work, ionic liquids 1 , 2 were shown to be efficient ionic solvents for fast synthesis of tryptanthrin natural product. Furthermore, a new affinity ionic liquid 3 was tailor-synthesized and displayed its effectiveness in chemoselective extraction of both Cu(II) ions and, for the first time, histidine-containing peptides.

  4. Chemoselective synthesis of sialic acid 1,7-lactones.

    PubMed

    Allevi, Pietro; Rota, Paola; Scaringi, Raffaella; Colombo, Raffaele; Anastasia, Mario

    2010-08-20

    The chemoselective synthesis of the 1,7-lactones of N-acetylneuraminic acid, N-glycolylneuraminic acid, and 3-deoxy-d-glycero-d-galacto-nononic acid is accomplished in two steps: a simple treatment of the corresponding free sialic acid with benzyloxycarbonyl chloride and a successive hydrogenolysis of the formed 2-benzyloxycarbonyl 1,7-lactone. The instability of the 1,7-lactones to protic solvents has been also evidenced together with the rationalization of the mechanism of their formation under acylation conditions. The results permit to dispose of authentic 1,7-sialolactones to be used as reference standards and of a procedure useful for the preparation of their isotopologues to be used as inner standards in improved analytical procedures for the gas liquid chromatography-mass spectrometry (GLC-MS) analysis of 1,7-sialolactones in biological media.

  5. Chemoselective Hydroxyl Group Transformation: An Elusive Target‡

    PubMed Central

    Trader, Darci J.; Carlson, Erin E.

    2012-01-01

    The selective reaction of one functional group in the presence of others is not a trivial task. A noteworthy amount of research has been dedicated to the chemoselective reaction of the hydroxyl moiety. This group is prevalent in many biologically important molecules including natural products and proteins. However, targeting the hydroxyl group is difficult for many reasons including its relatively low nucleophilicity in comparison to other ubiquitous functional groups such as amines and thiols. Additionally, many of the developed chemoselective reactions cannot be used in the presence of water. Despite these complications, chemoselective transformation of the hydroxyl moiety has been utilized in the synthesis of complex natural product derivatives, the reaction of tyrosine residues in proteins, the isolation of natural products and is the mechanism of action of myriad drugs. Here, methods for selective targeting of this group, as well as applications of several devised methods, are described. PMID:22695722

  6. Chemoselective reductive nucleophilic addition to tertiary amides, secondary amides, and N-methoxyamides.

    PubMed

    Nakajima, Minami; Oda, Yukiko; Wada, Takamasa; Minamikawa, Ryo; Shirokane, Kenji; Sato, Takaaki; Chida, Noritaka

    2014-12-22

    As the complexity of targeted molecules increases in modern organic synthesis, chemoselectivity is recognized as an important factor in the development of new methodologies. Chemoselective nucleophilic addition to amide carbonyl centers is a challenge because classical methods require harsh reaction conditions to overcome the poor electrophilicity of the amide carbonyl group. We have successfully developed a reductive nucleophilic addition of mild nucleophiles to tertiary amides, secondary amides, and N-methoxyamides that uses the Schwartz reagent [Cp2 ZrHCl]. The reaction took place in a highly chemoselective fashion in the presence of a variety of sensitive functional groups, such as methyl esters, which conventionally require protection prior to nucleophilic addition. The reaction will be applicable to the concise synthesis of complex natural alkaloids from readily available amide groups. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Assembly of Oriented Virus Arrays by Chemo-Selective Ligation Methods and Nanolithography Techniques

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Camarero, J A; Cheung, C L; Lin, T

    2002-12-02

    The present work describes our ongoing efforts towards the creation of nano-scaled ordered arrays of protein/virus covalently attached to site-specific chemical linkers patterned by different nanolithograpy techniques. We will present a new and efficient solid-phase approach for the synthesis of chemically modified long alkyl-thiols. These compounds can be used to introduce chemoselective reacting groups onto gold and silicon-based surfaces. Furthermore, these modified thiols have been used to create nanometric patterns by using different nanolithography techniques. We will show that these patterns can react chemoselectively with proteins and/or virus which have been chemically or recombinantly modified to contain complementary chemical groupsmore » at specific positions thus resulting in the oriented attachment of the protein or virus to the surface.« less

  8. N-Heterocyclic carbene-catalyzed direct cross-aza-benzoin reaction: Efficient synthesis of α-amino-β-keto esters.

    PubMed

    Uno, Takuya; Kobayashi, Yusuke; Takemoto, Yoshiji

    2012-01-01

    An efficient catalytic synthesis of α-amino-β-keto esters has been newly developed. Cross-coupling of various aldehydes with α-imino ester, catalyzed by N-heterocyclic carbene, leads chemoselectively to α-amino-β-keto esters in moderate to good yields with high atom efficiency. The reaction mechanism is discussed, and it is proposed that the α-amino-β-keto esters are formed under thermodynamic control.

  9. Palladium-metalated porous organic polymers as recyclable catalysts for chemoselective decarbonylation of aldehydes.

    PubMed

    Li, Wen-Hao; Li, Cun-Yao; Li, Yan; Tang, Hai-Tao; Wang, Heng-Shan; Pan, Ying-Ming; Ding, Yun-Jie

    2018-06-07

    A novel palladium nanoparticle (NP)-metalated porous organic ligand (Pd NPs/POL-xantphos) has been prepared for the chemoselective decarbonylation of aldehydes. This heterogenous catalyst not only has excellent catalytic activity and chemoselectivity, but also holds high activity after 10 runs of reuse. The effective usage of this method is demonstrated through the synthesis of biofuels such as furfuryl alcohol (FFA) via the highly chemoselective decarbonylation of biomass-derived 5-hydroxy-methylfurfural (HMF) with a TON up to 1540. More importantly, 9-fluorenone could be obtained in one step through the decarbonylation of 2-bromobenzaldehyde by using this heterogeneous catalyst.

  10. Visible-light-driven chemoselective hydrogenation of nitroarenes to anilines in water via graphitic carbon nitride metal-free photocatalysis.

    PubMed

    Xiao, Gang; Li, Peifeng; Zhao, Yilin; Xu, Shengnan; Su, Haijia

    2018-05-20

    Green and efficient procedures are highly required for the chemoselective hydrogenation of functionalized nitroarenes to industrially important anilines. Here, we show that visible-light-driven, chemoselective hydrogenation of functionalized nitroarenes bearing the sensitive groups to anilines can be achieved in good to excellent yields (82-100%) in water under relatively mild conditions, catalyzed by low-cost and recyclable graphitic carbon nitride. It is also applicable in gram-scale reaction with 86% yield of aniline. Mechanism study reveals that visible light induced electrons are responsible for the hydrogenation reactions and thermal energy can also promote the photocatalytic activity. Kinetics study shows that this reaction possibly occurs via one-step hydrogenation or stepwise condensation route. Wide applications can be expected using this green, efficient, and highly selective photocatalysis system in reduction reactions for fine chemical synthesis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Chemoselective ligation

    DOEpatents

    Saxon, Eliana [Albany, CA; Bertozzi, Carolyn Ruth [Berkeley, CA

    2011-12-13

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  12. Chemoselective ligation

    DOEpatents

    Saxon, Eliana; Bertozzi, Carolyn

    2006-10-17

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  13. Chemoselective ligation

    DOEpatents

    Saxon, Eliana [Albany, CA; Bertozzi, Carolyn R [Berkeley, CA

    2011-05-10

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  14. Chemoselective ligation

    DOEpatents

    Saxon, Eliana; Bertozzi, Carolyn Ruth

    2010-11-23

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  15. Chemoselective ligation

    DOEpatents

    Saxon, Eliana [Albany, CA; Bertozzi, Carolyn R [Berkeley, CA

    2011-04-12

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  16. Chemoselective ligation

    DOEpatents

    Saxon, Eliana; Bertozzi, Carolyn R.

    2010-02-23

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g. on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  17. Chemoselective ligation

    DOEpatents

    Saxon, Eliana [Albany, CA; Bertozzi, Carolyn [Berkeley, CA

    2003-05-27

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  18. Chemoselective room temperature E1cB N-N cleavage of oxazolidinone hydrazides from enantioselective aldehyde α-hydrazination: synthesis of (+)-1,4-dideoxyallonojirimycin.

    PubMed

    Ferreira, Jasmin; Rees-Jones, Sophie C M; Ramaotsoa, Valerie; Msutu, Ath'enkosi; Hunter, Roger

    2016-02-07

    Room temperature E1cB N-N cleavage of oxazolidinone hydrazides via N-alkylation with diethyl bromomalonate and potassium or caesium carbonate as base in acetonitrile is presented. The new method has a much improved chemoselectivity, which is illustrated by a concise total synthesis of the piperidine iminosugar (+)-1,4-dideoxyallonojirimycin.

  19. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    PubMed Central

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

    2016-01-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

  20. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai

    2016-08-30

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturatedmore » metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.« less

  1. Rethinking Cysteine Protective Groups: S-Alkylsulfonyl-l-Cysteines for Chemoselective Disulfide Formation.

    PubMed

    Schäfer, Olga; Huesmann, David; Muhl, Christian; Barz, Matthias

    2016-12-12

    The ability to reversibly cross-link proteins and peptides grants the amino acid cysteine its unique role in nature as well as in peptide chemistry. We report a novel class of S-alkylsulfonyl-l-cysteines and N-carboxy anhydrides (NCA) thereof for peptide synthesis. The S-alkylsulfonyl group is stable against amines and thus enables its use under Fmoc chemistry conditions and the controlled polymerization of the corresponding NCAs yielding well-defined homo- as well as block co-polymers. Yet, thiols react immediately with the S-alkylsulfonyl group forming asymmetric disulfides. Therefore, we introduce the first reactive cysteine derivative for efficient and chemoselective disulfide formation in synthetic polypeptides, thus bypassing additional protective group cleavage steps. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Chemoselective Reactions of Citral: Green Syntheses of Natural Perfumes for the Undergraduate Organic Laboratory

    ERIC Educational Resources Information Center

    Cunningham, Anna D.; Ham, Eun Y.; Vosburg, David A.

    2011-01-01

    Chemoselectivity is a central concept in organic synthesis and may be readily appreciated in the context of the fragrant, polyfunctional natural product citral. We describe three single-step reactions students may perform on citral to synthesize other natural perfumes: citronellal, geraniol, nerol, or epoxycitral. Each of the reactions uses a…

  3. One-pot chemoselective synthesis of novel pyrrole-substituted pyrido [2,3-d]pyrimidines using [γ-Fe2O3@HAp-SO3H] as an efficient nanocatalyst

    NASA Astrophysics Data System (ADS)

    Jahanshahi, Parivash; Mamaghani, Manouchehr; Haghbin, Fereshteh; Nia, Roghayeh Hossein; Rassa, Mehdi

    2018-03-01

    Novel (1-methyl-1H-pyrrol-2-yl)-[2,3-d]pyrimidine derivatives were synthesized chemoselectively in good to high yields (81-90%) and short reaction times (7-14 min) by hydroxyapatite-encapsulated-γ-Fe2O3 supported sulfonic acid ([γ-Fe2O3@HAp-SO3H]) catalyzed condensation of 3-(1-methyl-1H-pyrrol-2-yl)-3-oxopropanenitrile, 6-amino-2-(alkylthio)pyrimidin-4(3H)-one and various aromatic aldehydes. The easy work-up of the products, rapidity, high efficiency and recyclability of the catalyst are advantages of this protocol. The antibacterial activity of the newly synthesized products was investigated. Some of the products showed encouraging activity.

  4. Dearomatization Strategies in the Synthesis of Complex Natural Products

    PubMed Central

    Roche, Stéphane P.; Porco, John A.

    2014-01-01

    Evolution in the field of the total synthesis of natural products has led to exciting developments over the last decade. Numerous chemo-selective and enantioselective methodologies have emerged from total syntheses, resulting in efficient access to many important natural product targets. This Review highlights recent developments concerning dearomatization, a powerful strategy for the total synthesis of architecturally complex natural products wherein planar, aromatic scaffolds are converted to three-dimensional molecular architectures. PMID:21506209

  5. AN EFFICIENT AND CHEMOSELECTIVE CBZ-PROTECTION OF AMINES USING SILICA-SULFURIC ACID AT ROOM TEMPERATURE

    EPA Science Inventory

    A simple, facile, and chemoselective N-benzyloxycarbonylation of amines using silica-sulfuric acid that proceeds under solvent-free conditions at room temperature has been achieved. These reactions are applicable to a wide variety of primary (aliphatic, cyclic) secondary amines, ...

  6. Total Synthesis of Bryostatins. Development of Methodology for Atom-Economic and Stereoselective Synthesis of the C-ring Subunit

    PubMed Central

    Trost, Barry M.; Frontier, Alison J.; Thiel, Oliver R.; Yang, Hanbiao; Dong, Guangbin

    2012-01-01

    Bryostatins, a family of structurally complicated macrolides, exhibit an exceptional range of biological activities. The limited availability and structural complexity of these molecules makes development of an efficient total synthesis particularly important. This article describes our initial efforts towards the total synthesis of bryostatins, in which chemoselective and atom-economical methods for stereoselective assembly of the C-ring subunit were developed. A Pd-catalyzed tandem alkyne-alkyne coupling/6-endo-dig cyclization sequence was explored and successfully pursued in the synthesis of a dihydropyran ring system. Elaboration of this methodology ultimately led to a concise synthesis of the C-ring subunit of bryostatins. PMID:21793057

  7. Synthesis of Dibenzo[h,rst]pentaphenes and Dibenzo[fg,qr]pentacenes by the Chemoselective C-O Arylation of Dimethoxyanthraquinones.

    PubMed

    Suzuki, Yusuke; Yamada, Kohei; Watanabe, Kentaro; Kochi, Takuya; Ie, Yutaka; Aso, Yoshio; Kakiuchi, Fumitoshi

    2017-07-21

    A convenient method for the syntheses of dibenzo[h,rst]pentaphenes and dibenzo[fg,qr]pentacenes via the ruthenium-catalyzed chemoselective C-O arylation of 1,4- and 1,5-dimethoxyanthraquinones is described. Dimethoxyanthraquinones reacted selectively with arylboronates at the ortho C-O bonds to give diarylation products. An efficient two-step procedure consisting of a Corey-Chaykofsky reaction and subsequent dehydrative aromatization afforded derivatives of dibenzo[h,rst]pentaphenes and dibenzo[fg,qr]pentacenes. Hole-transporting characteristics were observed for a device with a bottom-contact configuration that was fabricated from one of these polycyclic aromatic hydrocarbons.

  8. Chemoselective Aliphatic C-H Bond Oxidation Enabled by Polarity Reversal.

    PubMed

    Dantignana, Valeria; Milan, Michela; Cussó, Olaf; Company, Anna; Bietti, Massimo; Costas, Miquel

    2017-12-27

    Methods for selective oxidation of aliphatic C-H bonds are called on to revolutionize organic synthesis by providing novel and more efficient paths. Realization of this goal requires the discovery of mechanisms that can alter in a predictable manner the innate reactivity of these bonds. Ideally, these mechanisms need to make oxidation of aliphatic C-H bonds, which are recognized as relatively inert, compatible with the presence of electron rich functional groups that are highly susceptible to oxidation. Furthermore, predictable modification of the relative reactivity of different C-H bonds within a molecule would enable rapid diversification of the resulting oxidation products. Herein we show that by engaging in hydrogen bonding, fluorinated alcohols exert a polarity reversal on electron rich functional groups, directing iron and manganese catalyzed oxidation toward a priori stronger and unactivated C-H bonds. As a result, selective hydroxylation of methylenic sites in hydrocarbons and remote aliphatic C-H oxidation of otherwise sensitive alcohol, ether, amide, and amine substrates is achieved employing aqueous hydrogen peroxide as oxidant. Oxidations occur in a predictable manner, with outstanding levels of product chemoselectivity, preserving the first-formed hydroxylation product, thus representing an extremely valuable tool for synthetic planning and development.

  9. Total synthesis of bryostatins: the development of methodology for the atom-economic and stereoselective synthesis of the ring C subunit.

    PubMed

    Trost, Barry M; Frontier, Alison J; Thiel, Oliver R; Yang, Hanbiao; Dong, Guangbin

    2011-08-22

    Bryostatins, a family of structurally complicated macrolides, exhibit an exceptional range of biological activities. The limited availability and structural complexity of these molecules makes development of an efficient total synthesis particularly important. This article describes our initial efforts towards the total synthesis of bryostatins, in which chemoselective and atom-economical methods for the stereoselective assembly of the ring C subunit were developed. A Pd-catalyzed tandem alkyne-alkyne coupling/6-endo-dig cyclization sequence was explored and successfully pursued in the synthesis of a dihydropyran ring system. Elaboration of this methodology ultimately led to a concise synthesis of the ring C subunit of bryostatins. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Fe-polyaniline composite nanofiber catalyst for chemoselective hydrolysis of oxime.

    PubMed

    Mahato, Sanjit Kumar; Bhaumik, Madhumita; Maji, Arun; Dutta, Abhijit; Maiti, Debabrata; Maity, Arjun

    2018-03-01

    A facile chemoselective one-pot strategy for the deprotection of oxime has been developed using Fe 0 -polyaniline composite nanofiber (Fe 0 -PANI), as a catalyst. Nano material based Fe 0 -PANI catalyst has been synthesized via in-situ polymerization of ANI monomer and followed by reductive deposition of Fe 0 onto PANI matrix. The catalyst was characterized by FE-SEM, HR-TEM, BET, XRD, ATR-FTIR, XPS and VSM techniques. The scope of the transformation was studied for aryl, alkyl and heteroarylketoxime with excellent chemoselectivity (>99%). Mechanistic investigations suggested the involvement of a cationic intermediate with Fe 3+ active catalytic species. Substituent effect showed a linear free energy relationship. The activation energy (E a ) was calculated to be 17.46 kJ mol -1 for acetophenone oxime to acetophenone conversion. The recyclability of the catalyst demonstrated up to 10 cycles without any significant loss of efficiency. Based on the preliminary experiments a plausible mechanism has been proposed involving a carbocationic intermediate. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. Highly chemoselective intermolecular cross-benzoin reactions using an ad hoc designed novel N-heterocyclic carbene catalyst.

    PubMed

    Delany, Eoghan G; Connon, Stephen J

    2018-01-31

    The design of a novel N-heterocyclic carbene catalyst incorporating a bulky yet highly electron-deficient N-aryl substituent has allowed the development of an efficient protocol for the first highly chemoselective intermolecular benzoin condensations between two non-identical aromatic aldehydes.

  12. Using Nazarov Electrocyclization to Stage Chemoselective [1,2]-Migrations: Stereoselective Synthesis of Functionalized Cyclopentenones

    PubMed Central

    Lebœuf, David; Huang, Jie; Gandon, Vincent

    2012-01-01

    Highly functionalized cyclopentenones are prepared stereospecifically based on a chemoselective copper(II)-mediated Nazarov/Wagner-Meerwein rearrangement sequence. After the initial 4π electrocyclization, this reaction involves two sequential [1,2]-migrations depending upon both migratory ability and steric bulk of the substituents at C1 and C5. This sequence can be achieved by using a catalytic quantity of copper(II) in combination with a weak Lewis acid. The mechanism of the reaction is also supported by DFT computations. PMID:21953873

  13. Chemoselective Aliphatic C–H Bond Oxidation Enabled by Polarity Reversal

    PubMed Central

    2017-01-01

    Methods for selective oxidation of aliphatic C–H bonds are called on to revolutionize organic synthesis by providing novel and more efficient paths. Realization of this goal requires the discovery of mechanisms that can alter in a predictable manner the innate reactivity of these bonds. Ideally, these mechanisms need to make oxidation of aliphatic C–H bonds, which are recognized as relatively inert, compatible with the presence of electron rich functional groups that are highly susceptible to oxidation. Furthermore, predictable modification of the relative reactivity of different C–H bonds within a molecule would enable rapid diversification of the resulting oxidation products. Herein we show that by engaging in hydrogen bonding, fluorinated alcohols exert a polarity reversal on electron rich functional groups, directing iron and manganese catalyzed oxidation toward a priori stronger and unactivated C–H bonds. As a result, selective hydroxylation of methylenic sites in hydrocarbons and remote aliphatic C–H oxidation of otherwise sensitive alcohol, ether, amide, and amine substrates is achieved employing aqueous hydrogen peroxide as oxidant. Oxidations occur in a predictable manner, with outstanding levels of product chemoselectivity, preserving the first-formed hydroxylation product, thus representing an extremely valuable tool for synthetic planning and development. PMID:29296677

  14. An efficient, second-generation synthesis of the signature dioxabicyclo[3.2.1]octane core of (+)-sorangicin A and elaboration of the (Z,Z,E)-triene acid system.

    PubMed

    Smith, Amos B; Dong, Shuzhi

    2009-03-05

    An efficient, second-generation synthesis of the signature dioxabicyclo[3.2.1]octane core of (+)-sorangicin A (1), in conjunction with an effective, stereocontrolled protocol to arrive at the requisite (Z,Z,E)-triene acid system has been developed. Highlights of the core construction entail a three-component union, a KHMDS-promoted epoxide ring formation-ring opening cascade, a Takai olefination, and a chemoselective Sharpless dihydroxylation. Assembly of the triene acid system was then achieved via Stille cross-coupling with the ethyl ester of (Z,Z)-5-tributylstannyl-2,4-pentadienoic acid, followed by mild hydrolysis preserving the triene configuration.

  15. Chemoselective synthesis and analysis of naturally occurring phosphorylated cysteine peptides

    PubMed Central

    Bertran-Vicente, Jordi; Penkert, Martin; Nieto-Garcia, Olaia; Jeckelmann, Jean-Marc; Schmieder, Peter; Krause, Eberhard; Hackenberger, Christian P. R.

    2016-01-01

    In contrast to protein O-phosphorylation, studying the function of the less frequent N- and S-phosphorylation events have lagged behind because they have chemical features that prevent their manipulation through standard synthetic and analytical methods. Here we report on the development of a chemoselective synthetic method to phosphorylate Cys side-chains in unprotected peptides. This approach makes use of a reaction between nucleophilic phosphites and electrophilic disulfides accessible by standard methods. We achieve the stereochemically defined phosphorylation of a Cys residue and verify the modification using electron-transfer higher-energy dissociation (EThcD) mass spectrometry. To demonstrate the use of the approach in resolving biological questions, we identify an endogenous Cys phosphorylation site in IICBGlc, which is known to be involved in the carbohydrate uptake from the bacterial phosphotransferase system (PTS). This new chemical and analytical approach finally allows further investigating the functions and significance of Cys phosphorylation in a wide range of crucial cellular processes. PMID:27586301

  16. "Clickable", trifunctional magnetite nanoparticles and their chemoselective biofunctionalization.

    PubMed

    Das, Manasmita; Bandyopadhyay, Debarati; Mishra, Debasish; Datir, Satyajit; Dhak, Prasanta; Jain, Sanyog; Maiti, Tapas Kumar; Basak, Amit; Pramanik, Panchanan

    2011-06-15

    A multifunctional iron oxide based nanoformulation for combined cancer-targeted therapy and multimodal imaging has been meticulously designed and synthesized using a chemoselective ligation approach. Novel superparamagnetic magnetite nanoparticles simultaneously functionalized with amine, carboxyl, and azide groups were fabricated through a sequence of stoichiometrically controllable partial succinylation and Cu (II) catalyzed diazo transfer on the reactive amine termini of 2-aminoethylphosphonate grafted magnetite nanoparticles (MNPs). Functional moieties associated with MNP surface were chemoselectively conjugated with rhodamine B isothiocyanate (RITC), propargyl folate (FA), and paclitaxel (PTX) via tandem nucleophic addition of amine to isothithiocyanates, Cu (I) catalyzed azide--alkyne click chemistry and carbodiimide-promoted esterification. An extensive in vitro study established that the bioactives chemoselectively appended to the magnetite core bequeathed multifunctionality to the nanoparticles without any loss of activity of the functional molecules. Multifunctional nanoparticles, developed in the course of the study, could selectively target and induce apoptosis to folate-receptor (FR) overexpressing cancer cells with enhanced efficacy as compared to the free drug. In addition, the dual optical and magnetic properties of the synthesized nanoparticles aided in the real-time tracking of their intracellular pathways also as apoptotic events through dual fluorescence and MR-based imaging.

  17. Synergistic Manganese(I) C-H Activation Catalysis in Continuous Flow: Chemoselective Hydroarylation.

    PubMed

    Wang, Hui; Pesciaioli, Fabio; Oliveira, João C A; Warratz, Svenja; Ackermann, Lutz

    2017-11-20

    Chemoselective hydroarylations were accomplished by a novel synergistic Brønsted acid/manganese(I)-catalyzed C-H activation manifold. Thus, alkynes bearing O-leaving groups could, for the first time, be employed for C-H alkenylations without concurrent β-O elimination, thereby setting the stage for versatile late-stage diversifications. Also described is the first manganese-catalyzed C-H activation in continuous flow, thus enabling efficient hydroarylations within only 20 minutes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Chemoselective Cleavage of p-Methoxybenzyl and 2-Naphthylmethyl Ethers Using a Catalytic Amount of HCl in Hexafluoro-2-propanol.

    PubMed

    Volbeda, Anne Geert; Kistemaker, Hans A V; Overkleeft, Herman S; van der Marel, Gijsbert A; Filippov, Dmitri V; Codée, Jeroen D C

    2015-09-04

    A new, fast, mild and chemoselective deprotection method to cleave p-methoxybenzyl and 2-naphthylmethyl ethers using catalytic amounts of hydrochloric acid in a 1:1 mixture of hexafluoro-2-propanol (HFIP) and methylene chloride (DCM) is described. The scope of the methodology becomes apparent from 14 examples of orthogonally protected monosaccharides that are subjected to HCl/HFIP treatment. The applicability of the HCl/HFIP method is illustrated by the synthesis of a sulfated β-mannuronic acid disaccharide.

  19. Origin of chemoselectivity in N-heterocyclic carbene catalyzed cross-benzoin reactions: DFT and experimental insights.

    PubMed

    Langdon, Steven M; Legault, Claude Y; Gravel, Michel

    2015-04-03

    An exploration into the origin of chemoselectivity in the NHC-catalyzed cross-benzoin reaction reveals several key factors governing the preferred pathway. In the first computational study to explore the cross-benzoin reaction, a piperidinone-derived triazolium catalyst produces kinetically controlled chemoselectivity. This is supported by (1)H NMR studies as well as a series of crossover experiments. Major contributors include the rapid and preferential formation of an NHC adduct with alkyl aldehydes, a rate-limiting carbon-carbon bond formation step benefiting from a stabilizing π-stacking/π-cation interaction, and steric penalties paid by competing pathways. The energy profile for the analogous pyrrolidinone-derived catalyst was found to be remarkably similar, despite experimental data showing that it is less chemoselective. The chemoselectivity could not be improved through kinetic control; however, equilibrating conditions show substantial preference for the same cross-benzoin product kinetically favored by the piperidinone-derived catalyst.

  20. Novel chemoselective hydrogenation of aromatic nitro compounds over ferric hydroxide supported nanocluster gold in the presence of CO and H2O.

    PubMed

    Liu, Lequan; Qiao, Botao; Chen, Zhengjian; Zhang, Juan; Deng, Youquan

    2009-02-14

    Chemoselective hydrogenation of aromatic nitro compounds were first efficiently achieved over Au/Fe(OH)(x) at 100-120 degrees C for 1.5-6 h (depending on different substrates) in the presence of CO and H(2)O.

  1. Catalytic asymmetric epoxidation of alpha,beta-unsaturated amides: efficient synthesis of beta-aryl alpha-hydroxy amides using a one-pot tandem catalytic asymmetric epoxidation-Pd-catalyzed epoxide opening process.

    PubMed

    Nemoto, Tetsuhiro; Kakei, Hiroyuki; Gnanadesikan, Vijay; Tosaki, Shin-Ya; Ohshima, Takashi; Shibasaki, Masakatsu

    2002-12-11

    The catalytic asymmetric epoxidation of alpha,beta-unsaturated amides using Sm-BINOL-Ph3As=O complex was succeeded. Using 5-10 mol % of the asymmetric catalyst, a variety of amides were epoxidized efficiently, yielding the corresponding alpha,beta-epoxy amides in up to 99% yield and in more than 99% ee. Moreover, the novel one-pot tandem process, one-pot tandem catalytic asymmetric epoxidation-Pd-catalyzed epoxide opening process, was developed. This method was successfully utilized for the efficient synthesis of beta-aryl alpha-hydroxy amides, including beta-aryllactyl-leucine methyl esters. Interestingly, it was found that beneficial modifications on the Pd catalyst were achieved by the constituents of the first epoxidation, producing a more suitable catalyst for the Pd-catalyzed epoxide opening reaction in terms of chemoselectivity.

  2. Chemoselective Amination of Propargylic C(sp3)–H Bonds via Co(II)-Based Metalloradical Catalysis**

    PubMed Central

    Li, Chaoqun; Jiang, Huiling; Lizardi, Christopher L.

    2014-01-01

    Highly chemoselective intramolecular amination of propargylic C(sp3)–H bonds has been demonstrated for N-bishomopropargylic sulfamoyl azides via Co(II)-based metalloradical catalysis. Supported by D2h-symmetric amidoporphyrin ligand 3,5-DitBu-IbuPhyrin, the Co(II)-catalyzed C–H amination process can proceed effectively under neutral and nonoxidative conditions without the need of any additives, generating N2 as the only byproduct. The metalloradical amination is suitable to both secondary and tertiary propargylic C–H substrates with an unusually high degree of functional group tolerance, providing a direct method for high-yielding synthesis of functionalized propargylamine derivatives. PMID:24840605

  3. Reactivity, chemoselectivity, and diastereoselectivity of the oxyfunctionalization of chiral allylic alcohols and derivatives in microemulsions: comparison of the chemical oxidation by the hydrogen peroxide/sodium molybdate system with the photooxygenation.

    PubMed

    Nardello, Véronique; Caron, Laurent; Aubry, Jean-Marie; Bouttemy, Sabine; Wirth, Thomas; Saha-Möller Chantu, R; Adam, Waldemar

    2004-09-01

    The chiral allylic alcohols 1a-d and their acetate (1e) and silyl ether (1f) derivatives have been oxidized by the H2O2/MoO4(2)- system, a convenient and efficient chemical source of singlet oxygen. This chemical peroxidation (formation of the allylic hydroperoxides 2) has been conducted in various media, which include aqueous solutions, organic solvents, and microemulsions. The reactivity, chemoselectivity, and diastereoselectivity of this chemical oxidation are compared to those of the sensitized photooxygenation, with the emphasis on preparative applications in microemulsion media. While a similar threo diastereoselectivity is observed for both modes of peroxidation, the chemoselectivity differs significantly, since in the chemical oxidation with the H2O2/MoO4(2)- system the undesirable epoxidation by the intermediary peroxomolybdate competes efficiently with the desirable peroxidation by the in situ generated singlet oxygen. A proper choice of the type of microemulsion and the reaction conditions furnishes a high chemoselectivity (up to 97%) in favor of threo-diastereoselective (up to 92%) peroxidation. Copyright 2004 American Chemical Society

  4. Phosphate Tether-Mediated Approach to the Formal Total Synthesis of (-)-Salicylihalamides A and B

    PubMed Central

    Chegondi, Rambabu; Tan, Mary M. L.; Hanson, Paul R.

    2011-01-01

    A concise formal synthesis of the cytotoxic macrolides (-)-salicylihalamides A and B is reported. Key features of the synthetic strategy include a chemoselective hydroboration, highly regio- and diastereoselective methyl cuprate addition, Pd-catalyzed formate reduction, and an E-selective ring-closing metathesis to construct the 12-membered macrocycle subunit. Overall, two routes have been developed from a readily prepared bicyclic phosphate (4-steps), a 13-step route and a more efficient 9-step sequence relying on regioselective esterification of a key diol. PMID:21504150

  5. Synthesis of Lipidated Proteins.

    PubMed

    Mejuch, Tom; Waldmann, Herbert

    2016-08-17

    Protein lipidation is one of the major post-translational modifications (PTM) of proteins. The attachment of the lipid moiety frequently determines the localization and the function of the lipoproteins. Lipidated proteins participate in many essential biological processes in eukaryotic cells, including vesicular trafficking, signal transduction, and regulation of the immune response. Malfunction of these cellular processes usually leads to various diseases such as cancer. Understanding the mechanism of cellular signaling and identifying the protein-protein and protein-lipid interactions in which the lipoproteins are involved is a crucial task. To achieve these goals, fully functional lipidated proteins are required. However, access to lipoproteins by means of standard expression is often rather limited. Therefore, semisynthetic methods, involving the synthesis of lipidated peptides and their subsequent chemoselective ligation to yield full-length lipoproteins, were developed. In this Review we summarize the commonly used methods for lipoprotein synthesis and the development of the corresponding chemoselective ligation techniques. Several key studies involving full-length semisynthetic lipidated Ras, Rheb, and LC3 proteins are presented.

  6. Copper(I)-Catalyzed Chemoselective Coupling of Cyclopropanols with Diazoesters: Ring-Opening C-C Bond Formations.

    PubMed

    Zhang, Hang; Wu, Guojiao; Yi, Heng; Sun, Tong; Wang, Bo; Zhang, Yan; Dong, Guangbin; Wang, Jianbo

    2017-03-27

    Reported herein is an exceptional chemoselective ring-opening/C(sp 3 )-C(sp 3 ) bond formation in the copper(I)-catalyzed reaction of cyclopropanols with diazo esters. The conventional O-H insertion product is essentially suppressed by judicious choice of reaction conditions. DFT calculations provide insights into the reaction mechanism and the rationale for this unusual chemoselectivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Expanding the chemical toolbox for the synthesis of large and uniquely modified proteins

    NASA Astrophysics Data System (ADS)

    Bondalapati, Somasekhar; Jbara, Muhammad; Brik, Ashraf

    2016-05-01

    Methods to prepare proteins that include a specific modification at a desired position are essential for understanding their cellular functions and physical properties in living systems. Chemical protein synthesis, which relies on the chemoselective ligation of unprotected peptides, enables the preparation of modified proteins that are not easily fabricated by other methods. In contrast to recombinant approaches, chemical synthesis can be used to prepare protein analogues such as D-proteins, which are useful in protein structure determination and the discovery of novel therapeutics. Post-translationally modifying proteins is another example where chemical protein synthesis proved itself as a powerful approach for preparing samples with high homogeneity and in workable quantities. In this Review, we discuss the basic principles of the field, focusing on novel chemoselective peptide ligation approaches such as native chemical ligation and the recent advances based on this method with a proven record of success in the synthesis of highly important protein targets.

  8. Reversible chemoselective tagging and functionalization of methionine containing peptides.

    PubMed

    Kramer, Jessica R; Deming, Timothy J

    2013-06-07

    Reagents were developed to allow chemoselective tagging of methionine residues in peptides and polypeptides, subsequent bioorthogonal functionalization of the tags, and cleavage of the tags when desired. This methodology can be used for triggered release of therapeutic peptides, or release of tagged protein digests from affinity columns.

  9. Chemoselective ratiometric imaging of protein S-sulfenylation.

    PubMed

    Tom, Christopher T M B; Crellin, John E; Motiwala, Hashim F; Stone, Matthew B; Davda, Dahvid; Walker, William; Kuo, Yu-Hsuan; Hernandez, Jeannie L; Labby, Kristin J; Gomez-Rodriguez, Lyanne; Jenkins, Paul M; Veatch, Sarah L; Martin, Brent R

    2017-06-29

    Here we report a ratiometric fluorescent probe for chemoselective conjugation to sulfenic acids in living cells. Our approach couples an α-fluoro-substituted dimedone to an aminonaphthalene fluorophore (F-DiNap), which upon sulfenic acid conjugation is locked as the 1,3-diketone, changing the fluorophore excitation. F-DiNap reacts with S-sulfenylated proteins at equivalent rates to current probes, but the α-fluorine substitution blocks side-reactions with biological aldehydes.

  10. Theoretical investigation on the chemoselective N-heterocyclic carbene-catalyzed cross-benzoin reactions.

    PubMed

    Liu, Tao; Han, Shu-Min; Han, Ling-Li; Wang, Lu; Cui, Xiang-Yang; Du, Chong-Yang; Bi, Siwei

    2015-03-28

    A density functional theory study was performed to understand the detailed mechanisms of the cross-benzoin reactions catalyzed by N-heterocyclic carbene (NHC) species. Our theoretical study predicted that the first H-transfer operates with water in solution as a mediator, and the second H-transfer undergoes a concerted mechanism rather than a stepwise one. In addition, the chemoselectivity of the reactions studied in this work has been explored. P1 was obtained as a major product mainly due to the more stable intermediate formed by reaction of NHC with reactant R1. Different steric effects resulting from the fused six-membered ring in transition state TS7 and the fused five-membered ring in transition state TS13 are the origin leading to the chemoselectivity.

  11. Lipases as catalysts in synthesis of fine chemicals.

    PubMed

    Baldessari, Alicia

    2012-01-01

    The application of lipases as catalysts in the synthesis of an intermediate of alfuzosin and lapyrium chloride is described. In the first case, the one-pot procedure to obtain the intermediate involves the treatment of tetrahydrofuroic acid with ethanol in the presence of Candida antarctica lipase followed by the addition of N-methyl-1,3-diaminopropane. In the second part of the chapter, an efficient route for large-scale preparation of lapyrium chloride is developed from chloroacetic acid in four steps, three of them enzymatic. Due to the chemoselective behavior of the lipases, both products described in the present chapter were obtained in a high degree of purity and yield, applying mild reaction conditions, and following a low environmental impact methodology.

  12. Unexpected regio- and chemoselectivity of cationic gold-catalyzed cycloisomerizations of propargylureas: access to tetrasubstituted 3,4-dihydropyrimidin-2(1H)-ones.

    PubMed

    Pereshivko, Olga P; Peshkov, Vsevolod A; Peshkov, Anatoly A; Jacobs, Jeroen; Van Meervelt, Luc; Van der Eycken, Erik V

    2014-03-21

    Cationic gold-catalyzed cycloisomerizations of propargylureas, derived in situ from secondary propargylamines and aryl or alkyl isocyanates, have been studied. The reaction outcome was found to be different from what was previously observed for the tosyl isocyanate-derived ureas in terms of both regio- and chemoselectivity. As a result, the current protocol offers efficient access to the 3,4-dihydropyrimidin-2(1H)-one core through the 6-endo-dig N-cyclization.

  13. Chemoselective Hydrogenation of Aldehydes under Mild, Base-Free Conditions: Manganese Outperforms Rhenium

    PubMed Central

    2018-01-01

    Several hydride Mn(I) and Re(I) PNP pincer complexes were applied as catalysts for the homogeneous chemoselective hydrogenation of aldehydes. Among these, [Mn(PNP-iPr)(CO)2(H)] was found to be one of the most efficient base metal catalysts for this process and represents a rare example which permits the selective hydrogenation of aldehydes in the presence of ketones and other reducible functionalities, such as C=C double bonds, esters, or nitriles. The reaction proceeds at room temperature under base-free conditions with catalyst loadings between 0.1 and 0.05 mol% and a hydrogen pressure of 50 bar (reaching TONs of up to 2000). A mechanism which involves an outer-sphere hydride transfer and reversible PNP ligand deprotonation/protonation is proposed. Analogous isoelectronic and isostructural Re(I) complexes were only poorly active. PMID:29755828

  14. Chemoselective reduction and oxidation of ketones in water through control of the electron transfer pathway

    PubMed Central

    Kim, Sun Min; Yoo, Ho Sung; Hosono, Hideo; Yang, Jung Woon; Kim, Sung Wng

    2015-01-01

    The selective synthesis of different products from the same starting materials in water, which is the most abundant solvent in nature, is a crucial issue as it maximizes the utilization of materials. Realizing such reactions for ketones is of considerable importance because numerous organic functionalities can be obtained via nucleophilic addition reactions. Herein, we report chemoselective reduction and oxidation reactions of 1,2-diketones in water, which initiates anionic electron transfer from the inorganic electride [Ca24Al28O64]4+·4e−, through controlling the pathway of the electrons to substrates. The generation of different radical species for transient intermediates was the key process required to control the reaction selectivity, which was achieved by reacting the anionic electrons with either diketones or O2, leading to the formation of ketyl dianion and superoxide radicals in the reduction and oxidation reactions, respectively. This methodology that utilizes electrides may provide an alternative to the pulse radiolysis of water in synthetic chemistry. PMID:26020413

  15. Recent Advances in the Catalytic One-Pot Synthesis of Flavonoids and Chromones.

    PubMed

    Mohadeszadeh, Manijeh; Iranshahi, Mehrdad

    2017-01-01

    Flavonoids and chromones are two important classes of natural products that have various biological properties. During the past 10 years, there has been a significant increase in studies on the one-pot synthesis of flavonoids and chromones as medicinal scaffolds in drug discovery. This review describes the scope, mechanistic properties and regio- and chemo-selectivity features of several recently developed one-pot procedures for the synthesis of substituted chromones and flavonoids that have recently been published. Special importance is placed on the most promising and exciting medicinal applications of flavonoids and chromones. In this review, we discuss the progress on the synthesis of flavonoid and chromone derivatives in the presence of metal catalysts, organocatalysts, solid surfaces, microwave irradiation, acid and base catalysis, etc. For example, flavones can be prepared via the catalytic coordination of palladium complexes in a short time and at a low temperature with a high yield. Additionally, the one-pot synthesis of 2-substituted chromones via metal triflate (Yb(OTf)3) has provided the best result for this type of reaction with a high yield and a high regio and chemoselectivity. Generally, this review proposes the first specific overview of this developing and rapidly expanding field of flavonoid synthesis. We also discuss the mechanisms and advantages and disadvantages of methods for the synthesis of flavonoids and chromones. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  16. Chemoselective tarantula toxins report voltage activation of wild-type ion channels in live cells

    PubMed Central

    Tilley, Drew C.; Eum, Kenneth S.; Fletcher-Taylor, Sebastian; Austin, Daniel C.; Dupré, Christophe; Patrón, Lilian A.; Garcia, Rita L.; Lam, Kit; Yarov-Yarovoy, Vladimir; Cohen, Bruce E.; Sack, Jon T.

    2014-01-01

    Electrically excitable cells, such as neurons, exhibit tremendous diversity in their firing patterns, a consequence of the complex collection of ion channels present in any specific cell. Although numerous methods are capable of measuring cellular electrical signals, understanding which types of ion channels give rise to these signals remains a significant challenge. Here, we describe exogenous probes which use a novel mechanism to report activity of voltage-gated channels. We have synthesized chemoselective derivatives of the tarantula toxin guangxitoxin-1E (GxTX), an inhibitory cystine knot peptide that binds selectively to Kv2-type voltage gated potassium channels. We find that voltage activation of Kv2.1 channels triggers GxTX dissociation, and thus GxTX binding dynamically marks Kv2 activation. We identify GxTX residues that can be replaced by thiol- or alkyne-bearing amino acids, without disrupting toxin folding or activity, and chemoselectively ligate fluorophores or affinity probes to these sites. We find that GxTX–fluorophore conjugates colocalize with Kv2.1 clusters in live cells and are released from channels activated by voltage stimuli. Kv2.1 activation can be detected with concentrations of probe that have a trivial impact on cellular currents. Chemoselective GxTX mutants conjugated to dendrimeric beads likewise bind live cells expressing Kv2.1, and the beads are released by channel activation. These optical sensors of conformational change are prototype probes that can indicate when ion channels contribute to electrical signaling. PMID:25331865

  17. Chemoselective Radical Dehalogenation and C-C Bond Formation on Aryl Halide Substrates Using Organic Photoredox Catalysts.

    PubMed

    Poelma, Saemi O; Burnett, G Leslie; Discekici, Emre H; Mattson, Kaila M; Treat, Nicolas J; Luo, Yingdong; Hudson, Zachary M; Shankel, Shelby L; Clark, Paul G; Kramer, John W; Hawker, Craig J; Read de Alaniz, Javier

    2016-08-19

    Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity.

  18. Chemoselective, Stereospecific, and Living Polymerization of Polar Divinyl Monomers by Chiral Zirconocenium Catalysts.

    PubMed

    Vidal, Fernando; Gowda, Ravikumar R; Chen, Eugene Y-X

    2015-07-29

    This contribution reports the first chemoselective, stereospecific, and living polymerization of polar divinyl monomers, enabled by chiral ansa-zirconocenium catalysts through an enantiomorphic-site controlled coordination-addition polymerization mechanism. Silyl-bridged-ansa-zirconocenium ester enolate 2 has been synthesized and structurally characterized, but it exhibits low to negligible activity and stereospecificity in the polymerization of polar divinyl monomers including vinyl methacrylate (VMA), allyl methacrylate (AMA), 4-vinylbenzyl methacrylate (VBMA), and N,N-diallyl acrylamide (DAA). In contrast, ethylene-bridged-ansa-zirconocenium ester enolate 1 is highly active and stereospecific in the polymerization of such monomers including AMA, VBMA, and DAA. The polymerization by 1 is perfectly chemoselective for all four polar divinyl monomers, proceeding exclusively through conjugate addition across the methacrylic C═C bond, while leaving the pendant C═C bonds intact. The polymerization of DAA is most stereospecific and controlled, producing essentially stereoperfect isotactic PDAA with [mmmm] > 99%, M(n) matching the theoretical value (thus a quantitative initiation efficiency), and a narrow molecular weight distribution (Đ = 1.06-1.16). The stereospecificity is slightly lower for the AMA polymerization but still leading to highly isotactic poly(allyl methacrylate) (PAMA) with 95-97% [mm]. The polymerization of VBMA is further less stereospecific, affording PVBMA with 90-94% [mm], while the polymerization VMA is least stereospecific. Several lines of evidence from both homo- and block copolymerization results have demonstrated living characteristics of the AMA polymerization by 1. Mechanistic studies of this polymerization have yielded a monometallic coordination-addition polymerization mechanism involving the eight-membered chelating intermediate. Post-functionalization of isotactic polymers bearing the pendant vinyl group on every repeating unit via

  19. Controlling Stereoselectivity and Chemoselectivity of Cyclopropyl Ketyl Radical Anions with Visible Light Photocatalysis

    NASA Astrophysics Data System (ADS)

    Amador, Adrian Gabriel

    A defining characteristic of research in the Yoon laboratory is a focus on the formation and utilization of high-energy reactive intermediates to accomplish difficult transformations. Recent efforts have been aimed at controlling the reactivity of open-shell radical intermediates; both in terms of chemoselectivity and stereoselectivity. Transition metal photocatalysis has proven to be a particularly successful strategy for accomplishing a wide variety of transformations ranging from net redox neutral as well as net reductive and oxidative transformations. This thesis describes one such approach where the combination of a photocatalyst and a Lewis acid can be used to achieve highly selective and high yielding [3 + 2] cycloadditions between aryl cyclopropyl ketones and a wide range of unsaturated (e.g. olefin and imine) coupling partners. Key to the success of these studies was understanding and carefully optimizing both photocatalyst and Lewis acid to achieve the desired reactivity. These studies have resulted in the development of a highly enantioselective [3 + 2] cycloaddition between cyclopropyl ketones and olefins for the synthesis of cyclopentanes as well as the development of a more general redox-auxiliary approach for the [3 + 2] cycloaddition of cyclopropyl ketones and simple olefins and imine derivatives.

  20. Iridium-Catalysed ortho-Directed Deuterium Labelling of Aromatic Esters--An Experimental and Theoretical Study on Directing Group Chemoselectivity.

    PubMed

    Devlin, Jennifer; Kerr, William J; Lindsay, David M; McCabe, Timothy J D; Reid, Marc; Tuttle, Tell

    2015-06-25

    Herein we report a combined experimental and theoretical study on the deuterium labelling of benzoate ester derivatives, utilizing our developed iridium N-heterocyclic carbene/phosphine catalysts. A range of benzoate esters were screened, including derivatives with electron-donating and -withdrawing groups in the para- position. The substrate scope, in terms of the alkoxy group, was studied and the nature of the catalyst counter-ion was shown to have a profound effect on the efficiency of isotope exchange. Finally, the observed chemoselectivity was rationalized by rate studies and theoretical calculations, and this insight was applied to the selective labelling of benzoate esters bearing a second directing group.

  1. Chemoselective N-arylation of aminobenzamides via copper catalysed Chan-Evans-Lam reactions.

    PubMed

    Liu, Shuai; Zu, Weisai; Zhang, Jinli; Xu, Liang

    2017-11-15

    Chemoselective N-arylation of unprotected aminobenzamides was achieved via Cu-catalysed Chan-Evans-Lam cross-coupling with aryl boronic acids for the first time. Simple copper catalysts enable the selective arylation of amino groups in ortho/meta/para-aminobenzamides under open-flask conditions. The reactions were scalable and compatible with a wide range of functional groups.

  2. Highly chemoselective esterification reactions and Boc/THP/TBDMS discriminating deprotections under samarium(III) catalysis.

    PubMed

    Gopinath, Pushparathinam; Nilaya, Surapaneni; Muraleedharan, Kannoth Manheri

    2011-04-15

    The usefulness of SmCl(3) as an excellent catalyst for chemoselective esterifications and selective removal of acid sensitive protecting groups such as Boc, THP, and TBDMS in the presence of one another is demonstrated through suitable examples. © 2011 American Chemical Society

  3. High Activity and Efficient Turnover by a Simple, Self-Assembled "Artificial Diels-Alderase".

    PubMed

    Martí-Centelles, Vicente; Lawrence, Andrew L; Lusby, Paul J

    2018-02-28

    The Diels-Alder (DA) reaction is a cornerstone of synthesis, yet Nature does not use catalysts for intermolecular [4+2] cycloadditions. Attempts to create artificial "Diels-Alderases" have also met with limited success, plagued by product inhibition. Using a simple Pd 2 L 4 capsule we now show DA catalysis that combines efficient turnover alongside enzyme-like hallmarks. This includes excellent activity (k cat /k uncat > 10 3 ), selective transition-state stabilization comparable to the most proficient DA catalytic antibodies, and control over regio- and chemoselectivity that would otherwise be difficult to achieve using small-molecule catalysts. Unlike other catalytic approaches that use synthetic capsules, this method is not defined by entropic effects; instead multiple H-bonding interactions modulate reactivity, reminiscent of enzymatic action.

  4. Efficient total synthesis of (S)-14-azacamptothecin.

    PubMed

    Liu, Guan-Sai; Yao, Yuan-Shan; Xu, Peng; Wang, Shaozhong; Yao, Zhu-Jun

    2010-06-01

    An efficient total synthesis of (S)-14-azacamptothecin has been accomplished in 10 steps and 56% overall yield from 5H-pyrano[4,3-d]pyrimidine 8. A mild Hendrickson reagent-triggered intramolecular cascade cyclization, a highly enantioselective dihydroxylation, and an efficient palladium-catalyzed transformation of an O-allyl into N-allyl group are the key steps in the synthesis. This work provides a much higher overall yield than the previous achievement and shows sound flexibility for the further applications that will lead to new bioactive analogues.

  5. Chemoselective amide formation using O-(4-nitrophenyl)hydroxylamines and pyruvic acid derivatives.

    PubMed

    Kumar, Sonali; Sharma, Rashi; Garcia, Megan; Kamel, Joseph; McCarthy, Caroline; Muth, Aaron; Phanstiel, Otto

    2012-12-07

    A series of O-(4-nitrophenyl)hydroxylamines were synthesized from their respective oximes using a pulsed addition of excess NaBH(3)CN at pH 3 in 65-75% yield. Steric hindrance near the oxime functional group played a key role in both the ease by which the oxime could be reduced and the subsequent reactivity of the respective hydroxylamine. Reaction of the respective hydroxylamines with pyruvic acid derivatives generated the desired amides in good yields. A comparison of phenethylamine systems bearing different leaving groups revealed significant differences in the rates of these systems and suggested that the leaving group ability of the N-OR substituent plays an important role in determining their reactivity with pyruvic acid. Competition experiments (in 68% DMSO/phosphate buffered saline) using 1 equiv of N-phenethyl-O-(4-nitrophenyl)hydroxylamine and 2 equiv of pyruvic acid in the presence of other nucleophiles such as glycine, cysteine, phenol, hexanoic acid, and lysine demonstrated that significant chemoselectivity is present in this reaction. The results suggest that this chemoselective reaction can occur in the presence of excess α-amino acids, phenols, acids, thiols, and amines.

  6. Dual Roles of β-Oxodithioesters in the Copper-Catalyzed Synthesis of Benzo[e]pyrazolo[1,5-c][1,3]thiazine Derivatives.

    PubMed

    Wen, Li-Rong; Yuan, Wen-Kui; Li, Ming

    2015-05-15

    A facile and efficient method for the chemoselective synthesis of benzo[e]pyrazolo[1,5-c][1,3]thiazine derivatives has been developed by tandem Ullmann coupling reactions of β-oxodithioesters (ODEs) with 3-(2-bromoaryl)-1H-pyrazoles in C-S bond formation manner, in which ODEs play dual roles as both a substrate and a ligand. A series of benzo[e]pyrazolo[1,5-c][1,3]thiazine derivatives were provided in good to excellent yields with CuI as the copper source in the presence of NaOH in CH3CN at 80 °C under a N2 atmosphere.

  7. Tandem Reactions for Streamlining Synthesis

    PubMed Central

    HUSSAIN, MAHMUD M.; WALSH, PATRICK J.

    2009-01-01

    CONSPECTUS In 1980 Sharpless and Katsuki introduced the asymmetric epoxidation of prochiral allylic alcohols (the Sharpless-Katsuki Asymmetric Epoxidation), which enabled the rapid synthesis of highly enantioenriched epoxy alcohols. This reaction was a milestone in the development of asymmetric catalysis because it was the first highly enantioselective oxidation reaction. Furthermore, it provided access to enantioenriched allylic alcohols that are now standard starting materials in natural product synthesis. In 1981 Sharpless and coworkers made another seminal contribution by describing the kinetic resolution (KR) of racemic allylic alcohols. This work demonstrated that small-molecule catalysts could compete with enzymatic catalysts in KRs. For these pioneering works, Sharpless was awarded the 2001 Nobel Prize with Knowles and Noyori. Despite these achievements, the Sharpless KR is not an efficient method to prepare epoxy alcohols with high enantiomeric excess (ee). First, the racemic allylic alcohol must be prepared and purified. KR of the racemic allylic alcohol must be stopped at low conversion, because the ee of the product epoxy alcohol decreases as the KR progresses. Thus, better methods to prepare epoxy alcohols containing stereogenic carbinol carbons are needed. This Account summarizes our efforts to develop one-pot methods for the synthesis of various epoxy alcohols and allylic epoxy alcohols with high enantio-, diastereo-, and chemoselectivity. Our laboratory developed titanium-based catalysts for use in the synthesis of epoxy alcohols with tertiary carbinols. The catalysts are involved in the first step, which is an asymmetric alkyl or allyl addition to enones. The resulting intermediates are then subjected to a titanium-directed diastereoselective epoxidation to provide tertiary epoxy alcohols. Similarly, the synthesis of acyclic epoxy alcohols begins with asymmetric additions to enals and subsequent epoxidation. The methods described here enable the

  8. Diazo Groups Endure Metabolism and Enable Chemoselectivity in Cellulo

    PubMed Central

    2015-01-01

    We introduce a stabilized diazo group as a reporter for chemical biology. ManDiaz, which is a diazo derivative of N-acetylmannosamine, is found to endure cellular metabolism and label the surface of a mammalian cell. There its diazo group can undergo a 1,3-dipolar cycloaddition with a strained alkyne, providing a signal comparable to that from the azido congener, ManNAz. The chemoselectivity of diazo and alkynyl groups enables dual labeling of cells that is not possible with azido and alkynyl groups. Thus, the diazo group, which is approximately half the size of an azido group, provides unique opportunities for orthogonal labeling of cellular components. PMID:25658416

  9. Diazo groups endure metabolism and enable chemoselectivity in cellulo.

    PubMed

    Andersen, Kristen A; Aronoff, Matthew R; McGrath, Nicholas A; Raines, Ronald T

    2015-02-25

    We introduce a stabilized diazo group as a reporter for chemical biology. ManDiaz, which is a diazo derivative of N-acetylmannosamine, is found to endure cellular metabolism and label the surface of a mammalian cell. There its diazo group can undergo a 1,3-dipolar cycloaddition with a strained alkyne, providing a signal comparable to that from the azido congener, ManNAz. The chemoselectivity of diazo and alkynyl groups enables dual labeling of cells that is not possible with azido and alkynyl groups. Thus, the diazo group, which is approximately half the size of an azido group, provides unique opportunities for orthogonal labeling of cellular components.

  10. Chemical protein synthesis: Inventing synthetic methods to decipher how proteins work.

    PubMed

    Kent, Stephen

    2017-09-15

    Total chemical synthesis of proteins has been rendered practical by the chemical ligation principle: chemoselective condensation of unprotected peptide segments equipped with unique, mutually reactive functional groups, enabled by formation of a non-native replacement for the peptide bond. Ligation chemistries are briefly described, including native chemical ligation - thioester-mediated, amide-forming reaction at Xaa-Cys sites - and its extensions. Case studies from the author's own works are used to illustrate the utility and applications of chemical protein synthesis. Selected recent developments in the field are briefly discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Tactical Synthesis Of Efficient Global Search Algorithms

    NASA Technical Reports Server (NTRS)

    Nedunuri, Srinivas; Smith, Douglas R.; Cook, William R.

    2009-01-01

    Algorithm synthesis transforms a formal specification into an efficient algorithm to solve a problem. Algorithm synthesis in Specware combines the formal specification of a problem with a high-level algorithm strategy. To derive an efficient algorithm, a developer must define operators that refine the algorithm by combining the generic operators in the algorithm with the details of the problem specification. This derivation requires skill and a deep understanding of the problem and the algorithmic strategy. In this paper we introduce two tactics to ease this process. The tactics serve a similar purpose to tactics used for determining indefinite integrals in calculus, that is suggesting possible ways to attack the problem.

  12. Tandem ring-closing metathesis/transfer hydrogenation: practical chemoselective hydrogenation of alkenes.

    PubMed

    Connolly, Timothy; Wang, Zhongyu; Walker, Michael A; McDonald, Ivar M; Peese, Kevin M

    2014-09-05

    An operationally simple chemoselective transfer hydrogenation of alkenes using ruthenium metathesis catalysts is presented. Of great practicality, the transfer hydrogenation reagents can be added directly to a metathesis reaction and effect hydrogenation of the product alkene in a single pot at ambient temperature without the need to seal the vessel to prevent hydrogen gas escape. The reduction is applicable to a range of alkenes and can be performed in the presence of aryl halides and benzyl groups, a notable weakness of Pd-catalyzed hydrogenations. Scope and mechanistic considerations are presented.

  13. Approximation concepts for efficient structural synthesis

    NASA Technical Reports Server (NTRS)

    Schmit, L. A., Jr.; Miura, H.

    1976-01-01

    It is shown that efficient structural synthesis capabilities can be created by using approximation concepts to mesh finite element structural analysis methods with nonlinear mathematical programming techniques. The history of the application of mathematical programming techniques to structural design optimization problems is reviewed. Several rather general approximation concepts are described along with the technical foundations of the ACCESS 1 computer program, which implements several approximation concepts. A substantial collection of structural design problems involving truss and idealized wing structures is presented. It is concluded that since the basic ideas employed in creating the ACCESS 1 program are rather general, its successful development supports the contention that the introduction of approximation concepts will lead to the emergence of a new generation of practical and efficient, large scale, structural synthesis capabilities in which finite element analysis methods and mathematical programming algorithms will play a central role.

  14. Remarkable biomimetic chemoselective aerobic oxidation of flavano-ellagitannins found in oak-aged wine.

    PubMed

    Petit, Emilie; Lefeuvre, Dorothée; Jacquet, Rémi; Pouységu, Laurent; Deffieux, Denis; Quideau, Stéphane

    2013-10-25

    Under the auspices of Bacchus! Acutissimins, natural flavano-ellagitannins, occur in oak-aged wine as a result of a diastereoselective condensation reaction of the flavan-3-ol catechin, a component of grapes, with the C-glucosidic ellagitannin vescalagin, found in oak. The acutissimins are further converted into natural mongolicains and analogues of camelliatannin G in a remarkably chemoselective fashion by simple aerobic oxidation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Chemoselective ligation and antigen vectorization.

    PubMed

    Gras-Masse, H

    2001-01-01

    The interest in cocktail-lipopeptide vaccines has now been confirmed by phase I clinical trials: highly diversified B-, T-helper or cytotoxic T-cell epitopes can be combined with a lipophilic vector for the induction of B- and T-cell responses of predetermined specificity. With the goal of producing an improved vaccine that should ideally induce a multispecific response in non-selected populations, increasing the diversity of the immunizing mixture represents one of the most obvious strategies.The selective delivery of antigens to professional antigen-presenting cells represents another promising approach for the improvement of vaccine efficacy. In this context, the mannose-receptor represents an attractive entry point for the targeting to dendritic cells of antigens linked to clustered glycosides or glycomimetics. In all cases, highly complex but fully characterized molecules must be produced. To develop a modular and flexible strategy which could be generally applicable to a large set of peptide antigens, we elected to explore the potentialities of chemoselective ligation methods. The hydrazone bond was found particularly reliable and fully compatible with sulphide ligation. Hydrazone/thioether orthogonal ligation systems could be developed to account for the nature of the antigens and the solubility of the vector systems. Copyright 2001 The International Association for Biologicals.

  16. Enantioselective total synthesis of (-)-strychnine using the catalytic asymmetric Michael reaction and tandem cyclization.

    PubMed

    Ohshima, Takashi; Xu, Youjun; Takita, Ryo; Shimizu, Satoshi; Zhong, Dafang; Shibasaki, Masakatsu

    2002-12-11

    The enantioselective total synthesis of (-)-strychnine was accomplished through the use of the highly practical catalytic asymmetric Michael reaction (0.1 mol % of (R)-ALB, more than kilogram scale, without chromatography, 91% yield and >99% ee) as well as a tandem cyclization that simultaneously constructed B- and D-rings (>77% yield). Moreover, newly developed reaction conditions for thionium ion cyclization, NaBH3CN reduction of the imine moiety in the presence of Lewis acid to prevent ring opening reaction, and chemoselective reduction of the thioether (desulfurization) in the presence of exocyclic olefin were pivotal to complete the synthesis. The described chemistry paves the way for the synthesis of more advanced Strychnos alkaloids.

  17. An Efficient Synthesis of Dicycloalkylacetylenes: 1,2-Dicyclopropylethyne and (cyclopropylethynyl)cyclobutane (Preprint)

    DTIC Science & Technology

    2008-11-05

    ANSI Std. 239.18 The Distribution A : “Approved for public release; distribution unlimited.” An Efficient Synthesis of Dicycloalkylacetylenes: 1 ... synthesis of terminal/internal alkynes involve the alkynylation of alkylhalide with metal acetylide 1 or base promoted dehydrohalogenation 2 of...chloropent- 1 -yne (5, 57%) 9 and 1,8- dichlorooct- 1 -yne(9, 36%). 8 We report here an efficient and economical synthesis of dicycloalkylethynes namely

  18. Catalyst-Dependent Chemoselective Formal Insertion of Diazo Compounds into C-C or C-H Bonds of 1,3-Dicarbonyl Compounds.

    PubMed

    Liu, Zhaohong; Sivaguru, Paramasivam; Zanoni, Giuseppe; Anderson, Edward A; Bi, Xihe

    2018-05-08

    A catalyst-dependent chemoselective one-carbon insertion of diazo compounds into the C-C or C-H bonds of 1,3-dicarbonyl species is reported. In the presence of silver(I) triflate, diazo insertion into the C(=O)-C bond of the 1,3-dicarbonyl substrate leads to a 1,4-dicarbonyl product containing an all-carbon α-quaternary center. This reaction constitutes the first example of an insertion of diazo-derived carbenoids into acyclic C-C bonds. When instead scandium(III) triflate was applied as the catalyst, the reaction pathway switched to formal C-H insertion, affording 2-alkylated 1,3-dicarbonyl products. Different reaction pathways are proposed to account for this powerful catalyst-dependent chemoselectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Chemoselective covalent coupling of oligonucleotide probes to self-assembled monolayers.

    PubMed

    Devaraj, Neal K; Miller, Gregory P; Ebina, Wataru; Kakaradov, Boyko; Collman, James P; Kool, Eric T; Chidsey, Christopher E D

    2005-06-22

    A chemoselective route to routinely and rapidly attach oligonucleotide probes to well-defined surfaces is presented. Cu(I) tris(benzyltriazolylmethyl)amine-catalyzed coupling of terminal acetylenes to azides on a self-assembled monolayer is used instead of traditional nucleophilic-electrophilic coupling reactions. The reaction proceeds well even in the presence of purposely introduced nucleophilic and electrophilic impurities. The density of oligonucleotide probes can be controlled by controlling the amount of azide functionality. Although most of our work was done on gold surfaces, this technique should be readily applicable to any surface on which an azide-containing monolayer can be assembled as we have preliminarily demonstrated by derivatizing azidotrimethoxysilane-modified glass slides with fluorescein-containing oligonucleotides.

  20. Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

    PubMed Central

    2015-01-01

    Summary Amino acids, whether natural, semisynthetic or synthetic, are among the most important and useful chiral building blocks available for organic chemical synthesis. In principle, they can function as inexpensive, chiral and densely functionalized starting materials. On the other hand, the use of amino acid starting materials routinely necessitates protective group chemistry, and in reality, large-scale preparations of even the simplest side-chain derivatives of many amino acids often become annoyingly strenuous due to the necessity of employing protecting groups, on one or more of the amino acid functionalities, during the synthetic sequence. However, in the case of hydroxyamino acids such as hydroxyproline, serine, threonine, tyrosine and 3,4-dihydroxyphenylalanine (DOPA), many O-acyl side-chain derivatives are directly accessible via a particularly expedient and scalable method not commonly applied until recently. Direct acylation of unprotected hydroxyamino acids with acyl halides or carboxylic anhydrides under appropriately acidic reaction conditions renders possible chemoselective O-acylation, furnishing the corresponding side-chain esters directly, on multigram-scale, in a single step, and without chromatographic purification. Assuming a certain degree of stability under acidic reaction conditions, the method is also applicable for a number of related compounds, such as various amino alcohols and the thiol-functional amino acid cysteine. While the basic methodology underlying this approach has been known for decades, it has evolved through recent developments connected to amino acid-derived chiral organocatalysts to become a more widely recognized procedure for large-scale preparation of many useful side-chain derivatives of hydroxyamino acids and related compounds. Such derivatives are useful in peptide chemistry and drug development, as amino acid amphiphiles for asymmetric catalysis, and as amino acid acrylic precursors for preparation of

  1. A statistical view of protein chemical synthesis using NCL and extended methodologies.

    PubMed

    Agouridas, Vangelis; El Mahdi, Ouafâa; Cargoët, Marine; Melnyk, Oleg

    2017-09-15

    Native chemical ligation and extended methodologies are the most popular chemoselective reactions for protein chemical synthesis. Their combination with desulfurization techniques can give access to small or challenging proteins that are exploited in a large variety of research areas. In this report, we have conducted a statistical review of their use for protein chemical synthesis in order to provide a flavor of the recent trends and identify the most popular chemical tools used by protein chemists. To this end, a protein chemical synthesis (PCS) database (http://pcs-db.fr) was created by collecting a set of relevant data from more than 450 publications covering the period 1994-2017. A preliminary account of what this database tells us is presented in this report. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Total synthesis of the thiopeptide antibiotic amythiamicin D.

    PubMed

    Hughes, Rachael A; Thompson, Stewart P; Alcaraz, Lilian; Moody, Christopher J

    2005-11-09

    The thiopeptide (or thiostrepton) antibiotics are a class of sulfur containing highly modified cyclic peptides with interesting biological properties, including reported activity against MRSA and malaria. Described herein is the total synthesis of the thiopeptide natural product amythiamicin D, which utilizes a biosynthesis-inspired hetero-Diels-Alder route to the pyridine core of the antibiotic as a key step. Preliminary studies using a range of serine-derived 1-ethoxy-2-azadienes established that hetero-Diels-Alder reaction with N-acetylenamines proceeded efficiently under microwave irradiation to give 2,3,6-trisubstituted pyridines. The thiazole building blocks of the antibiotic were obtained by either classical Hantzsch reactions or by dirhodium(II)-catalyzed chemoselective carbene N-H insertion followed by thionation, and were combined to give the bis-thiazole that forms the left-hand fragment of the antibiotic. The key Diels-Alder reaction of a tris-thiazolyl azadiene with benzyl 2-(1-acetylaminoethenyl)thiazole-4-carboxylate gave the core tetrathiazolyl pyridine, which was elaborated into the natural product by successive incorporation of glycine and bis-thiazole fragments followed by macrocyclization.

  3. Synthesis of a novel fused pyrrolodiazepine-based library with anti-cancer activity.

    PubMed

    Malik, Neha; Iyamu, Iredia D; Scheidt, Karl A; Schiltz, Gary E

    2018-04-11

    Development of drugs for new and persistent diseases will increasingly rely on the expansion of accessible chemical space to allow exploration of novel molecular targets. Here we report the synthesis of a library of novel fused heterobicyclic small molecules based on the 1,4-diazepine and 2,4-pyrrolidinedione scaffolds. Key chemical transformations included a Mannich-type condensation and chemoselective N-acylation reactions. Screening shows anti-cancer activity of several library compounds which suggests translational potential of this novel chemical scaffold.

  4. Efficient and Highly Selective Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Bucky Nanodiamond.

    PubMed

    Lin, Yangming; Wu, Kuang-Hsu Tim; Yu, Linhui; Heumann, Saskia; Su, Dang Sheng

    2017-09-11

    Selective oxidation of alcohols to aldehydes is widely applicable to the synthesis of various green chemicals. The poor chemoselectivity for complicated primary aldehydes over state-of-the-art metal-free or metal-based catalysts represents a major obstacle for industrial application. Bucky nanodiamond is a potential green catalyst that exhibits excellent chemoselectivity and cycling stability for the selective oxidation of primary alcohols in diverse structures (22 examples, including aromatic, substituted aromatic, unsaturated, heterocyclic, and linear chain alcohols) to their corresponding aldehydes. The results are comparable to reported transition-metal catalysts including conventional Pt/C and Ru/C catalysts for certain substrates under solvent-free conditions. The possible activation process of the oxidant and substrates by the surface oxygen groups and defect species are revealed with model catalysts, ex situ electrochemical measurements, and ex situ attenuated total reflectance. The zigzag edges of sp 2 carbon planes are shown to play a key role in these reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Chemoselective formation of unsymmetrically substituted ethers from catalytic reductive coupling of aldehydes and ketones with alcohols in aqueous solution.

    PubMed

    Kalutharage, Nishantha; Yi, Chae S

    2015-04-03

    A well-defined cationic Ru-H complex catalyzes reductive etherification of aldehydes and ketones with alcohols. The catalytic method employs environmentally benign water as the solvent and cheaply available molecular hydrogen as the reducing agent to afford unsymmetrical ethers in a highly chemoselective manner.

  6. Chemoselective N-heterocyclic carbene-catalyzed cross-benzoin reactions: importance of the fused ring in triazolium salts.

    PubMed

    Langdon, Steven M; Wilde, Myron M D; Thai, Karen; Gravel, Michel

    2014-05-28

    Morpholinone- and piperidinone-derived triazolium salts are shown to catalyze highly chemoselective cross-benzoin reactions between aliphatic and aromatic aldehydes. The reaction scope includes ortho-, meta-, and para-substituted benzaldehyde derivatives with a range of electron-donating and -withdrawing groups as well as branched and unbranched aliphatic aldehydes. Catalytic loadings as low as 5 mol % give excellent yields in these reactions (up to 99%).

  7. The thermodynamic efficiency of ATP synthesis in oxidative phosphorylation.

    PubMed

    Nath, Sunil

    2016-12-01

    As the chief energy source of eukaryotic cells, it is important to determine the thermodynamic efficiency of ATP synthesis in oxidative phosphorylation (OX PHOS). Previous estimates of the thermodynamic efficiency of this vital process have ranged from Lehninger's original back-of-the-envelope calculation of 38% to the often quoted value of 55-60% in current textbooks of biochemistry, to high values of 90% from recent information theoretic considerations, and reports of realizations of close to ideal 100% efficiencies by single molecule experiments. Hence this problem has been reinvestigated from first principles. The overall thermodynamic efficiency of ATP synthesis in the mitochondrial energy transduction OX PHOS process has been found to lie between 40 and 41% from four different approaches based on a) estimation using structural and biochemical data, b) fundamental nonequilibrium thermodynamic analysis, c) novel insights arising from Nath's torsional mechanism of energy transduction and ATP synthesis, and d) the overall balance of cellular energetics. The torsional mechanism also offers an explanation for the observation of a thermodynamic efficiency approaching 100% in some experiments. Applications of the unique, molecular machine mode of functioning of F 1 F O -ATP synthase involving direct inter-conversion of chemical and mechanical energies in the design and fabrication of novel, man-made mechanochemical devices have been envisaged, and some new ways to exorcise Maxwell's demon have been proposed. It is hoped that analysis of the fundamental problem of energy transduction in OX PHOS from a fresh perspective will catalyze new avenues of research in this interdisciplinary field. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Deciphering the chemoselectivity of nickel-dependent quercetin 2,4-dioxygenase.

    PubMed

    Wang, Wen-Juan; Wei, Wen-Jie; Liao, Rong-Zhen

    2018-06-13

    The reaction mechanism and chemoselectivity of nickel-dependent quercetin 2,4-dioxygenase (2,4-QueD) have been investigated using the QM/MM approach. The protonation state of the Glu74 residue, a first-shell ligand of Ni, has been considered to be either neutral or deprotonated. QM/MM calculations predict that Glu74 must be deprotonated to rationalize the chemoselectivity and steer the 2,4-dioxygenolytic cleavage of quercetin, which harvests the experimentally-observed product, 2-protocatechuoylphloroglucinol carboxylic acid, coupled with the release of carbon monoxide. If the enzyme has a neutral Glu74 residue, the undesired 2,3-dioxygenolytic cleavage of quercetin becomes the dominant pathway, leading to the formation of α-keto acid. The calculations suggest that the reaction takes place via three major steps: (1) attack of the superoxide on the C2 of the substrate pyrone ring to generate a NiII-peroxide intermediate; (2) formation of the second C-O bond between C4 and the peroxide to produce a peroxide bridge; (3) simultaneous cleavage of the C2-C3, C3-C4, and O1-O2 bonds with the formation of 2-protocatechuoylphloroglucinol carboxylic acid and carbon monoxide. The third step was found to be rate-limiting, with a barrier of 17.4 kcal mol-1, which is in very good agreement with the experimental kinetic data. For the second C-O bond formation, an alternative pathway is that the peroxide attacks the C3 of the substrate pyrone ring, leading to the formation of a four-membered ring intermediate, which then undergoes concerted C2-C3 and O1-O2 bond cleavages to produce an α-keto acid. This pathway is associated with a barrier of 30.6 kcal mol-1, which is much higher than the major pathway. When Glu74 is protonated, the 2,3-dioxygenolytic pathway, however, has a lower barrier (21.8 kcal mol-1) than the 2,4-dioxygenolytic pathway.

  9. N-Heterocyclic carbene-catalyzed chemoselective cross-aza-benzoin reaction of enals with isatin-derived ketimines: access to chiral quaternary aminooxindoles.

    PubMed

    Xu, Jianfeng; Mou, Chengli; Zhu, Tingshun; Song, Bao-An; Chi, Yonggui Robin

    2014-06-20

    A chemo- and enantioselective cross-aza-benzoin reaction between enals and isatin-derived ketimines is disclosed. The high chemoselectivity (of the acyl anion reaction over enal α- and β-carbon reactions) is enabled by the electronic and steric properties of the N-heterocyclic carbene organocatalyst.

  10. Key Building Blocks via Enzyme-Mediated Synthesis

    NASA Astrophysics Data System (ADS)

    Fischer, Thomas; Pietruszka, Jörg

    Biocatalytic approaches to valuable building blocks in organic synthesis have emerged as an important tool in the last few years. While first applications were mainly based on hydrolases, other enzyme classes such as oxidoreductases or lyases moved into the focus of research. Nowadays, a vast number of biotransformations can be found in the chemical and pharmaceutical industries delivering fine chemicals or drugs. The mild reaction conditions, high stereo-, regio-, and chemoselectivities, and the often shortened reaction pathways lead to economical and ecological advantages of enzymatic conversions. Due to the enormous number of enzyme-mediated syntheses, the present chapter is not meant to be a complete review, but to deliver comprehensive insights into well established enzymatic systems and recent advances in the application of enzymes in natural product synthesis. Furthermore, it is focused on the most frequently used enzymes or enzyme classes not covered elsewhere in the present volume.

  11. The role of carbon dioxide in chemoselective hydrogenation of halonitroaromatics over supported noble metal catalysts in supercritical carbon dioxide.

    PubMed

    Ichikawa, Shinichiro; Tada, Mizuki; Iwasawa, Yasuhiro; Ikariya, Takao

    2005-02-21

    Chemoselective hydrogenation of halogenated nitrobenzenes over Pt/C catalysts proceeds effectively in supercritical carbon dioxide (scCO2) to produce halogenated anilines with excellent selectivity; the rate of the hydrogenation of nitro groups is markedly enhanced in scCO2 compared to the neat reaction, and the dehalogenation reaction is significantly suppressed.

  12. Synthesis of (-)-pseudotabersonine, (-)-pseudovincadifformine, and (+)-coronaridine enabled by photoredox catalysis in flow.

    PubMed

    Beatty, Joel W; Stephenson, Corey R J

    2014-07-23

    Natural product modification with photoredox catalysis allows for mild, chemoselective access to a wide array of related structures in complex areas of chemical space, providing the possibility for novel structural motifs as well as useful quantities of less abundant congeners. While amine additives have been used extensively as stoichiometric electron donors for photocatalysis, the controlled modification of amine substrates through single-electron oxidation is ideal for the synthesis and modification of alkaloids. Here, we report the conversion of the amine (+)-catharanthine into the natural products (-)-pseudotabersonine, (-)-pseudovincadifformine, and (+)-coronaridine utilizing visible light photoredox catalysis.

  13. Chemoselective chromium(II)-catalyzed cross-coupling reactions of dichlorinated heteroaromatics with functionalized aryl grignard reagents.

    PubMed

    Steib, Andreas K; Kuzmina, Olesya M; Fernandez, Sarah; Malhotra, Sushant; Knochel, Paul

    2015-01-26

    Chromium(II) chloride catalyzes the chemoselective cross-coupling reaction of dichloropyridines with a range of functionalized (hetero)aromatic Grignard reagents at room temperature. Functional groups, such as esters and acetals, are well tolerated in this transformation. Previously challenging substrates, quinolines and isoquinolines, participate in the selective Cr-catalyzed cross-coupling in cyclopentyl methyl ether (CPME) as the solvent. The effective purging of Cr salts is demonstrated by using various solid supports. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Thermally robust Au99(SPh)42 nanoclusters for chemoselective hydrogenation of nitrobenzaldehyde derivatives in water.

    PubMed

    Li, Gao; Zeng, Chenjie; Jin, Rongchao

    2014-03-05

    We report the synthesis and catalytic application of thermally robust gold nanoclusters formulated as Au99(SPh)42. The formula was determined by electrospray ionization and matrix-assisted laser desorption ionization mass spectrometry in conjunction with thermogravimetric analysis. The optical spectrum of Au99(SPh)42 nanoclusters shows absorption peaks at ~920 nm (1.35 eV), 730 nm (1.70 eV), 600 nm (2.07 eV), 490 nm (2.53 eV), and 400 nm (3.1 eV) in contrast to conventional gold nanoparticles, which exhibit a plasmon resonance band at 520 nm (for spherical particles). The ceria-supported Au99(SPh)42 nanoclusters were utilized as a catalyst for chemoselective hydrogenation of nitrobenzaldehyde to nitrobenzyl alcohol in water using H2 gas as the hydrogen source. The selective hydrogenation of the aldehyde group catalyzed by nanoclusters is a surprise because conventional nanogold catalysts instead give rise to the product resulting from reduction of the nitro group. The Au99(SPh)42/CeO2 catalyst gives high catalytic activity for a range of nitrobenzaldehyde derivatives and also shows excellent recyclability due to its thermal robustness. We further tested the size-dependent catalytic performance of Au25(SPh)18 and Au36(SPh)24 nanoclusters, and on the basis of their crystal structures we propose a molecular adsorption site for nitrobenzaldehyde. The nanocluster material is expected to find wide application in catalytic reactions.

  15. An efficient chemical synthesis of nicotinamide riboside (NAR) and analogues.

    PubMed

    Tanimori, Shinji; Ohta, Takeshi; Kirihata, Mitsunori

    2002-04-22

    A simple and efficient synthesis of nicotinamide riboside (NAR) 1 and derivatives 4 and 5 via trimethylsilyl trifluoromethanesulfonate (TMSOTf)-mediated N-glycosilation followed by spontaneous deacetylation by treating with methanol is reported.

  16. Racemic & quasi-racemic protein crystallography enabled by chemical protein synthesis.

    PubMed

    Kent, Stephen Bh

    2018-04-04

    A racemic protein mixture can be used to form centrosymmetric crystals for structure determination by X-ray diffraction. Both the unnatural d-protein and the corresponding natural l-protein are made by total chemical synthesis based on native chemical ligation-chemoselective condensation of unprotected synthetic peptide segments. Racemic protein crystallography is important for structure determination of the many natural protein molecules that are refractory to crystallization. Racemic mixtures facilitate the crystallization of recalcitrant proteins, and give diffraction-quality crystals. Quasi-racemic crystallization, using a single d-protein molecule, can facilitate the determination of the structures of a series of l-protein analog molecules. Copyright © 2018 Elsevier Ltd. All rights reserved.

  17. ortho-Methoxyphenols as Convenient Oxidative Bioconjugation Reagents with Application to Site-Selective Heterobifunctional Cross-Linkers.

    PubMed

    ElSohly, Adel M; MacDonald, James I; Hentzen, Nina B; Aanei, Ioana L; El Muslemany, Kareem M; Francis, Matthew B

    2017-03-15

    The synthesis of complex protein-based bioconjugates has been facilitated greatly by recent developments in chemoselective methods for biomolecular modification. The oxidative coupling of o-aminophenols or catechols with aniline functional groups is chemoselective, mild, and rapid; however, the oxidatively sensitive nature of the electron-rich aromatics and the paucity of commercial sources pose some obstacles to the general use of these reactive strategies. Herein, we identify o-methoxyphenols as air-stable, commercially available derivatives that undergo efficient oxidative couplings with anilines in the presence of periodate as oxidant. Mechanistic considerations informed the development of a preoxidation protocol that can greatly reduce the amount of periodate necessary for effective coupling. The stability and versatility of these reagents was demonstrated through the synthesis of complex protein-protein bioconjugates using a site-selective heterobifunctional cross-linker comprising both o-methoxyphenol and 2-pyridinecarboxaldehyde moieties. This compound was used to link epidermal growth factor to genome-free MS2 viral capsids, affording nanoscale delivery vectors that can target a variety of cancer cell types.

  18. Total Synthesis of Plakilactones C, B and des-Hydroxyplakilactone B by the Oxidative Cleavage of Gracilioether Furanylidenes.

    PubMed

    Norris, Matthew D; Perkins, Michael V

    2016-08-05

    A chemoselective oxidative cleavage of synthetic gracilioether B, 11-epi-gracilioether C benzoate, and des-hydroxygracilioether C with pyridinium chlorochromate, which proceeds with loss of the furanyl acetate, has enabled total synthesis and stereochemical elucidation of the marine sponge metabolites (4R,6R)-plakilactone C, (4R,6R,9R)-plakilactone B, and (4R,6R)-des-hydroxyplakilactone B. des-Hydroxygracilioether C, the putative biosynthetic precursor to hippolachnin A, was also found to undergo a facile ene cyclization on treatment with SnCl4.

  19. Chemoselective methylation of phenolic hydroxyl group prevents quinone methide formation and repolymerization during lignin depolymerization

    DOE PAGES

    Kim, Kwang Ho; Dutta, Tanmoy; Walter, Eric D.; ...

    2017-03-22

    Chemoselective blocking of the phenolic hydroxyl (Ar–OH) group by methylation was found to suppress secondary repolymerization and charring during lignin depolymerization. Methylation of Ar–OH prevents formation of reactive quinone methide intermediates, which are partly responsible for undesirable secondary repolymerization reactions. Instead, this structurally modified lignin produces more relatively low molecular weight products from lignin depolymerization compared to unmodified lignin. This result demonstrates that structural modification of lignin is desirable for production of low molecular weight phenolic products. Finally, this approach could be directed toward alteration of natural lignification processes to produce biomass that is more amenable to chemical depolymerization.

  20. Energy efficiency in nanoscale synthesis using nanosecond plasmas.

    PubMed

    Pai, David Z; Ken Ostrikov, Kostya; Kumar, Shailesh; Lacoste, Deanna A; Levchenko, Igor; Laux, Christophe O

    2013-01-01

    We report a nanoscale synthesis technique using nanosecond-duration plasma discharges. Voltage pulses 12.5 kV in amplitude and 40 ns in duration were applied repetitively at 30 kHz across molybdenum electrodes in open ambient air, generating a nanosecond spark discharge that synthesized well-defined MoO₃ nanoscale architectures (i.e. flakes, dots, walls, porous networks) upon polyamide and copper substrates. No nitrides were formed. The energy cost was as low as 75 eV per atom incorporated into a nanostructure, suggesting a dramatic reduction compared to other techniques using atmospheric pressure plasmas. These findings show that highly efficient synthesis at atmospheric pressure without catalysts or external substrate heating can be achieved in a simple fashion using nanosecond discharges.

  1. Efficient synthesis of phosphatidylserine in 2-methyltetrahydrofuran.

    PubMed

    Duan, Zhang-Qun; Hu, Fei

    2013-01-10

    2-Methyltetrahydrofuran has recently been described as a promising and green solvent. Herein, it was successfully used as the reaction medium for enzyme-mediated transphosphatidylation of phosphatidylcholine with L-serine with the aim of phosphatidylserine synthesis for the first time. Our results indicated that as high as 90% yield of phosphatidylserine could be achieved after 12 h combined with no byproduct (phosphatidic acid) forming. The present work accommodated a facilely and efficiently enzymatic strategy for preparing phosphatidylserine, which possessed obvious advantages over the reported processes in terms of high efficiency and environmental friendliness. This work is also a proof-of-concept opening the use of 2-methyltetrahydrofuran in biosynthesis as well. Copyright © 2012 Elsevier B.V. All rights reserved.

  2. Area-Selective Atomic Layer Deposition of SiO2 Using Acetylacetone as a Chemoselective Inhibitor in an ABC-Type Cycle

    PubMed Central

    2017-01-01

    Area-selective atomic layer deposition (ALD) is rapidly gaining interest because of its potential application in self-aligned fabrication schemes for next-generation nanoelectronics. Here, we introduce an approach for area-selective ALD that relies on the use of chemoselective inhibitor molecules in a three-step (ABC-type) ALD cycle. A process for area-selective ALD of SiO2 was developed comprising acetylacetone inhibitor (step A), bis(diethylamino)silane precursor (step B), and O2 plasma reactant (step C) pulses. Our results show that this process allows for selective deposition of SiO2 on GeO2, SiNx, SiO2, and WO3, in the presence of Al2O3, TiO2, and HfO2 surfaces. In situ Fourier transform infrared spectroscopy experiments and density functional theory calculations underline that the selectivity of the approach stems from the chemoselective adsorption of the inhibitor. The selectivity between different oxide starting surfaces and the compatibility with plasma-assisted or ozone-based ALD are distinct features of this approach. Furthermore, the approach offers the opportunity of tuning the substrate-selectivity by proper selection of inhibitor molecules. PMID:28850774

  3. Synthesis of (−)-Pseudotabersonine, (−)-Pseudovincadifformine, and (+)-Coronaridine Enabled by Photoredox Catalysis in Flow

    PubMed Central

    2015-01-01

    Natural product modification with photoredox catalysis allows for mild, chemoselective access to a wide array of related structures in complex areas of chemical space, providing the possibility for novel structural motifs as well as useful quantities of less abundant congeners. While amine additives have been used extensively as stoichiometric electron donors for photocatalysis, the controlled modification of amine substrates through single-electron oxidation is ideal for the synthesis and modification of alkaloids. Here, we report the conversion of the amine (+)-catharanthine into the natural products (−)-pseudotabersonine, (−)-pseudovincadifformine, and (+)-coronaridine utilizing visible light photoredox catalysis. PMID:25003992

  4. Water-Assisted Highly Efficient Synthesis of Impurity-Free Single-Walled Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Hata, Kenji; Futaba, Don N.; Mizuno, Kohei; Namai, Tatsunori; Yumura, Motoo; Iijima, Sumio

    2004-11-01

    We demonstrate the efficient chemical vapor deposition synthesis of single-walled carbon nanotubes where the activity and lifetime of the catalysts are enhanced by water. Water-stimulated enhanced catalytic activity results in massive growth of superdense and vertically aligned nanotube forests with heights up to 2.5 millimeters that can be easily separated from the catalysts, providing nanotube material with carbon purity above 99.98%. Moreover, patterned, highly organized intrinsic nanotube structures were successfully fabricated. The water-assisted synthesis method addresses many critical problems that currently plague carbon nanotube synthesis.

  5. Energy efficiency in nanoscale synthesis using nanosecond plasmas

    PubMed Central

    Pai, David Z.; (Ken) Ostrikov, Kostya; Kumar, Shailesh; Lacoste, Deanna A.; Levchenko, Igor; Laux, Christophe O.

    2013-01-01

    We report a nanoscale synthesis technique using nanosecond-duration plasma discharges. Voltage pulses 12.5 kV in amplitude and 40 ns in duration were applied repetitively at 30 kHz across molybdenum electrodes in open ambient air, generating a nanosecond spark discharge that synthesized well-defined MoO3 nanoscale architectures (i.e. flakes, dots, walls, porous networks) upon polyamide and copper substrates. No nitrides were formed. The energy cost was as low as 75 eV per atom incorporated into a nanostructure, suggesting a dramatic reduction compared to other techniques using atmospheric pressure plasmas. These findings show that highly efficient synthesis at atmospheric pressure without catalysts or external substrate heating can be achieved in a simple fashion using nanosecond discharges. PMID:23386976

  6. General chemoselective and redox-responsive ligation and release strategy.

    PubMed

    Park, Sungjin; Westcott, Nathan P; Luo, Wei; Dutta, Debjit; Yousaf, Muhammad N

    2014-03-19

    We report a switchable redox click and cleave reaction strategy for conjugating and releasing a range of molecules on demand. This chemoselective redox-responsive ligation (CRRL) and release strategy is based on a redox switchable oxime linkage that is controlled by mild chemical or electrochemical redox signals and can be performed at physiological conditions without the use of a catalyst. Both conjugation and release reactions are kinetically well behaved and quantitative. The CRRL strategy is synthetically modular and easily monitored and characterized by routine analytical techniques. We demonstrate how the CRRL strategy can be used for the dynamic generation of cyclic peptides and the ligation of two different peptides that are stable but can be selectively cleaved upon changes in the redox environment. We also demonstrate a new redox based delivery of cargoes to live cells strategy via the CRRL methodology by synthesizing a FRET redox-responsive probe that is selectively activated within a cellular environment. We believe the ease of the CRRL strategy should find wide use in a range of applications in biology, tissue engineering, nanoscience, synthetic chemistry, and material science and will expand the suite of current conjugation and release strategies.

  7. Native Chemical Ligation Strategy to Overcome Side Reactions during Fmoc-Based Synthesis of C-Terminal Cysteine-Containing Peptides.

    PubMed

    Lelièvre, Dominique; Terrier, Victor P; Delmas, Agnès F; Aucagne, Vincent

    2016-03-04

    The Fmoc-based solid phase synthesis of C-terminal cysteine-containing peptides is problematic, due to side reactions provoked by the pronounced acidity of the Cα proton of cysteine esters. We herein describe a general strategy consisting of the postsynthetic introduction of the C-terminal Cys through a key chemoselective native chemical ligation reaction with N-Hnb-Cys peptide crypto-thioesters. This method was successfully applied to the demanding peptide sequences of two natural products of biological interest, giving remarkably high overall yields compared to that of a state of the art strategy.

  8. Expedient generation of patterned surface aldehydes by microfluidic oxidation for chemoselective immobilization of ligands and cells.

    PubMed

    Westcott, Nathan P; Pulsipher, Abigail; Lamb, Brian M; Yousaf, Muhammad N

    2008-09-02

    An expedient and inexpensive method to generate patterned aldehydes on self-assembled monolayers (SAMs) of alkanethiolates on gold with control of density for subsequent chemoselective immobilization from commercially available starting materials has been developed. Utilizing microfluidic cassettes, primary alcohol oxidation of tetra(ethylene glycol) undecane thiol and 11-mercapto-1-undecanol SAMs was performed directly on the surface generating patterned aldehyde groups with pyridinium chlorochromate. The precise density of surface aldehydes generated can be controlled and characterized by electrochemistry. For biological applications, fibroblast cells were seeded on patterned surfaces presenting biospecifc cell adhesive (Arg-Glyc-Asp) RGD peptides.

  9. Environmentally friendly chemoselective oxidation of primary aliphatic amines by using a biomimetic electrocatalytic system.

    PubMed

    Largeron, Martine; Chiaroni, Angèle; Fleury, Maurice-Bernard

    2008-01-01

    Environmentally friendly oxidation of primary aliphatic amines to imines has been successfully achieved, under metal-free conditions, by the use of diverse electrogenerated o-azaquinone mediators. High catalytic performance, together with high chemoselectivity, were observed with electron-poor o-azaquinone catalysts generated from 2-aminoresorcinol derivatives. Similar to copper amine oxidase enzymes, these mediators exhibited lower reactivity toward alpha-branched primary amines and no reactivity toward secondary amines. In the case of 3,4-aminophenol derivatives lacking a 2-hydroxy group, the generated o-azaquinone species failed to catalyze the oxidation of the amine to the corresponding imine. Further mechanistic considerations allowed a rationalization of the crucial role of the 2-hydroxy group in converting a catalytically inert species into a highly effective biomimetic catalyst.

  10. Chemoselective Hydrodehalogenation of Organic Halides Utilizing Two-Dimensional Anionic Electrons of Inorganic Electride [Ca2N]+·e.

    PubMed

    Kim, Ye Ji; Kim, Sun Min; Yu, Chunghyeon; Yoo, YoungMin; Cho, Eun Jin; Yang, Jung Woon; Kim, Sung Wng

    2017-01-31

    Halogenated organic compounds are important anthropogenic chemicals widely used in chemical industry, biology, and pharmacology; however, the persistence and inertness of organic halides cause human health problems and considerable environmental pollution. Thus, the elimination or replacement of halogen atoms with organic halides has been considered a central task in synthetic chemistry. In dehalogenation reactions, the consecutive single-electron transfer from reducing agents generates the radical and corresponding carbanion and thus removes the halogen atom as the leaving group. Herein, we report a new strategy for an efficient chemoselective hydrodehalogenation through the formation of stable carbanion intermediates, which are simply achieved by using highly mobile two-dimensional electrons of inorganic electride [Ca 2 N] + ·e - with effective electron transfer ability. The consecutive single-electron transfer from inorganic electride [Ca 2 N] + ·e - stabilized free carbanions, which is a key step in achieving the selective reaction. Furthermore, a determinant more important than leaving group ability is the stability control of free carbanions according to the s character determined by the backbone structure. We anticipate that this approach may provide new insight into selective chemical formation, including hydrodehalogenation.

  11. Synthesis, structure, and reactivity of N-benzoyl iminophosphoranes ortho lithiated at the benzoyl group.

    PubMed

    Aguilar, David; Fernández, Ignacio; Cuesta, Luciano; Yañez-Rodríguez, Víctor; Soler, Tatiana; Navarro, Rafael; Urriolabeitia, Esteban P; López Ortiz, Fernando

    2010-10-01

    Ortho lithiation of N-benzamido-P,P,P-triaryliminophosphoranes through deprotonation with alkyllithium bases was achieved with ortho-C═O and ortho-P═N chemoselectivity. However, the synthetic scope of these processes was rather limited. Ortho-lithiated N-benzamido-P,P,P-triphenyliminophosphorane 8 was efficiently prepared via lithium/halogen exchange of the corresponding ortho-brominated precursor with s-BuLi in THF at -90 °C. The reaction of 8 with a variety of electrophiles provides an easy and mild method for the regioselective synthesis of ortho-modified iminophosphoranes via C-C (alkylation and hydroxyalkylation) and C-X (X = I, Si, P, Sn, and Hg) bond-forming reactions. NMR characterization of 8 in THF solution showed that 8 exists as an equilibrium mixture of one monomer and two dimers. The Li atoms of these species become members of five-membered rings through chelation by the ortho-metalated carbon and the carbonyl oxygen. The dimers differ in the relative orientation of the two chelates with respect to the plane defined by the C(2)Li(2) core. The equilibrium between all species is established by splitting the dimers into monomers and subsequent recombination with formation of a different dimer.

  12. Applications of Lawesson's reagent in the synthesis of naturally occurring steroids and terpenoids.

    PubMed

    Saeed, Aamer; Mehfooz, Haroon; Larik, Fayaz Ali; Faisal, Muhammad; Channar, Pervaiz Ali

    2017-11-01

    Steroids and terpenoids are among the most biologically significant classes of natural products possessing a variety of biological activities. The replacement of one or more oxygen atoms in a steroid or terpenoid molecule by a heteroatom affects the chemical properties of that particular steroid or terpenoid, and that replacement often results in alterations of its biological properties, which is sometimes valuable. One possible modification is the thionation that could have some influence on such activity. Among the various thionating reagents, Lawesson's reagent was found to be most suitable and showed versatile properties, including chemoselectivity and functional group tolerance. In this review, we present the role of Lawesson's reagent in the synthesis of thioanalogues of natural steroids and terpenoids.

  13. Efficiency, error and yield in light-directed maskless synthesis of DNA microarrays

    PubMed Central

    2011-01-01

    Background Light-directed in situ synthesis of DNA microarrays using computer-controlled projection from a digital micromirror device--maskless array synthesis (MAS)--has proved to be successful at both commercial and laboratory scales. The chemical synthetic cycle in MAS is quite similar to that of conventional solid-phase synthesis of oligonucleotides, but the complexity of microarrays and unique synthesis kinetics on the glass substrate require a careful tuning of parameters and unique modifications to the synthesis cycle to obtain optimal deprotection and phosphoramidite coupling. In addition, unintended deprotection due to scattering and diffraction introduce insertion errors that contribute significantly to the overall error rate. Results Stepwise phosphoramidite coupling yields have been greatly improved and are now comparable to those obtained in solid phase synthesis of oligonucleotides. Extended chemical exposure in the synthesis of complex, long oligonucleotide arrays result in lower--but still high--final average yields which approach 99%. The new synthesis chemistry includes elimination of the standard oxidation until the final step, and improved coupling and light deprotection. Coupling Insertions due to stray light are the limiting factor in sequence quality for oligonucleotide synthesis for gene assembly. Diffraction and local flare are by far the largest contributors to loss of optical contrast. Conclusions Maskless array synthesis is an efficient and versatile method for synthesizing high density arrays of long oligonucleotides for hybridization- and other molecular binding-based experiments. For applications requiring high sequence purity, such as gene assembly, diffraction and flare remain significant obstacles, but can be significantly reduced with straightforward experimental strategies. PMID:22152062

  14. Melamine-Schiff base/manganese complex with denritic structure: An efficient catalyst for oxidation of alcohols and one-pot synthesis of nitriles.

    PubMed

    Kazemnejadi, Milad; Nikookar, Mahsa; Mohammadi, Mohammad; Shakeri, Alireza; Esmaeilpour, Mohsen

    2018-05-18

    Efficient and selective oxidation of alcohol to the corresponding carbonyl and/or nitrile was carried out by a new water-soluble melamine-based dendritic Mn(III) complex (Melamine-Mn (III)-Schiff base complex) in the presence of 2,4,6-trichloro-1,3,5-triazine (TCT) and O 2 at room temperature. Also, the oxidation of amine to the corresponding nitrile with high selectivity and conversion was performed at room temperature using the current method and high amounts of turnover frequencies (TOFs) were obtained for reactions. This system was also applicable for direct preparation of oxime through oxidation of alcohol. The catalyst was characterized by Fourier-transform infrared (FTIR), ultraviolet-visible (UV-Vis), thermogravimetric analysis (TGA), energy-dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS), CHN and inductively coupled plasma (ICP) analyses. Also, oxidation/reduction behavior of the catalyst was studied by cyclic voltammetry (CV). Moreover, chemoselectivity of the catalyst was discussed with various combinations. The water-soluble catalyst could be recycled from the reaction mixture and reused for several times with a very low losing in efficiency. The recovered catalyst was also investigated with various analyses. Finally, gram scale preparation of nitrile was evaluated by present method. Copyright © 2018 Elsevier Inc. All rights reserved.

  15. Kinetic analysis of inhibition of glucoamylase and active site mutants via chemoselective oxime immobilization of acarbose on SPR chip surfaces.

    PubMed

    Sauer, Jørgen; Abou Hachem, Maher; Svensson, Birte; Jensen, Knud J; Thygesen, Mikkel B

    2013-06-28

    We here report a quantitative study on the binding kinetics of inhibition of the enzyme glucoamylase and how individual active site amino acid mutations influence kinetics. To address this challenge, we have developed a fast and efficient method for anchoring native acarbose to gold chip surfaces for surface plasmon resonance studies employing wild type glucoamylase and active site mutants, Y175F, E180Q, and R54L, as analytes. The key method was the chemoselective and protecting group-free oxime functionalization of the pseudo-tetrasaccharide-based inhibitor acarbose. By using this technique we have shown that at pH 7.0 the association and dissociation rate constants for the acarbose-glucoamylase interaction are 10(4)M(-1)s(-1) and 10(3)s(-1), respectively, and that the conformational change to a tight enzyme-inhibitor complex affects the dissociation rate constant by a factor of 10(2)s(-1). Additionally, the acarbose-presenting SPR surfaces could be used as a glucoamylase sensor that allowed rapid, label-free affinity screening of small carbohydrate-based inhibitors in solution, which is otherwise difficult with immobilized enzymes or other proteins. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Enhancement of the reduction efficiency of soluble starch for platinum nanoparticles synthesis.

    PubMed

    Tongsakul, Duangta; Wongravee, Kanet; Thammacharoen, Chuchaat; Ekgasit, Sanong

    2012-08-01

    In this work, the efficiency of soluble starch as a reducing and a stabilizing agent in the synthesis of platinum nanoparticles under acidic-alkaline treatment is systematically studied. The degraded intermediates with reducing potential (i.e., small molecules containing aldehyde and α-hydroxy ketone moieties) are concomitantly generated when the alkaline concentration is greater than 0.025 M. The in situ generated species could completely reduce platinum ions (20 mM) and sufficiently stabilize the obtained platinum nanoparticles (5 mM) of uniform particle size (2-4 nm). The reduction is efficient and rapid as a complete conversion is achieved within 5 min. In a stronger alkaline condition, the platinum nanoparticles tend to aggregate and form a bigger domain because extensive degradation generates small starch fragments with less stabilization efficiency. This observation suggests that starch is a promising green material which could be chemically treated and transformed to a powerful reducing agent and stabilizer for the synthesis of metal nanoparticles. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. One-pot synthesis and cytotoxicity studies of new Mannich base derivatives of polyether antibiotic--lasalocid acid.

    PubMed

    Huczyński, Adam; Rutkowski, Jacek; Borowicz, Izabela; Wietrzyk, Joanna; Maj, Ewa; Brzezinski, Bogumil

    2013-09-15

    Seven Mannich base derivatives of polyether antibiotic Lasalocid acid (2a-2g) were synthesized and screened for their antiproliferative activity against various human cancer cell lines. A novel chemoselective one-pot synthesis of these Mannich bases was developed. Compounds 2a-2c and 2g with sterically smaller dialkylamine substituent, displayed potent antiproliferative activity (IC50: 3.2-7.3 μM), and demonstrated higher than twofold selectivity for specific type of cancer. The nature of Mannich base substituent on C-2 atom at the aromatic ring may be critical in the search for selectivity towards a particular cancer cell. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Chemoselectivity-induced multiple interfaces in MWCNT/Fe3O4@ZnO heterotrimers for whole X-band microwave absorption.

    PubMed

    Wang, Zhijiang; Wu, Lina; Zhou, Jigang; Jiang, Zhaohua; Shen, Baozhong

    2014-11-07

    A chemoselective route to induce Fe3O4@ZnO core-shell nanoparticles decorating carbon nanotubes to form MWCNT/Fe3O4@ZnO heterotrimers has been developed. Charges are redistributed in the heterotrimers through C-O-Zn, C-O-Fe and Fe-O-Zn bondings, giving rise to multiple electronic phases. The generated significant interfacial polarization and synergetic interaction between dielectric and magnetic absorbers result in the MWCNT/Fe3O4@ZnO heterotrimers with high-performance microwave absorption in an entire X band.

  19. Chemoselective SN2' Allylations of Detrifluoroacetylatively In Situ Generated 3-Fluoroindolin-2-one-Derived Tertiary Enolates with Morita-Baylis-Hillman Carbonates.

    PubMed

    Zhu, Yi; Mei, Haibo; Han, Jianlin; Soloshonok, Vadim A; Zhou, Jie; Pan, Yi

    2017-12-15

    The first example of the S N 2' reaction type of the detrifluoroacetylatively in situ generated tertiary fluoro-enolates in the uncatalyzed reactions with Morita-Baylis-Hillman derivatives has been described. The S N 2' substitution takes place in a highly chemoselective manner as no corresponding S N 2 products were observed in the reaction mixtures. Due to the excellent stereochemical outcome, the reactions seem to have an apparent synthetic value for the preparation of structurally new fluorinated oxindoles.

  20. Copper-free route to triazole-modified peptidomimetic by the combination of two multicomponent reactions in one pot.

    PubMed

    Niu, Teng-fei; Gu, Lin; Yi, Wen-bin; Cai, Chun

    2012-05-14

    An efficient copper-free protocol for the synthesis of 5-methyl-1H-1,2,3-triazole-modified peptidomimetics through the combination of Ugi four-component reaction with a three-component cycloaddition, has been developed. The copper-free straightforward process is suitable for drug discovery. The chemoselective preparation of 1,4-disubstituted, triazole-modified peptidomimetics by using alkynyl substituted amines may have potential biological and synthetic application. At last, a "Lapinski type" analysis of the physical properties was performed, which is expected to help drug discovery.

  1. Monosaccharides as Scaffolds for the Synthesis of Novel Compounds

    NASA Astrophysics Data System (ADS)

    Murphy, Paul V.; Velasco-Torrijos, Trinidad

    This chapter focuses on monosaccharides and scaffolds their derivatives as scaffolds for the synthesis of primarily bioactive compounds. Such carbohydrate derivatives have been designed to modulate mainly protein-protein and peptide-protein interactions although modulators of carbohydrate-protein and carbohydrate-nucleic acid interactions have also been of interest. The multiple hydroxyl groups that are present on saccharides have made pyranose, furanose and iminosugars ideal templates or scaffolds to which recognition or pharmacophoric groups can be grafted to generate novel compounds for medicinal chemistry. The synthesis of compounds for evaluations require strategies for regioselective reactions of saccharide hydroxyl groups and use of orthogonally stable protecting groups. Syntheses have been carried out on the solid phase and in solution. Also the use of uronic acids, amino sugars and sugar amino acids has facilitated the synthesis of peptidomimetics and prospecting libraries as they enable, through presence of amino or carboxylic acid groups, chemoselective approaches to be employed in solution and on solid phase. Sugar amino acids are readily incorporated, as peptide isosteres, to generate sugar-peptide hybrids or for the synthesis of novel carbopeptoids . The synthesis of new cyclic compounds, derived in part from saccharides, and their application as scaffolds is an emerging area and recent examples include spirocyclic compounds, benzodiazepine-saccharide hybrids and macrolide-saccharide hybrids. Potent bioactive saccharide derivatives have been identified that include enzyme inhibitors , somatostatin receptor ligands, integrin ligands, anti-viral compounds, shiga toxin inhibitors and cell growth inhibitors. Some saccharide derivatives have demonstrated improved cellular permeability when compared with peptides and are in clinical trials.

  2. Magnetic nanoparticle supported phosphotungstic acid: An efficient catalyst for the synthesis of xanthene derivatives

    NASA Astrophysics Data System (ADS)

    Patel, Nipun; Katheriya, Deepak; Dadhania, Harsh; Dadhania, Abhishek

    2018-05-01

    Magnetic nanoparticle supported phosphotungstic acid (Fe3O4@SiO2-HPW) was applied as a highly efficient catalyst for the synthesis of 14H-dibenzoxanthene derivatives via condensation reaction of 2-naphthol and aryl aldehydes. The catalyst was found highly efficient for the synthesis of xanthene derivatives under solvent free condition. The catalyst showed high activity and stability during the reaction and provided excellent yield of the corresponding products in short reaction time. All the synthesized compounds were characterized through FT-IR, 1H-NMR and 13C-NMR spectroscopic techniques. Furthermore, the catalyst is magnetically recoverable and can be reused several times without significant loss of its catalytic activity.

  3. Water-Assisted Highly Efficient Synthesis of Impurity-Free Single-Walled Carbon Nanotubes-``Super-Growth''

    NASA Astrophysics Data System (ADS)

    Hata, Kenji

    2005-03-01

    We demonstrate an extremely efficient chemical vapour deposition synthesis of single-walled carbon nanotubes where the activity and lifetime of the catalysts are enhanced by water [1]. Water-stimulated enhanced catalytic activity results in massive growth of super-dense and vertically-aligned nanotube forests with heights up to 2.5 millimeters that can be easily separated from the catalysts, providing nanotube material with carbon purity above 99.98%. Moreover, patterned highly organized intrinsic nanotube structures were successfully fabricated. The water-assisted synthesis method addresses many critical problems that currently plague carbon nanotube synthesis. [1] K. Hata, et al., Science, 306, 1362 (2004).

  4. Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

    NASA Astrophysics Data System (ADS)

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-12-01

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.

  5. Micelle-template synthesis of nitrogen-doped mesoporous graphene as an efficient metal-free electrocatalyst for hydrogen production.

    PubMed

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-12-19

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.

  6. Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

    PubMed Central

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-01-01

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications. PMID:25523276

  7. Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs.

    PubMed

    Xu, Pengfei; Wu, Lei; Dong, Liqiu; Xu, Xin

    2018-02-08

    This work reports the chemoselective polymerization of polar divinyl monomers, including allyl methacrylate (AMA), vinyl methacrylate (VMA), and 4-vinylbenzyl methacrylate (VBMA), by using simple Lewis pairs comprised of homoleptic rare-earth (RE) aryloxide complexes RE(OAr)₃ (RE = Sc ( 1 ), Y ( 2 ), Sm ( 3 ), La ( 4 ), Ar = 2,6- t Bu₂C₆H₃) and phosphines PR₃ (R = Ph, Cy, Et, Me). Catalytic activities of polymerizations relied heavily upon the cooperation of Lewis acid and Lewis base components. The produced polymers were soluble in common organic solvents and often had a narrow molecular weight distribution. A highly syndiotactic poly(allyl methacrylate) (PAMA) with rr ~88% could be obtained by the scandium complex 1 /PEt₃ pair at -30 °C. In the case of poly(4-vinylbenzyl methacrylate) (PVBMA), it could be post-functionalized with PhCH₂SH. Mechanistic study, including the isolation of the zwitterionic active species and the end-group analysis, revealed that the frustrated Lewis pair (FLP)-type addition was the initiating step in the polymerization.

  8. Synthesis of energy-efficient FSMs implemented in PLD circuits

    NASA Astrophysics Data System (ADS)

    Nawrot, Radosław; Kulisz, Józef; Kania, Dariusz

    2017-11-01

    The paper presents an outline of a simple synthesis method of energy-efficient FSMs. The idea consists in using local clock gating to selectively block the clock signal, if no transition of a state of a memory element is required. The research was dedicated to logic circuits using Programmable Logic Devices as the implementation platform, but the conclusions can be applied to any synchronous circuit. The experimental section reports a comparison of three methods of implementing sequential circuits in PLDs with respect to clock distribution: the classical fully synchronous structure, the structure exploiting the Enable Clock inputs of memory elements, and the structure using clock gating. The results show that the approach based on clock gating is the most efficient one, and it leads to significant reduction of dynamic power consumed by the FSM.

  9. Versatile Synthesis of Stable, Functional Polypeptides via Reaction with Epoxides.

    PubMed

    Gharakhanian, Eric G; Deming, Timothy J

    2015-06-08

    Methodology was developed for efficient alkylation of methionine residues using epoxides as a general strategy to introduce a wide range of functional groups onto polypeptides. Use of a spacer between epoxide and functional groups further allowed addition of sterically demanding functionalities. Contrary to other methods to alkylate methionine residues, epoxide alkylations allow the reactions to be conducted in wet protic media and give sulfonium products that are stable against dealkylation. These functionalizations are notable since they are chemoselective, utilize stable and readily available epoxides, and allow facile incorporation of an unprecedented range of functional groups onto simple polypeptides using stable linkages.

  10. Suppression of HLA Expression by Lentivirus-mediated Gene Transfer of siRNA Cassettes and In Vivo Chemoselection to Enhance Hematopoietic Stem Cell Transplantation

    PubMed Central

    Hacke, Katrin; Falahati, Rustom; Flebbe-Rehwaldt, Linda; Kasahara, Noriyuki; Gaensler, Karin M. L.

    2010-01-01

    Current approaches for hematopoietic stem cell (HSC) and organ transplantation are limited by donor and host-mediated immune responses to allo-antigens. Application of these therapies is limited by the toxicity of preparative and post-transplant immunosuppressive regimens and a shortage of appropriate HLA-matched donors. We have been exploring two complementary approaches for genetically modifying donor cells that achieve long-term suppression of cellular proteins that elicit host immune responses to mismatched donor antigens, and provide a selective advantage to genetically engineered donor cells after transplantation. The first approach is based on recent advances that make feasible targeted down-regulation of HLA expression. Suppression of HLA expression could help to overcome limitations imposed by extensive HLA polymorphisms that restrict the availability of suitable donors. Accordingly, we have recently investigated whether knockdown of HLA by RNA interference (RNAi) enables allogeneic cells to evade immune recognition. For efficient and stable delivery of short hairpin-type RNAi constructs (shRNA), we employed lentivirus-based gene transfer vectors that integrate into genomic DNA, thereby permanently modifying transduced donor cells. Lentivirus-mediated delivery of shRNA targeting pan-Class I and allele-specific HLA achieved efficient and dose-dependent reduction in surface expression of HLA in human cells, and enhanced resistance to allo-reactive T lymphocyte-mediated cytotoxicity, while avoiding non-MHC restricted killing. Complementary strategies for genetic engineering of HSC that would provide a selective advantage for transplanted donor cells and enable successful engraftment with less toxic preparative and immunosuppressive regimens would increase the numbers of individuals to whom HLA suppression therapy could be offered. Our second strategy is to provide a mechanism for in vivo selection of genetically modified HSC and other donor cells. We have

  11. Simplified Application of Material Efficiency Green Metrics to Synthesis Plans: Pedagogical Case Studies Selected from "Organic Syntheses"

    ERIC Educational Resources Information Center

    Andraos, John

    2015-01-01

    This paper presents a simplified approach for the application of material efficiency metrics to linear and convergent synthesis plans encountered in organic synthesis courses. Computations are facilitated and automated using intuitively designed Microsoft Excel spreadsheets without invoking abstract mathematical formulas. The merits of this…

  12. Non-nucleoside building blocks for copper-assisted and copper-free click chemistry for the efficient synthesis of RNA conjugates.

    PubMed

    Jayaprakash, K N; Peng, Chang Geng; Butler, David; Varghese, Jos P; Maier, Martin A; Rajeev, Kallanthottathil G; Manoharan, Muthiah

    2010-12-03

    Novel non-nucleoside alkyne monomers compatible with oligonucleotide synthesis were designed, synthesized, and efficiently incorporated into RNA and RNA analogues during solid-phase synthesis. These modifications allowed site-specific conjugation of ligands to the RNA oligonucleotides through copper-assisted (CuAAC) and copper-free strain-promoted azide-alkyne cycloaddition (SPAAC) reactions. The SPAAC click reactions of cyclooctyne-oligonucleotides with various classes of azido-functionalized ligands in solution phase and on solid phase were efficient and quantitative and occurred under mild reaction conditions. The SPAAC reaction provides a method for the synthesis of oligonucleotide-ligand conjugates uncontaminated with copper ions.

  13. Engineering Streptomyces coelicolor Carbonyl Reductase for Efficient Atorvastatin Precursor Synthesis

    PubMed Central

    Li, Min; Zhang, Zhi-Jun; Kong, Xu-Dong; Yu, Hui-Lei

    2017-01-01

    ABSTRACT Streptomyces coelicolor CR1 (ScCR1) has been shown to be a promising biocatalyst for the synthesis of an atorvastatin precursor, ethyl-(S)-4-chloro-3-hydroxybutyrate [(S)-CHBE]. However, limitations of ScCR1 observed for practical application include low activity and poor stability. In this work, protein engineering was employed to improve the catalytic efficiency and stability of ScCR1. First, the crystal structure of ScCR1 complexed with NADH and cosubstrate 2-propanol was solved, and the specific activity of ScCR1 was increased from 38.8 U/mg to 168 U/mg (ScCR1I158V/P168S) by structure-guided engineering. Second, directed evolution was performed to improve the stability using ScCR1I158V/P168S as a template, affording a triple mutant, ScCR1A60T/I158V/P168S, whose thermostability (T5015, defined as the temperature at which 50% of initial enzyme activity is lost following a heat treatment for 15 min) and substrate tolerance (C5015, defined as the concentration at which 50% of initial enzyme activity is lost following incubation for 15 min) were 6.2°C and 4.7-fold higher than those of the wild-type enzyme. Interestingly, the specific activity of the triple mutant was further increased to 260 U/mg. Protein modeling and docking analysis shed light on the origin of the improved activity and stability. In the asymmetric reduction of ethyl-4-chloro-3-oxobutyrate (COBE) on a 300-ml scale, 100 g/liter COBE could be completely converted by only 2 g/liter of lyophilized ScCR1A60T/I158V/P168S within 9 h, affording an excellent enantiomeric excess (ee) of >99% and a space-time yield of 255 g liter−1 day−1. These results suggest high efficiency of the protein engineering strategy and good potential of the resulting variant for efficient synthesis of the atorvastatin precursor. IMPORTANCE Application of the carbonyl reductase ScCR1 in asymmetrically synthesizing (S)-CHBE, a key precursor for the blockbuster drug Lipitor, from COBE has been hindered by its low

  14. Chemoselective Alteration of Fluorophore Scaffolds as a Strategy for the Development of Ratiometric Chemodosimeters.

    PubMed

    Zhou, Xinqi; Lesiak, Lauren; Lai, Rui; Beck, Jon R; Zhao, Jia; Elowsky, Christian G; Li, Hui; Stains, Cliff I

    2017-04-03

    Ratiometric sensors generally couple binding events or chemical reactions at a distal site to changes in the fluorescence of a core fluorophore scaffold. However, such approaches are often hindered by spectral overlap of the product and reactant species. We provide a strategy to design ratiometric sensors that display dramatic spectral shifts by leveraging the chemoselective reactivity of novel functional groups inserted within fluorophore scaffolds. As a proof-of-principle, fluorophores containing a borinate (RF 620 ) or silanediol (SiOH2R) functionality at the bridging position of the xanthene ring system are developed as endogenous H 2 O 2 sensors. Both these fluorophores display far-red to near-infrared excitation and emission prior to reaction. Upon oxidation by H 2 O 2 both sensors are chemically converted to tetramethylrhodamine, producing significant (≥66 nm) blue-shifts in excitation and emission maxima. This work provides a new concept for the development of ratiometric probes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Efficient synthesis of dichlorodenafil, an unapproved sildenafil analogue appearing in non-prescription supplements.

    PubMed

    Kim, Jong Yup; Hwang, In Gyun; Oh, Jae Ho; Kang, Il Hyun; Kwon, Sung Won; Kim, Deukjoon

    2013-01-01

    We have developed an efficient synthesis of dichlorodenafil (4), an unapproved sildenafil analogue isolated from dietary supplements. Our sequence employs POCl(3)-mediated chlorination of readily available chloroacetyl compound 7 followed by selective hydrolysis of the chloro-heterocycle function. Our synthesis confirms the structure of the illegal additive, and will provide regulatory agencies with ready access to authentic standard samples of dichlorodenafil (4) to aid in their mission to protect the public from unapproved and potentially harmful erectile dysfunction (ED) drug analogues that are added to herbal and dietary supplements without providing users with appropriate toxicological or pharmacological information.

  16. In Situ Synthesis of Lipid Membranes

    NASA Astrophysics Data System (ADS)

    Devaraj, N. K.

    2017-07-01

    We have a strong interest in applying covalent coupling reactions to the formation and modification of lipid membranes. We have utilized chemoselective reactions, such as copper-catalyzed triazole formation or the native chemical ligation.

  17. Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(-)-myrtenol nitrate.

    PubMed

    Bew, Sean P; Hiatt-Gipson, Glyn D; Mills, Graham P; Reeves, Claire E

    2016-01-01

    Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a 'halide for nitrate' substitution. Employing readily available starting materials, reagents and Horner-Wadsworth-Emmons chemistry the synthesis of easily separable, synthetically versatile 'key building blocks' (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, 'off the shelf' materials. Exploiting their reactivity we have studied their ability to undergo an 'allylic halide for allylic nitrate' substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates ('isoprene nitrates') in 66-80% overall yields. Using NOESY experiments the elucidation of the carbon-carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our 'halide for nitrate' substitution chemistry we outline the straightforward transformation of (1R,2S)-(-)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(-)-myrtenol nitrate.

  18. The double-edged effects of annealing MgO underlayers on the efficient synthesis of single-wall carbon nanotube forests.

    PubMed

    Tsuji, Takashi; Hata, Kenji; Futaba, Don N; Sakurai, Shunsuke

    2017-11-16

    Recently, the millimetre-scale, highly efficient synthesis of single-wall carbon nanotube (SWCNT) forests from Fe catalysts has been reported through the annealing of the magnesia (MgO) underlayer. Here, we report the double-edged effects of underlayer annealing on the efficiency and structure of the SWCNT forest synthesis through a temperature-dependent examination. Our results showed that the efficiency of the SWCNT forests sharply increased with increased underlayer annealing temperatures from 600 °C up to 900 °C due to a temperature-dependent structural modification, characterized by increased grain size and reduced defects, of the MgO underlayer. Beyond this temperature, the SWCNT fraction also decreased as a result of further structural modification of the MgO underlayer. This exemplifies the double-edged effects of annealing. Specifically, for underlayer annealing below 600 °C, the catalyst subsurface diffusion was found to limit the growth efficiency, and for excessively high underlayer annealing temperatures (>900 °C), catalyst coalescence/ripening led to the formation of double-wall carbon nanotubes. As a result, three distinct regions of synthesis were observed: (i) a "low yield" region below a threshold temperature (∼600 °C); (ii) an "increased yield" region from 600 to 900 °C, and (iii) a "saturation" region above 900 °C. The efficient SWCNT forest synthesis could only occur within a specific annealing temperature window as a result of this double-edged effects of underlayer annealing.

  19. An efficient synthesis of tetramic acid derivatives with extended conjugation from L-Ascorbic Acid

    PubMed Central

    Singh, Biswajit K; Bisht, Surendra S; Tripathi, Rama P

    2006-01-01

    Background Tetramic acids with polyenyl substituents are an important class of compounds in medicinal chemistry. Both solid and solution phase syntheses of such molecules have been reported recently. Thiolactomycin, a clinical candidate for treatment of tuberculosis has led to further explorations in this class. We have recently developed an efficient synthesis of tetramic acids derivatives from L- ascorbic acid. In continuation of this work, we have synthesised dienyl tetramic acid derivatives. Results 5,6-O-Isopropylidene-ascorbic acid on reaction with DBU led to the formation of tetronolactonyl allyl alcohol, which on oxidation with pyridinium chlorochromate gave the respective tetranolactonyl allylic aldehydes. Wittig olefination followed by reaction of the resulting tetranolactonyl dienyl esters with different amines resulted in the respective 5-hydroxy lactams. Subsequent dehydration of the hydroxy lactams with p-toluene sulphonic acid afforded the dienyl tetramic acid derivatives. All reactions were performed at ambient temperature and the yields are good. Conclusion An efficient and practical method for the synthesis of dienyl tetramic acid derivatives from inexpensive and easily accessible ascorbic acid has been developed. The compounds bear structural similarities to the tetramic acid based polyenic antibiotics and thus this method offers a new and short route for the synthesis of tetramic acid derivatives of biological significance. PMID:17147830

  20. An efficient synthesis of tetramic acid derivatives with extended conjugation from L-ascorbic acid.

    PubMed

    Singh, Biswajit K; Bisht, Surendra S; Tripathi, Rama P

    2006-12-06

    Tetramic acids with polyenyl substituents are an important class of compounds in medicinal chemistry. Both solid and solution phase syntheses of such molecules have been reported recently. Thiolactomycin, a clinical candidate for treatment of tuberculosis has led to further explorations in this class. We have recently developed an efficient synthesis of tetramic acids derivatives from L-ascorbic acid. In continuation of this work, we have synthesised dienyl tetramic acid derivatives. 5,6-O-isopropylidene-ascorbic acid on reaction with DBU led to the formation of tetronolactonyl allyl alcohol, which on oxidation with pyridinium chlorochromate gave the respective tetranolactonyl allylic aldehydes. Wittig olefination followed by reaction of the resulting tetranolactonyl dienyl esters with different amines resulted in the respective 5-hydroxy lactams. Subsequent dehydration of the hydroxy lactams with p-toluene sulphonic acid afforded the dienyl tetramic acid derivatives. All reactions were performed at ambient temperature and the yields are good. An efficient and practical method for the synthesis of dienyl tetramic acid derivatives from inexpensive and easily accessible ascorbic acid has been developed. The compounds bear structural similarities to the tetramic acid based polyenic antibiotics and thus this method offers a new and short route for the synthesis of tetramic acid derivatives of biological significance.

  1. Practical Aerobic Oxidations of Alcohols and Amines with Homogeneous Cu/TEMPO and Related Catalyst Systems

    PubMed Central

    Ryland, Bradford L.; Stahl, Shannon S.

    2014-01-01

    Alcohol and amine oxidations are common reactions in laboratory and industrial synthesis of organic molecules. Aerobic oxidation methods have long been sought for these transformations, but few practical methods exist that offer advantages over traditional oxidation methods. Recently developed homogeneous Cu/TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidinyl-N-oxyl) and related catalyst systems appear to fill this void. The reactions exhibit high levels of chemoselectivity and broad functional-group tolerance, and they often operate efficiently at room temperature with ambient air as the oxidant. These advances, together with their historical context and recent applications, are highlighted in this minireview. PMID:25044821

  2. A highly efficient green synthesis of 1, 8-dioxo-octahydroxanthenes

    PubMed Central

    2011-01-01

    SmCl3 (20 mol%) has been used as an efficient catalyst for reaction between aromatic aldehydes and 5,5-dimethyl-1,3-cyclohexanedione at 120°C to give 1,8-dioxo-octahydroxanthene derivatives in high yield. The same reaction in water, at room temperature gave only the open chain analogue of 1,8-dioxo-octahydroxanthene. Use of eco-friendly green Lewis acid, readily available catalyst and easy isolation of the product makes this a convenient method for the synthesis of either of the products. PMID:22152051

  3. Efficient synthesis of 3-O-thia-cPA and preliminary analysis of its biological activity toward autotaxin.

    PubMed

    Tanaka, Ryo; Kato, Masaru; Suzuki, Takahiro; Nakazaki, Atsuo; Nozaki, Emi; Gotoh, Mari; Murakami-Murofushi, Kimiko; Kobayashi, Susumu

    2011-07-15

    The efficient synthesis of 3-O-thia-cPAs (4a-d), sulfur analogues of cyclic phosphatidic acid (cPA), has been achieved. The key step of the synthesis is an intramolecular Arbuzov reaction to construct the cyclic thiophosphate moiety. The present synthetic route enables the synthesis of 4a-d in only four steps from the commercially available glycidol. Preliminary biological experiments showed that 4a-d exhibited a similar inhibitory effect on autotaxin (ATX) as original cPA. Copyright © 2011 Elsevier Ltd. All rights reserved.

  4. Compound Synthesis or Growth and Development of Roots/Stomata Regulate Plant Drought Tolerance or Water Use Efficiency/Water Uptake Efficiency.

    PubMed

    Meng, Lai-Sheng

    2018-04-11

    Water is crucial to plant growth and development because it serves as a medium for all cellular functions. Thus, the improvement of plant drought tolerance or water use efficiency/water uptake efficiency is important in modern agriculture. In this review, we mainly focus on new genetic factors for ameliorating drought tolerance or water use efficiency/water uptake efficiency of plants and explore the involvement of these genetic factors in the regulation of improving plant drought tolerance or water use efficiency/water uptake efficiency, which is a result of altered stomata density and improving root systems (primary root length, hair root growth, and lateral root number) and enhanced production of osmotic protectants, which is caused by transcription factors, proteinases, and phosphatases and protein kinases. These results will help guide the synthesis of a model for predicting how the signals of genetic and environmental stress are integrated at a few genetic determinants to control the establishment of either water use efficiency or water uptake efficiency. Collectively, these insights into the molecular mechanism underpinning the control of plant drought tolerance or water use efficiency/water uptake efficiency may aid future breeding or design strategies to increase crop yield.

  5. Highly efficient water-mediated approach to access benzazoles: metal catalyst and base-free synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles.

    PubMed

    Bala, Manju; Verma, Praveen Kumar; Sharma, Deepika; Kumar, Neeraj; Singh, Bikram

    2015-05-01

    An efficient water-catalyzed method has been developed for the synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles in one step. The present method excludes the usage of toxic metal catalysts and bases to produce benzazoles in good to excellent yields. An efficient and versatile water-mediated method has been established for the synthesis of various 2-arylbenzazoles. The present protocol excludes the usage of any catalyst and additive provided excellent selectivities and yields with high functional group tolerance for the synthesis of 2-arylated benzimidazoles, benzoxazoles, and benzothiazoles. Benzazolones were also synthesized using similar reaction protocol.

  6. Chemical Synthesis of Circular Proteins*

    PubMed Central

    Tam, James P.; Wong, Clarence T. T.

    2012-01-01

    Circular proteins, once thought to be rare, are now commonly found in plants. Their chemical synthesis, once thought to be difficult, is now readily achievable. The enabling methodology is largely due to the advances in entropic chemical ligation to overcome the entropy barrier in coupling the N- and C-terminal ends of large peptide segments for either intermolecular ligation or intramolecular ligation in end-to-end cyclization. Key elements of an entropic chemical ligation consist of a chemoselective capture step merging the N and C termini as a covalently linked O/S-ester intermediate to permit the subsequent step of an intramolecular O/S-N acyl shift to form an amide. Many ligation methods exploit the supernucleophilicity of a thiol side chain at the N terminus for the capture reaction, which makes cysteine-rich peptides ideal candidates for the entropy-driven macrocyclization. Advances in desulfurization and modification of the thiol-containing amino acids at the ligation sites to other amino acids add extra dimensions to the entropy-driven ligation methods. This minireview describes recent advances of entropy-driven ligation to prepare circular proteins with or without a cysteinyl side chain. PMID:22700959

  7. Highly efficient one-pot three-component synthesis of naphthopyran derivatives in water catalyzed by hydroxyapatite

    EPA Science Inventory

    An expeditious and efficient protocol for the synthesis of naphthopyrans has been developed that proceeds via one-pot three-component sequential reaction in water catalyzed by hydroxyapatite or sodium-modified-hydroxyapatite. The title compounds have been obtained in high yield a...

  8. Synthesis of β-Nicotinamide Riboside Using an Efficient Two-Step Methodology.

    PubMed

    Zhang, Ning; Sauve, Anthony A

    2017-12-24

    A two-step chemical method for the synthesis of β-nicotinamide riboside (NR) is described. NR has achieved wide use as an NAD + precursor (vitamin B3) and can significantly increase central metabolite NAD + concentrations in mammalian cells. β-NR can be prepared with an efficient two-step procedure. The synthesis is initiated via coupling of commercially available 1,2,3,5-tetra-O-acetyl-β-D-ribofuranose with ethyl nicotinate in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf). 1 H NMR showed that the product was formed with complete stereoselectivity to produce only the β-isomer in high yield (>90% versus starting sugar). The clean stereochemical result suggests that the coupling proceeds via a cationic cis-1,2-acyloxonium-sugar intermediate, which controls addition by nucleophiles to generate predominantly β-stereochemistry. The subsequent deprotection of esters in methanolic ammonia generates the desired product in 85% overall yield versus sugar. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

  9. Efficiency and Fidelity of Human DNA Polymerases λ and β during Gap-Filling DNA Synthesis

    PubMed Central

    Brown, Jessica A.; Pack, Lindsey R.; Sanman, Laura E.; Suo, Zucai

    2010-01-01

    The base excision repair (BER) pathway coordinates the replacement of 1 to 10 nucleotides at sites of single-base lesions. This process generates DNA substrates with various gap sizes which can alter the catalytic efficiency and fidelity of a DNA polymerase during gap-filling DNA synthesis. Here, we quantitatively determined the substrate specificity and base substitution fidelity of human DNA polymerase λ (Pol λ), an enzyme proposed to support the known BER DNA polymerase β (Pol β), as it filled 1- to 10-nucleotide gaps at 1-nucleotide intervals. Pol λ incorporated a correct nucleotide with relatively high efficiency until the gap size exceeded 9 nucleotides. Unlike Pol λ, Pol β did not have an absolute threshold on gap size as the catalytic efficiency for a correct dNTP gradually decreased as the gap size increased from 2 to 10 nucleotides and then recovered for non-gapped DNA. Surprisingly, an increase in gap size resulted in lower polymerase fidelity for Pol λ, and this downregulation of fidelity was controlled by its non-enzymatic N-terminal domains. Overall, Pol λ was up to 160-fold more error-prone than Pol β, thereby suggesting Pol λ would be more mutagenic during long gap-filling DNA synthesis. In addition, dCTP was the preferred misincorporation for Pol λ and its N-terminal domain truncation mutants. This nucleotide preference was shown to be dependent upon the identity of the adjacent 5′-template base. Our results suggested that both Pol λ and Pol β would catalyze nucleotide incorporation with the highest combination of efficiency and accuracy when the DNA substrate contains a single-nucleotide gap. Thus, Pol λ, like Pol β, is better suited to catalyze gap-filling DNA synthesis during short-patch BER in vivo, although, Pol λ may play a role in long-patch BER. PMID:20961817

  10. Peptide/protein-polymer conjugates: synthetic strategies and design concepts.

    PubMed

    Gauthier, Marc A; Klok, Harm-Anton

    2008-06-21

    This feature article provides a compilation of tools available for preparing well-defined peptide/protein-polymer conjugates, which are defined as hybrid constructs combining (i) a defined number of peptide/protein segments with uniform chain lengths and defined monomer sequences (primary structure) with (ii) a defined number of synthetic polymer chains. The first section describes methods for post-translational, or direct, introduction of chemoselective handles onto natural or synthetic peptides/proteins. Addressed topics include the residue- and/or site-specific modification of peptides/proteins at Arg, Asp, Cys, Gln, Glu, Gly, His, Lys, Met, Phe, Ser, Thr, Trp, Tyr and Val residues and methods for producing peptides/proteins containing non-canonical amino acids by peptide synthesis and protein engineering. In the second section, methods for introducing chemoselective groups onto the side-chain or chain-end of synthetic polymers produced by radical, anionic, cationic, metathesis and ring-opening polymerization are described. The final section discusses convergent and divergent strategies for covalently assembling polymers and peptides/proteins. An overview of the use of chemoselective reactions such as Heck, Sonogashira and Suzuki coupling, Diels-Alder cycloaddition, Click chemistry, Staudinger ligation, Michael's addition, reductive alkylation and oxime/hydrazone chemistry for the convergent synthesis of peptide/protein-polymer conjugates is given. Divergent approaches for preparing peptide/protein-polymer conjugates which are discussed include peptide synthesis from synthetic polymer supports, polymerization from peptide/protein macroinitiators or chain transfer agents and the polymerization of peptide side-chain monomers.

  11. Sequence and structure-specific elements of HERG mRNA determine channel synthesis and trafficking efficiency

    PubMed Central

    Sroubek, Jakub; Krishnan, Yamini; McDonald, Thomas V.

    2013-01-01

    Human ether-á-gogo-related gene (HERG) encodes a potassium channel that is highly susceptible to deleterious mutations resulting in susceptibility to fatal cardiac arrhythmias. Most mutations adversely affect HERG channel assembly and trafficking. Why the channel is so vulnerable to missense mutations is not well understood. Since nothing is known of how mRNA structural elements factor in channel processing, we synthesized a codon-modified HERG cDNA (HERG-CM) where the codons were synonymously changed to reduce GC content, secondary structure, and rare codon usage. HERG-CM produced typical IKr-like currents; however, channel synthesis and processing were markedly different. Translation efficiency was reduced for HERG-CM, as determined by heterologous expression, in vitro translation, and polysomal profiling. Trafficking efficiency to the cell surface was greatly enhanced, as assayed by immunofluorescence, subcellular fractionation, and surface labeling. Chimeras of HERG-NT/CM indicated that trafficking efficiency was largely dependent on 5′ sequences, while translation efficiency involved multiple areas. These results suggest that HERG translation and trafficking rates are independently governed by noncoding information in various regions of the mRNA molecule. Noncoding information embedded within the mRNA may play a role in the pathogenesis of hereditary arrhythmia syndromes and could provide an avenue for targeted therapeutics.—Sroubek, J., Krishnan, Y., McDonald, T V. Sequence- and structure-specific elements of HERG mRNA determine channel synthesis and trafficking efficiency. PMID:23608144

  12. Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

    PubMed Central

    Hiatt-Gipson, Glyn D; Mills, Graham P; Reeves, Claire E

    2016-01-01

    Summary Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a ’halide for nitrate’ substitution. Employing readily available starting materials, reagents and Horner–Wadsworth–Emmons chemistry the synthesis of easily separable, synthetically versatile ‘key building blocks’ (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, ’off the shelf’ materials. Exploiting their reactivity we have studied their ability to undergo an ‘allylic halide for allylic nitrate’ substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates (‘isoprene nitrates’) in 66–80% overall yields. Using NOESY experiments the elucidation of the carbon–carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our ‘halide for nitrate’ substitution chemistry we outline the straightforward transformation of (1R,2S)-(−)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(−)-myrtenol nitrate. PMID:27340495

  13. Exploiting Deep Eutectic Solvents and Organolithium Reagent Partnerships: Chemoselective Ultrafast Addition to Imines and Quinolines Under Aerobic Ambient Temperature Conditions.

    PubMed

    Vidal, Cristian; García-Álvarez, Joaquín; Hernán-Gómez, Alberto; Kennedy, Alan R; Hevia, Eva

    2016-12-23

    Shattering the long-held dogma that organolithium chemistry needs to be performed under inert atmospheres in toxic organic solvents, chemoselective addition of organolithium reagents to non-activated imines and quinolines has been accomplished in green, biorenewable deep eutectic solvents (DESs) at room temperature and in the presence of air, establishing a novel and sustainable access to amines. Improving on existing methods, this approach proceeds in the absence of additives; occurs without competitive enolization, reduction or coupling processes; and reactions were completed in seconds. Comparing RLi reactivities in DESs with those observed in pure glycerol or THF suggests a kinetic anionic activation of the alkylating reagents occurs, favoring nucleophilic addition over competitive hydrolysis. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Synthesis of Structurally Diverse 2,3-Fused Indoles via Microwave-Assisted AgSbF6-Catalysed Intramolecular Difunctionalization of o-Alkynylanilines

    PubMed Central

    Huang, Yuanqiong; Yang, Yan; Song, Hongjian; Liu, Yuxiu; Wang, Qingmin

    2015-01-01

    2,3-Fused indoles are found in numerous natural products and drug molecules. Although several elegant methods for the synthesis of this structural motif have been reported, long reaction times and harsh conditions are sometimes required, and the yields tend to be low. Herein, we report a microwave method for straightforward access to various types of 2,3-fused indoles via AgSbF6-catalysed intramolecular difunctionalization of o-alkynylanilines. AgSbF6 played a role in both the hydroamination step and the imine-formation step. This method, which exhibited excellent chemoselectivity (no ring-fused 1,2-dihydroquinolines were formed), was used for formal syntheses of the natural products conolidine and ervaticine and the antihistamine drug latrepirdine. PMID:26310858

  15. Time- and energy-efficient solution combustion synthesis of binary metal tungstate nanoparticles with enhanced photocatalytic activity.

    PubMed

    Thomas, Abegayl; Janáky, Csaba; Samu, Gergely F; Huda, Muhammad N; Sarker, Pranab; Liu, J Ping; van Nguyen, Vuong; Wang, Evelyn H; Schug, Kevin A; Rajeshwar, Krishnan

    2015-05-22

    In the search for stable and efficient photocatalysts beyond TiO2 , the tungsten-based oxide semiconductors silver tungstate (Ag2 WO4 ), copper tungstate (CuWO4 ), and zinc tungstate (ZnWO4 ) were prepared using solution combustion synthesis (SCS). The tungsten precursor's influence on the product was of particular relevance to this study, and the most significant effects are highlighted. Each sample's photocatalytic activity towards methyl orange degradation was studied and benchmarked against their respective commercial oxide sample obtained by solid-state ceramic synthesis. Based on the results herein, we conclude that SCS is a time- and energy-efficient method to synthesize crystalline binary tungstate nanomaterials even without additional excessive heat treatment. As many of these photocatalysts possess excellent photocatalytic activity, the discussed synthetic strategy may open sustainable materials chemistry avenues to solar energy conversion and environmental remediation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Efficient utilization of greenhouse gases in a gas-to-liquids process combined with CO2/steam-mixed reforming and Fe-based Fischer-Tropsch synthesis.

    PubMed

    Zhang, Chundong; Jun, Ki-Won; Ha, Kyoung-Su; Lee, Yun-Jo; Kang, Seok Chang

    2014-07-15

    Two process models for carbon dioxide utilized gas-to-liquids (GTL) process (CUGP) mainly producing light olefins and Fischer-Tropsch (F-T) synthetic oils were developed by Aspen Plus software. Both models are mainly composed of a reforming unit, an F-T synthesis unit and a recycle unit, while the main difference is the feeding point of fresh CO2. In the reforming unit, CO2 reforming and steam reforming of methane are combined together to produce syngas in flexible composition. Meanwhile, CO2 hydrogenation is conducted via reverse water gas shift on the Fe-based catalysts in the F-T synthesis unit to produce hydrocarbons. After F-T synthesis, the unreacted syngas is recycled to F-T synthesis and reforming units to enhance process efficiency. From the simulation results, it was found that the carbon efficiencies of both CUGP options were successfully improved, and total CO2 emissions were significantly reduced, compared with the conventional GTL processes. The process efficiency was sensitive to recycle ratio and more recycle seemed to be beneficial for improving process efficiency and reducing CO2 emission. However, the process efficiency was rather insensitive to split ratio (recycle to reforming unit/total recycle), and the optimum split ratio was determined to be zero.

  17. An Easy-to-Machine Electrochemical Flow Microreactor: Efficient Synthesis of Isoindolinone and Flow Functionalization.

    PubMed

    Folgueiras-Amador, Ana A; Philipps, Kai; Guilbaud, Sébastien; Poelakker, Jarno; Wirth, Thomas

    2017-11-27

    Flow electrochemistry is an efficient methodology to generate radical intermediates. An electrochemical flow microreactor has been designed and manufactured to improve the efficiency of electrochemical flow reactions. With this device only little or no supporting electrolytes are needed, making processes less costly and enabling easier purification. This is demonstrated by the facile synthesis of amidyl radicals used in intramolecular hydroaminations to produce isoindolinones. The combination with inline mass spectrometry facilitates a much easier combination of chemical steps in a single flow process. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  18. Chemoenzymatic Syntheses of Sialylated Oligosaccharides Containing C5-Modified Neuraminic Acids for Dual Inhibition of Hemagglutinins and Neuraminidases.

    PubMed

    Birikaki, Lémonia; Pradeau, Stéphanie; Armand, Sylvie; Priem, Bernard; Márquez-Domínguez, Luis; Reyes-Leyva, Julio; Santos-López, Gerardo; Samain, Eric; Driguez, Hugues; Fort, Sébastien

    2015-07-20

    A fast chemoenzymatic synthesis of sialylated oligosaccharides containing C5-modified neuraminic acids is reported. Analogues of GM3 and GM2 ganglioside saccharidic portions where the acetyl group of NeuNAc has been replaced by a phenylacetyl (PhAc) or a propanoyl (Prop) moiety have been efficiently prepared with metabolically engineered E. coli bacteria. GM3 analogues were either obtained by chemoselective modification of biosynthetic N-acetyl-sialyllactoside (GM3 NAc) or by direct bacterial synthesis using C5-modified neuraminic acid precursors. The latter strategy proved to be very versatile as it led to an efficient synthesis of GM2 analogues. These glycomimetics were assessed against hemagglutinins and sialidases. In particular, the GM3 NPhAc displayed a binding affinity for Maackia amurensis agglutinin (MAA) similar to that of GM3 NAc, while being resistant to hydrolysis by Vibrio cholerae (VC) neuraminidase. A preliminary study with influenza viruses also confirmed a selective inhibition of N1 neuraminidase by GM3 NPhAc, suggesting potential developments for the detection of flu viruses and for fighting them. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Intramolecular carbolithiation of N-allyl-ynamides: an efficient entry to 1,4-dihydropyridines and pyridines - application to a formal synthesis of sarizotan.

    PubMed

    Gati, Wafa; Rammah, Mohamed M; Rammah, Mohamed B; Evano, Gwilherm

    2012-01-01

    We have developed a general synthesis of polysubstituted 1,4-dihydropyridines and pyridines based on a highly regioselective lithiation/6-endo-dig intramolecular carbolithiation from readily available N-allyl-ynamides. This reaction, which has been successfully applied to the formal synthesis of the anti-dyskinesia agent sarizotan, further extends the use of ynamides in organic synthesis and further demonstrates the synthetic efficiency of carbometallation reactions.

  20. Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

    PubMed Central

    Matthessen, Roman; Fransaer, Jan; Binnemans, Koen

    2014-01-01

    Summary The near-unlimited availability of CO2 has stimulated a growing research effort in creating value-added products from this greenhouse gas. This paper presents the trends on the most important methods used in the electrochemical synthesis of carboxylic acids from carbon dioxide. An overview is given of different substrate groups which form carboxylic acids upon CO2 fixation, including mechanistic considerations. While most work focuses on the electrocarboxylation of substrates with sacrificial anodes, this review considers the possibilities and challenges of implementing other synthetic methodologies. In view of potential industrial application, the choice of reactor setup, electrode type and reaction pathway has a large influence on the sustainability and efficiency of the process. PMID:25383120

  1. Porous Pt-Ni Nanowires within In Situ Generated Metal-Organic Frameworks for Highly Chemoselective Cinnamaldehyde Hydrogenation.

    PubMed

    Zhang, Nan; Shao, Qi; Wang, Pengtang; Zhu, Xing; Huang, Xiaoqing

    2018-05-01

    Although chemoselective hydrogenation of unsaturated aldehydes is the major route to highly valuable industrially demanded unsaturated alcohols, it is still challenging, as the production of saturated aldehydes is more favorable over unsaturated alcohols from the view of thermodynamics. By combining the structural features of porous nanowires (NWs) and metal-organic frameworks (MOFs), a unique class of porous Pt-Ni NWs in situ encapsuled by MOFs (Pt-Ni NWs@Ni/Fex-MOFs) is designed to enhance the unsaturated alcohols selectivity in the cinnamaldehyde (CAL) hydrogenation. A detailed catalytic study shows that the porous Pt-Ni NWs@Ni/Fe x -MOFs exhibit volcano-type activity and selectivity in CAL hydrogenation as a function of Fe content. The optimized porous PtNi 2.20 NWs@Ni/Fe 4 -MOF is highly active and selective with 99.5% CAL conversion and 83.3% cinnamyl alcohol selectivity due to the confinement effect, appropriate thickness of MOF and its optimized electronic structure, and excellent durability with negligible activity and selectivity loss after five runs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Emulsion Synthesis of Size-Tunable CH3NH3PbBr3 Quantum Dots: An Alternative Route toward Efficient Light-Emitting Diodes.

    PubMed

    Huang, Hailong; Zhao, Fangchao; Liu, Lige; Zhang, Feng; Wu, Xian-gang; Shi, Lijie; Zou, Bingsuo; Pei, Qibing; Zhong, Haizheng

    2015-12-30

    We report a facile nonaqueous emulsion synthesis of colloidal halide perovskite quantum dots by controlled addition of a demulsifier into an emulsion of precursors. The size of resulting CH3NH3PbBr3 quantum dots can be tuned from 2 to 8 nm by varying the amount of demulsifier. Moreover, this emulsion synthesis also allows the purification of these quantum dots by precipitation from the colloidal solution and obtains solid-state powder which can be redissolved for thin film coating and device fabrication. The photoluminescence quantum yields of the quantum dots is generally in the range of 80-92%, and can be well-preserved after purification (∼80%). Green light-emitting diodes fabricated comprising a spin-cast layer of the colloidal CH3NH3PbBr3 quantum dots exhibited maximum current efficiency of 4.5 cd/A, power efficiency of 3.5 lm/W, and external quantum efficiency of 1.1%. This provides an alternative route toward high efficient solution-processed perovskite-based light-emitting diodes. In addition, the emulsion synthesis is versatile and can be extended for the fabrication of inorganic halide perovskite colloidal CsPbBr3 nanocrystals.

  3. Efficient synthesis of a fluorine-18 labeled biotin derivative.

    PubMed

    Claesener, Michael; Breyholz, Hans-Jörg; Hermann, Sven; Faust, Andreas; Wagner, Stefan; Schober, Otmar; Schäfers, Michael; Kopka, Klaus

    2012-11-01

    The natural occurring vitamin biotin, also known as vitamin H or vitamin B(7), plays a major role in various metabolic reactions. Caused by its high binding affinity to the protein avidin with a dissociation constant of about 10(-15)M the biotin-avidin system was extensively examined for multiple applications. We have synthesized a fluorine-18 labeled biotin derivative [(18)F]4 for a potential application in positron emission tomography (PET). Mesylate precursor 3 was obtained by an efficient two-step reaction via a copper catalyzed azide-alkyne cycloaddition (CuAAC) from easily accessible starting materials. [(18)F]4 was successfully synthesized by a nucleophilic radiofluorination of precursor 3. A biodistribution study by means of small-animal PET imaging in wt-mice was performed and serum stability was examined. Compound [(18)F]4 was obtained from precursor compound 3 with an average specific activity of 16GBq/μmol within 45min and a radiochemical yield of 45±5% (decay corrected). [(18)F]4 demonstrated only negligible decomposition in human serum. A qualitative binding study revealed the high affinity of the synthesized biotin derivative to avidin. Blocking experiments with native biotin showed that binding was site-specific. Biodistribution studies showed that [(18)F]4 was cleared quickly and efficiently from the body by hepatobiliary and renal elimination. An efficient synthesis for [(18)F]4 was established. In vivo characteristics were determined and demonstrated the pharmacokinetic behaviour of [(18)F]4. Copyright © 2012 Elsevier Inc. All rights reserved.

  4. Synthesis and evaluation of fluorogenic triglycerides as lipase assay substrates.

    PubMed

    Andersen, Rokhsana J; Brask, Jesper

    2016-06-01

    Three racemic fluorogenic triglycerides are synthesized and evaluated as lipase assay substrates. The presented synthesis route goes through a key triglyceride intermediate which can be chemoselectively functionalized with a wide range of different probes. Hence the substrate can be tailor-made for a specific assay, or focus can be on low cost in larger scale for applications in high-throughput screening (HTS) assays. In the specific examples, TG-ED, TG-FD and TG-F2 are assembled with the Edans-Dabcyl or the fluorescein-Dabcyl FRET pair, or relying on fluorescein self-quenching, respectively. Proof-of-concept assays allowed determination of 1st order kinetic parameters (kcat/KM) of 460s(-1)M(-1), 59s(-1)M(-1) and 346s(-1)M(-1), respectively, for the three substrates. Commercially available EnzChek lipase substrate provided 204s(-1)M(-1). Substrate concentration was identified as a critical parameter, with measured reaction rates decreasing at higher concentrations when intermolecular quenching becomes significant. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  5. Energy efficient room temperature synthesis of cardanol-based novolac resin using acoustic cavitation.

    PubMed

    Jadhav, Nilesh L; Sastry, Sai Krishna C; Pinjari, Dipak V

    2018-04-01

    The present study deals with synthesis of cardanol-cased novolac (CBN) resin by the condensation reaction between cardanol and formaldehyde using acoustic cavitation. It is a step-growth polymerization which occurs in the presence of an acid catalyst such as adipic acid, citric acid, oxalic acid, sulphuric acid and hydrochloric acid. CBN was also synthesised by a conventional method for the sake of comparison of techniques. The effect of molar ratio, effect of catalyst, effect of different catalyst and effect of power on the conversion to CBN has been studied. The synthesised CBN was characterized using the Fourier Transform Infra Red Spectroscopy (FTIR), Gel Permeation Chromatography (GPC), Nuclear Magnetic Resonance (NMR) Spectroscopy and Thermogravimetric Analysis (TGA). The reaction was monitored by the Acid value, free formaldehyde content and viscosity of the synthesised product. The reaction time required for the conventionally synthesised CBN was 5 h (300 min) with 120 °C as an operating temperature while sonochemically the time reduced to 30 min at room temperature. The amount of time and energy saved can be quantified. Ultrasound facilitated synthesis was found to be an energy efficient and time-saving method for the synthesis of novolac resin. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Efficient synthesis of silver nanoparticles from Prosopis juliflora leaf extract and its antimicrobial activity using sewage

    NASA Astrophysics Data System (ADS)

    Raja, K.; Saravanakumar, A.; Vijayakumar, R.

    2012-11-01

    In this paper, aqueous extract of fresh leaves of Prosopis juliflora was used for the synthesis of silver (Ag) nanoparticles. UV-Vis spectroscopy studies were carried out to asses silver nanoparticles formation within 5 min, scanning electron microscopic was used to characterize shape of the Ag nanoparticles, X-ray diffraction analysis confirms the nanoparticles as crystalline silver and facecentered cubic type and Fourier transform infra-red assed that shows biomolecule compounds which are responsible for reduction and capping material of silver nanoparticles. The anti microbial activity of silver nanoparticle was performed using sewage. The approach of plant-mediated synthesis appears to be cost efficient, eco-friendly and easy methods.

  7. Eco-efficient one-pot synthesis of quinazoline-2,4(1H,3H)-diones at room temperature in water.

    PubMed

    Tian, Xin-Chuan; Huang, Xing; Wang, Dan; Gao, Feng

    2014-01-01

    An efficient one-pot synthesis of quinazoline-2,4(1H,3H)-diones was developed. First, the reactions of anthranilic acid derivatives with potassium cyanate afforded the corresponding urea derivatives. Then, cyclization of the urea derivatives with NaOH afforded the monosodium salts of benzoylene urea. Finally, HCl treatment afforded the desired products in near-quantitative yields. This is an eco-efficient method because all the reactions were carried out in water, and the desired products were obtained simply by filtration. The aqueous filtrate was the only waste generated from the reaction. We scaled up the reaction to 1 kg starting material, thus establishing an alternative approach for the green synthesis of quinazoline-2,4(1H,3H)-diones in the chemical and pharmaceutical industries.

  8. Intramolecular carbolithiation of N-allyl-ynamides: an efficient entry to 1,4-dihydropyridines and pyridines – application to a formal synthesis of sarizotan

    PubMed Central

    Gati, Wafa; Rammah, Mohamed M; Rammah, Mohamed B

    2012-01-01

    Summary We have developed a general synthesis of polysubstituted 1,4-dihydropyridines and pyridines based on a highly regioselective lithiation/6-endo-dig intramolecular carbolithiation from readily available N-allyl-ynamides. This reaction, which has been successfully applied to the formal synthesis of the anti-dyskinesia agent sarizotan, further extends the use of ynamides in organic synthesis and further demonstrates the synthetic efficiency of carbometallation reactions. PMID:23365632

  9. Total synthesis of marinomycin A using salicylate as a molecular switch to mediate dimerization

    NASA Astrophysics Data System (ADS)

    Evans, P. Andrew; Huang, Mu-Hua; Lawler, Michael J.; Maroto, Sergio

    2012-08-01

    Antibiotics play a significant role in human health because of their ability to treat life-threatening bacterial infections. The growing problems with antibiotic resistance have made the development of new antibiotics a World Health Organization priority. Marinomycin A is a member of a new class of bis-salicylate-containing polyene macrodiolides, which have potent antibiotic activity against methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococcus faecium. Herein, we describe a triply convergent synthesis of this agent using the salicylate as a novel molecular switch for the chemoselective construction of the macrodiolide. This strategy raises new questions regarding the biosynthetic role of the salicylate and its potential impact on the mechanism of action of these types of agents. For instance, in contrast to penicillin, which enhances the electrophilicity of the cyclic amide through ring strain, salicylates reduce the electrophilicity of the aryl ester through an intramolecular resonance-assisted hydrogen bond to provide an amide surrogate.

  10. Practical aerobic oxidations of alcohols and amines with homogeneous copper/TEMPO and related catalyst systems.

    PubMed

    Ryland, Bradford L; Stahl, Shannon S

    2014-08-18

    Oxidations of alcohols and amines are common reactions in the synthesis of organic molecules in the laboratory and industry. Aerobic oxidation methods have long been sought for these transformations, but few practical methods exist that offer advantages over traditional oxidation methods. Recently developed homogeneous Cu/TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidinyl-N-oxyl) and related catalyst systems appear to fill this void. The reactions exhibit high levels of chemoselectivity and broad functional-group tolerance, and they often operate efficiently at room temperature with ambient air as the oxidant. These advances, together with their historical context and recent applications, are highlighted in this Minireview. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Effect of additives on chemoselectivity and diastereoselectivity in the catalytic epoxidation of chiral allylic alcohols with hydrogen peroxide and binuclear manganese complexes.

    PubMed

    Kilic, Hamdullah; Adam, Waldemar; Alsters, Paul L

    2009-02-06

    The catalytic oxidations of chiral allylic alcohols 2 by manganese complexes of the cyclic triamine 1,4,7-trimethyl-1,4,7-triazacyclononane (tmtacn) 1 and hydrogen peroxide as oxygen donor in the presence of co-catalyst are investigated to understand the factors that affect the catalyst selectivity. Chemoselectivity and diastereoselectivity of catalyst 1 are significantly affected by the structure of the allylic alcohol and the nature and amount of co-catalyst. More pronounced is the influence of the amount of added molar equivalents of H(2)O(2) (20-110 mol % with respect to the substrate). Our present results reflect the complex redox chemistry of the Mn catalyst 1/H(2)O(2)/co-catalyst system in the early phase of the alkene oxidation.

  12. Tailor Made Synthesis of T-Shaped and π-STACKED Dimers in the Gas Phase: Concept for Efficient Drug Design and Material Synthesis

    NASA Astrophysics Data System (ADS)

    Kumar, Sumit; Das, Aloke

    2013-06-01

    Non-covalent interactions play a key role in governing the specific functional structures of biomolecules as well as materials. Thus molecular level understanding of these intermolecular interactions can help in efficient drug design and material synthesis. It has been found from X-ray crystallography that pure hydrocarbon solids (i.e. benzene, hexaflurobenzene) have mostly slanted T-shaped (herringbone) packing arrangement whereas mixed solid hydrocarbon crystals (i.e. solid formed from mixtures of benzene and hexafluorobenzene) exhibit preferentially parallel displaced (PD) π-stacked arrangement. Gas phase spectroscopy of the dimeric complexes of the building blocks of solid pure benzene and mixed benzene-hexafluorobenzene adducts exhibit similar structural motifs observed in the corresponding crystal strcutures. In this talk, I will discuss about the jet-cooled dimeric complexes of indole with hexafluorobenzene and p-xylene in the gas phase using Resonant two photon ionzation and IR-UV double resonance spectroscopy combined with quantum chemistry calculations. In stead of studying benzene...p-xylene and benzene...hexafluorobenzene dimers, we have studied corresponding indole complexes because N-H group is much more sensitive IR probe compared to C-H group. We have observed that indole...hexafluorobenzene dimer has parallel displaced (PD) π-stacked structure whereas indole...p-xylene has slanted T-shaped structure. We have shown here selective switching of dimeric structure from T-shaped to π-stacked by changing the substituent from electron donating (-CH3) to electron withdrawing group (fluorine) in one of the complexing partners. Thus, our results demonstrate that efficient engineering of the non-covalent interactions can lead to efficient drug design and material synthesis.

  13. Facile solvothermal synthesis of cube-like Ag@AgCl: a highly efficient visible light photocatalyst

    NASA Astrophysics Data System (ADS)

    Han, Lei; Wang, Ping; Zhu, Chengzhou; Zhai, Yueming; Dong, Shaojun

    2011-07-01

    In this paper, a stable and highly efficient plasmonic photocatalyst, Ag@AgCl, with cube-like morphology, has been successfully prepared via a simple hydrothermal method. Using methylene dichloride as chlorine source in the synthesis can efficiently control the morphology of Ag@AgCl, due to the low release rate of chloride ions. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectra were used to characterize the obtained product. The photocatalytic activity of the obtained product was evaluated by the photodegradation of methyl orange (MO) under visible light irradiation, and it was found, interestingly, that Ag@AgCl exhibits high visible light photocatalytic activity and good stability.In this paper, a stable and highly efficient plasmonic photocatalyst, Ag@AgCl, with cube-like morphology, has been successfully prepared via a simple hydrothermal method. Using methylene dichloride as chlorine source in the synthesis can efficiently control the morphology of Ag@AgCl, due to the low release rate of chloride ions. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectra were used to characterize the obtained product. The photocatalytic activity of the obtained product was evaluated by the photodegradation of methyl orange (MO) under visible light irradiation, and it was found, interestingly, that Ag@AgCl exhibits high visible light photocatalytic activity and good stability. Electronic supplementary information (ESI) available: SEM images of the AgCl samples synthesized by changing the addition amount of PVP and AgNO3. See DOI: 10.1039/c1nr10247h

  14. A general and efficient palladium-catalyzed carbonylative synthesis of 2-aryloxazolines and 2-aryloxazines from aryl bromides.

    PubMed

    Wu, Xiao-Feng; Neumann, Helfried; Neumann, Stephan; Beller, Matthias

    2012-10-22

    Oxazoline is OK! A general and efficient method for the synthesis of oxazolines has been developed. This allowed the preparation of 27 five-membered-ring heterocycles and 11 six-membered-ring heterocycles in moderate to good yields. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Solid phase synthesis of phosphorothioate oligonucleotides utilizing diethyldithiocarbonate disulfide (DDD) as an efficient sulfur transfer reagent.

    PubMed

    Cheruvallath, Zacharia S; Kumar, R Krishna; Rentel, Claus; Cole, Douglas L; Ravikumar, Vasulinga T

    2003-04-01

    Diethyldithiodicarbonate (DDD), a cheap and easily prepared compound, is found to be a rapid and efficient sulfurizing reagent in solid phase synthesis of phosphorothioate oligodeoxyribonucleotides via the phosphoramidite approach. Product yield and quality based on IP-LC-MS compares well with high quality oligonucleotides synthesized using phenylacetyl disulfide (PADS) which is being used for manufacture of our antisense drugs.

  16. Efficient synthesis of silver nanoparticles from Prosopis juliflora leaf extract and its antimicrobial activity using sewage.

    PubMed

    Raja, K; Saravanakumar, A; Vijayakumar, R

    2012-11-01

    In this paper, aqueous extract of fresh leaves of Prosopis juliflora was used for the synthesis of silver (Ag) nanoparticles. UV-Vis spectroscopy studies were carried out to asses silver nanoparticles formation within 5 min, scanning electron microscopic was used to characterize shape of the Ag nanoparticles, X-ray diffraction analysis confirms the nanoparticles as crystalline silver and facecentered cubic type and Fourier transform infra-red assed that shows biomolecule compounds which are responsible for reduction and capping material of silver nanoparticles. The anti microbial activity of silver nanoparticle was performed using sewage. The approach of plant-mediated synthesis appears to be cost efficient, eco-friendly and easy methods. Copyright © 2012 Elsevier B.V. All rights reserved.

  17. Phase II study of chemoselection with docetaxel plus cisplatin and 5-fluorouracil induction chemotherapy and subsequent conversion surgery for locally advanced unresectable oesophageal cancer.

    PubMed

    Yokota, Tomoya; Kato, Ken; Hamamoto, Yasuo; Tsubosa, Yasuhiro; Ogawa, Hirofumi; Ito, Yoshinori; Hara, Hiroki; Ura, Takashi; Kojima, Takashi; Chin, Keisho; Hironaka, Shuichi; Kii, Takayuki; Kojima, Yasushi; Akutsu, Yasunori; Matsushita, Hisayuki; Kawakami, Kentaro; Mori, Keita; Nagai, Yushi; Asami, Chika; Kitagawa, Yuko

    2016-11-22

    The standard treatment for locally advanced unresectable squamous cell carcinoma (SCC) of the oesophagus is chemoradiation with cisplatin and 5-fluorouracil (CF-RT). This multicentre phase II trial assessed the safety and efficacy of chemoselection with docetaxel plus cisplatin and 5-fluorouracil (DCF) induction chemotherapy (ICT) and subsequent conversion surgery (CS) for initially unresectable locally advanced SCC of the oesophagus. Patients with clinical T4 and/or unresectable supraclavicular lymph node metastasis were eligible. Treatment started with three cycles of DCF-ICT, followed by CS if resectable, or by CF-RT if unresectable. The resectability was re-evaluated at 30-40 Gy of CF-RT, followed by CS if resectable, or by completion of 60 Gy of CF-RT. If resectable after CF-RT, CS was performed. The primary end point was 1-year overall survival (OS). From April 2013 to July 2014, 48 patients were enrolled. CS was performed in 41.7% (n=20), including DCF-CS (n=18), DCF-CF-RT40Gy-CS (n=1), and DCF-CF-RT60Gy-CS (n=1). R0 resection was confirmed in 19 patients (39.6%). Grade ⩾3 postoperative complications included one event each of recurrent laryngeal nerve palsy, lung infection, wound infection, pulmonary fistula, and dysphagia; but no serious postoperative complications were observed in patients undergoing CS. Clinical complete response after CF-RT was confirmed in 4 patients (8.3%). The estimated 1-year OS was 67.9% and lower limit of 80% confidence interval was 59.7%. There was one treatment-related death in patient receiving DCF-CF-RT60Gy. Chemoselection with DCF-ICT followed by CS as a multidisciplinary treatment strategy showed promising signs of tolerability and efficacy in patients with locally advanced unresectable SCC of the oesophagus.

  18. Phase II study of chemoselection with docetaxel plus cisplatin and 5-fluorouracil induction chemotherapy and subsequent conversion surgery for locally advanced unresectable oesophageal cancer

    PubMed Central

    Yokota, Tomoya; Kato, Ken; Hamamoto, Yasuo; Tsubosa, Yasuhiro; Ogawa, Hirofumi; Ito, Yoshinori; Hara, Hiroki; Ura, Takashi; Kojima, Takashi; Chin, Keisho; Hironaka, Shuichi; Kii, Takayuki; Kojima, Yasushi; Akutsu, Yasunori; Matsushita, Hisayuki; Kawakami, Kentaro; Mori, Keita; Nagai, Yushi; Asami, Chika; Kitagawa, Yuko

    2016-01-01

    Background: The standard treatment for locally advanced unresectable squamous cell carcinoma (SCC) of the oesophagus is chemoradiation with cisplatin and 5-fluorouracil (CF-RT). This multicentre phase II trial assessed the safety and efficacy of chemoselection with docetaxel plus cisplatin and 5-fluorouracil (DCF) induction chemotherapy (ICT) and subsequent conversion surgery (CS) for initially unresectable locally advanced SCC of the oesophagus. Methods: Patients with clinical T4 and/or unresectable supraclavicular lymph node metastasis were eligible. Treatment started with three cycles of DCF-ICT, followed by CS if resectable, or by CF-RT if unresectable. The resectability was re-evaluated at 30–40 Gy of CF-RT, followed by CS if resectable, or by completion of 60 Gy of CF-RT. If resectable after CF-RT, CS was performed. The primary end point was 1-year overall survival (OS). Results: From April 2013 to July 2014, 48 patients were enrolled. CS was performed in 41.7% (n=20), including DCF-CS (n=18), DCF-CF-RT40Gy-CS (n=1), and DCF-CF-RT60Gy-CS (n=1). R0 resection was confirmed in 19 patients (39.6%). Grade ⩾3 postoperative complications included one event each of recurrent laryngeal nerve palsy, lung infection, wound infection, pulmonary fistula, and dysphagia; but no serious postoperative complications were observed in patients undergoing CS. Clinical complete response after CF-RT was confirmed in 4 patients (8.3%). The estimated 1-year OS was 67.9% and lower limit of 80% confidence interval was 59.7%. There was one treatment-related death in patient receiving DCF-CF-RT60Gy. Conclusions: Chemoselection with DCF-ICT followed by CS as a multidisciplinary treatment strategy showed promising signs of tolerability and efficacy in patients with locally advanced unresectable SCC of the oesophagus. PMID:27811857

  19. ACCESS 1: Approximation Concepts Code for Efficient Structural Synthesis program documentation and user's guide

    NASA Technical Reports Server (NTRS)

    Miura, H.; Schmit, L. A., Jr.

    1976-01-01

    The program documentation and user's guide for the ACCESS-1 computer program is presented. ACCESS-1 is a research oriented program which implements a collection of approximation concepts to achieve excellent efficiency in structural synthesis. The finite element method is used for structural analysis and general mathematical programming algorithms are applied in the design optimization procedure. Implementation of the computer program, preparation of input data and basic program structure are described, and three illustrative examples are given.

  20. Determining the microwave coupling and operational efficiencies of a microwave plasma assisted chemical vapor deposition reactor under high pressure diamond synthesis operating conditions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Nad, Shreya; Department of Physics and Astronomy, Michigan State University, East Lansing, Michigan 48824; Gu, Yajun

    2015-07-15

    The microwave coupling efficiency of the 2.45 GHz, microwave plasma assisted diamond synthesis process is investigated by experimentally measuring the performance of a specific single mode excited, internally tuned microwave plasma reactor. Plasma reactor coupling efficiencies (η) > 90% are achieved over the entire 100–260 Torr pressure range and 1.5–2.4 kW input power diamond synthesis regime. When operating at a specific experimental operating condition, small additional internal tuning adjustments can be made to achieve η > 98%. When the plasma reactor has low empty cavity losses, i.e., the empty cavity quality factor is >1500, then overall microwave discharge coupling efficienciesmore » (η{sub coup}) of >94% can be achieved. A large, safe, and efficient experimental operating regime is identified. Both substrate hot spots and the formation of microwave plasmoids are eliminated when operating within this regime. This investigation suggests that both the reactor design and the reactor process operation must be considered when attempting to lower diamond synthesis electrical energy costs while still enabling a very versatile and flexible operation performance.« less

  1. Design and Synthesis of Novel Block Copolymers for Efficient Opto-Electronic Applications

    NASA Technical Reports Server (NTRS)

    Sun, Sam-Shajing; Fan, Zhen; Wang, Yiqing; Taft, Charles; Haliburton, James; Maaref, Shahin

    2002-01-01

    It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.

  2. Chemoselective Nitro Group Reduction and Reductive Dechlorination Initiate Degradation of 2-Chloro-5-Nitrophenol by Ralstonia eutropha JMP134

    PubMed Central

    Schenzle, Andreas; Lenke, Hiltrud; Spain, Jim C.; Knackmuss, Hans-Joachim

    1999-01-01

    Ralstonia eutropha JMP134 utilizes 2-chloro-5-nitrophenol as a sole source of nitrogen, carbon, and energy. The initial steps for degradation of 2-chloro-5-nitrophenol are analogous to those of 3-nitrophenol degradation in R. eutropha JMP134. 2-Chloro-5-nitrophenol is initially reduced to 2-chloro-5-hydroxylaminophenol, which is subject to an enzymatic Bamberger rearrangement yielding 2-amino-5-chlorohydroquinone. The chlorine of 2-amino-5-chlorohydroquinone is removed by a reductive mechanism, and aminohydroquinone is formed. 2-Chloro-5-nitrophenol and 3-nitrophenol induce the expression of 3-nitrophenol nitroreductase, of 3-hydroxylaminophenol mutase, and of the dechlorinating activity. 3-Nitrophenol nitroreductase catalyzes chemoselective reduction of aromatic nitro groups to hydroxylamino groups in the presence of NADPH. 3-Nitrophenol nitroreductase is active with a variety of mono-, di-, and trinitroaromatic compounds, demonstrating a relaxed substrate specificity of the enzyme. Nitrosobenzene serves as a substrate for the enzyme and is converted faster than nitrobenzene. PMID:10347008

  3. A metalloenzyme-like catalytic system for the chemoselective oxidative cross-coupling of primary amines to imines under ambient conditions.

    PubMed

    Largeron, Martine; Fleury, Maurice-Bernard

    2015-02-23

    The direct oxidative cross-coupling of primary amines is a challenging transformation as homocoupling is usually preferred. We report herein the chemoselective preparation of cross-coupled imines through the synergistic combination of low loadings of Cu(II) metal-catalyst and o-iminoquinone organocatalyst under ambient conditions. This homogeneous cooperative catalytic system has been inspired by the reaction of copper amine oxidases, a family of metalloenzymes with quinone organic cofactors that mediate the selective oxidation of primary amines to aldehydes. After optimization, the desired cross-coupled imines are obtained in high yields with broad substrate scope through a transamination process that leads to the homocoupled imine intermediate, followed by dynamic transimination. The ability to carry out the reactions at room temperature and with ambient air, rather than molecular oxygen as the oxidant, and equimolar amounts of each coupling partner is particularly attractive from an environmentally viewpoint. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Ferric hydroxide supported gold subnano clusters or quantum dots: enhanced catalytic performance in chemoselective hydrogenation.

    PubMed

    Liu, Lequan; Qiao, Botao; Ma, Yubo; Zhang, Juan; Deng, Youquan

    2008-05-21

    An attempt to prepare ferric hydroxide supported Au subnano clusters via modified co-precipitation without any calcination was made. High resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) have been employed to study the structure and chemical states of these catalysts. No Au species could be observed in the HRTEM image nor from the XRD pattern, suggesting that the sizes of the Au species in and on the ferric hydroxide support were less than or around 1 nm. Chemoselective hydrogenation of aromatic nitro compounds and alpha,beta-unsaturated aldehydes was selected as a probe reaction to examine the catalytic properties of this catalyst. Under the same reaction conditions, such as 100 degrees C and 1 MPa H2 in the hydrogenation of aromatic nitro compounds, a 96-99% conversion (except for 4-nitrobenzonitrile) with 99% selectivity was obtained over the ferric hydroxide supported Au catalyst, and the TOF values were 2-6 times higher than that of the corresponding ferric oxide supported catalyst with 3-5 nm size Au particles. For further evaluation of this Au catalyst in the hydrogenation of citral and cinnamaldehyde, selectivity towards unsaturated alcohols was 2-20 times higher than that of the corresponding ferric oxide Au catalyst.

  5. Chemoselective Installation of Amine Bonds on Proteins through Aza-Michael Ligation.

    PubMed

    Freedy, Allyson M; Matos, Maria J; Boutureira, Omar; Corzana, Francisco; Guerreiro, Ana; Akkapeddi, Padma; Somovilla, Víctor J; Rodrigues, Tiago; Nicholls, Karl; Xie, Bangwen; Jiménez-Osés, Gonzalo; Brindle, Kevin M; Neves, André A; Bernardes, Gonçalo J L

    2017-12-20

    Chemical modification of proteins is essential for a variety of important diagnostic and therapeutic applications. Many strategies developed to date lack chemo- and regioselectivity as well as result in non-native linkages that may suffer from instability in vivo and adversely affect the protein's structure and function. We describe here the reaction of N-nucleophiles with the amino acid dehydroalanine (Dha) in a protein context. When Dha is chemically installed in proteins, the addition of a wide-range N-nucleophiles enables the rapid formation of amine linkages (secondary and tertiary) in a chemoselective manner under mild, biocompatible conditions. These new linkages are stable at a wide range of pH values (pH 2.8 to 12.8), under reducing conditions (biological thiols such as glutathione) and in human plasma. This method is demonstrated for three proteins and is shown to be fully compatible with disulfide bridges, as evidenced by the selective modification of recombinant albumin that displays 17 structurally relevant disulfides. The practicability and utility of our approach is further demonstrated by the construction of a chemically modified C2A domain of Synaptotagmin-I protein that retains its ability to preferentially bind to apoptotic cells at a level comparable to the native protein. Importantly, the method was useful for building a homogeneous antibody-drug conjugate with a precise drug-to-antibody ratio of 2. The kinase inhibitor crizotinib was directly conjugated to Dha through its piperidine motif, and its antibody-mediated intracellular delivery results in 10-fold improvement of its cancer cell-killing efficacy. The simplicity and exquisite site-selectivity of the aza-Michael ligation described herein allows the construction of stable secondary and tertiary amine-linked protein conjugates without affecting the structure and function of biologically relevant proteins.

  6. Highly Chemoselective Reduction of Amides (Primary, Secondary, Tertiary) to Alcohols using SmI2/Amine/H2O under Mild Conditions

    PubMed Central

    2014-01-01

    Highly chemoselective direct reduction of primary, secondary, and tertiary amides to alcohols using SmI2/amine/H2O is reported. The reaction proceeds with C–N bond cleavage in the carbinolamine intermediate, shows excellent functional group tolerance, and delivers the alcohol products in very high yields. The expected C–O cleavage products are not formed under the reaction conditions. The observed reactivity is opposite to the electrophilicity of polar carbonyl groups resulting from the nX → π*C=O (X = O, N) conjugation. Mechanistic studies suggest that coordination of Sm to the carbonyl and then to Lewis basic nitrogen in the tetrahedral intermediate facilitate electron transfer and control the selectivity of the C–N/C–O cleavage. Notably, the method provides direct access to acyl-type radicals from unactivated amides under mild electron transfer conditions. PMID:24460078

  7. Efficient Nazarov Cyclization/Wagner-Meerwein Rearrangement Terminated by a Cu(II)-Promoted Oxidation: Synthesis of 4-Alkylidene Cyclopentenones

    PubMed Central

    Lebœuf, David; Theiste, Eric; Gandon, Vincent; Daifuku, Stephanie L.; Neidig, Michael L.

    2013-01-01

    The discovery and elucidation of a novel Nazarov cyclization/Wagner-Meerwein rearrangement/oxidation sequence is described, which constitutes an efficient strategy for the synthesis of 4-alkylidene cyclopentenones. DFT computations and EPR experiments were conducted to gain further mechanistic insight into the reaction pathways. PMID:23436470

  8. ACCESS 3. Approximation concepts code for efficient structural synthesis: User's guide

    NASA Technical Reports Server (NTRS)

    Fleury, C.; Schmit, L. A., Jr.

    1980-01-01

    A user's guide is presented for ACCESS-3, a research oriented program which combines dual methods and a collection of approximation concepts to achieve excellent efficiency in structural synthesis. The finite element method is used for structural analysis and dual algorithms of mathematical programming are applied in the design optimization procedure. This program retains all of the ACCESS-2 capabilities and the data preparation formats are fully compatible. Four distinct optimizer options were added: interior point penalty function method (NEWSUMT); second order primal projection method (PRIMAL2); second order Newton-type dual method (DUAL2); and first order gradient projection-type dual method (DUAL1). A pure discrete and mixed continuous-discrete design variable capability, and zero order approximation of the stress constraints are also included.

  9. Common Distribution of gad Operon in Lactobacillus brevis and its GadA Contributes to Efficient GABA Synthesis toward Cytosolic Near-Neutral pH

    PubMed Central

    Wu, Qinglong; Tun, Hein Min; Law, Yee-Song; Khafipour, Ehsan; Shah, Nagendra P.

    2017-01-01

    Many strains of lactic acid bacteria (LAB) and bifidobacteria have exhibited strain-specific capacity to produce γ-aminobutyric acid (GABA) via their glutamic acid decarboxylase (GAD) system, which is one of amino acid-dependent acid resistance (AR) systems in bacteria. However, the linkage between bacterial AR and GABA production capacity has not been well established. Meanwhile, limited evidence has been provided to the global diversity of GABA-producing LAB and bifidobacteria, and their mechanisms of efficient GABA synthesis. In this study, genomic survey identified common distribution of gad operon-encoded GAD system in Lactobacillus brevis for its GABA production among varying species of LAB and bifidobacteria. Importantly, among four commonly distributed amino acid-dependent AR systems in Lb. brevis, its GAD system was a major contributor to maintain cytosolic pH homeostasis by consuming protons via GABA synthesis. This highlights that Lb. brevis applies GAD system as the main strategy against extracellular and intracellular acidification demonstrating its high capacity of GABA production. In addition, the abundant GadA retained its activity toward near-neutral pH (pH 5.5–6.5) of cytosolic acidity thus contributing to efficient GABA synthesis in Lb. brevis. This is the first global report illustrating species-specific characteristic and mechanism of efficient GABA synthesis in Lb. brevis. PMID:28261168

  10. I. Development of Metal-Mediated SPOT-Synthesis Methods for the Efficient Construction of Small-Molecule Macroarrays. II. Design and Synthesis of Novel Bacterial Biofilm Inhibitors

    NASA Astrophysics Data System (ADS)

    Frei, Reto

    I. The use of small molecule probes to explore biological phenomena has become a valuable tool in chemical biology. As a result, methods that permit the rapid synthesis and biological evaluation of such compounds are highly sought-after. The small molecule macroarray represents one such approach for the synthesis and identification of novel bioactive agents. Macroarrays are readily constructed via the SPOT-synthesis technique on planar cellulose membranes, yielding spatially addressed libraries of ˜10-1000 unique compounds. We sought to expand the arsenal of chemical reactions compatible with this solid-phase platform, and developed highly efficient SPOT-synthesis protocols for the Mizoroki-Heck, Suzuki-Miyaura, and copper-catalyzed azide-alkyne cycloaddition reaction. We demonstrated that these metal-mediated reactions can be implemented, either individually or sequentially, for the efficient construction of small molecules in high purity on rapid time scales. Utilizing these powerful C-C and C-N bond forming coupling reactions, we constructed a series of macroarrays based on novel stilbene, phenyl-naphthalene, and triazole scaliblds. Subsequent biological testing of the stilbene and phenyl-naphthalene libraries revealed several potent antagonists and agonists, respectively, of the quorum sensing (QS) receptor LuxR in Vibrio fischeri. II. Bacteria living within biofilms are notorious for their resistance to known antibiotic agents, and constitute a major human health threat. Methods to attenuate biofilm growth would have a significant impact on the management of bacterial infections. Despite intense research efforts, small molecules capable of either inhibiting or dispersing biolilms remain scarce. We utilized natural products with purported anti-biofilm or QS inhibitory activity as sources of structural insight to guide the synthesis of novel biofilm modulators with improved activities. These studies revealed 2-aminobenzimidazole derivatives as highly potent

  11. Development of a gene synthesis platform for the efficient large scale production of small genes encoding animal toxins.

    PubMed

    Sequeira, Ana Filipa; Brás, Joana L A; Guerreiro, Catarina I P D; Vincentelli, Renaud; Fontes, Carlos M G A

    2016-12-01

    Gene synthesis is becoming an important tool in many fields of recombinant DNA technology, including recombinant protein production. De novo gene synthesis is quickly replacing the classical cloning and mutagenesis procedures and allows generating nucleic acids for which no template is available. In addition, when coupled with efficient gene design algorithms that optimize codon usage, it leads to high levels of recombinant protein expression. Here, we describe the development of an optimized gene synthesis platform that was applied to the large scale production of small genes encoding venom peptides. This improved gene synthesis method uses a PCR-based protocol to assemble synthetic DNA from pools of overlapping oligonucleotides and was developed to synthesise multiples genes simultaneously. This technology incorporates an accurate, automated and cost effective ligation independent cloning step to directly integrate the synthetic genes into an effective Escherichia coli expression vector. The robustness of this technology to generate large libraries of dozens to thousands of synthetic nucleic acids was demonstrated through the parallel and simultaneous synthesis of 96 genes encoding animal toxins. An automated platform was developed for the large-scale synthesis of small genes encoding eukaryotic toxins. Large scale recombinant expression of synthetic genes encoding eukaryotic toxins will allow exploring the extraordinary potency and pharmacological diversity of animal venoms, an increasingly valuable but unexplored source of lead molecules for drug discovery.

  12. Biocompatible PEGylated MoS2 nanosheets: controllable bottom-up synthesis and highly efficient photothermal regression of tumor.

    PubMed

    Wang, Shige; Li, Kai; Chen, Yu; Chen, Hangrong; Ma, Ming; Feng, Jingwei; Zhao, Qinghua; Shi, Jianlin

    2015-01-01

    Two-dimensional transition metal dichalcogenides, particularly MoS2 nanosheets, have been deemed as a novel category of NIR photothermal transducing agent. Herein, an efficient and versatile one-pot solvothermal synthesis based on "bottom-up" strategy has been, for the first time, proposed for the controlled synthesis of PEGylated MoS2 nanosheets by using a novel "integrated" precursor containing both Mo and S elements. This facile but unique PEG-mediated solvothermal procedure endowed MoS2 nanosheets with controlled size, increased crystallinity and excellent colloidal stability. The photothermal performance of nanosheets was optimized via modulating the particulate size and surface PEGylation. PEGylated MoS2 nanosheets with desired photothermal conversion performance and excellent colloidal and photothermal stability were further utilized for highly efficient photothermal therapy of cancer in a tumor-bearing mouse xenograft. Without showing observable in vitro and in vivo hemolysis, coagulation and toxicity, the optimized MoS2-PEG nanosheets showed promising in vitro and in vivo anti-cancer efficacy. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Symmetrically tetrasubstituted [2.2]paracyclophanes: their systematization and regioselective synthesis of several types of bis-bifunctional derivatives by double electrophilic substitution.

    PubMed

    Vorontsova, Natalia V; Rozenberg, Valeria I; Sergeeva, Elena V; Vorontsov, Evgenii V; Starikova, Zoya A; Lyssenko, Konstantin A; Hopf, Henning

    2008-01-01

    The possible number of chiral and achiral tetrasubstituted [2.2]paracyclophanes possessing different types of symmetry (C(2), C(i), C(s), C(2v), C(2h)) is evaluated and a unified independent trivial naming descriptor system is introduced. The reactivity and regioselectivity of the electrophilic substitution of the chiral pseudo-meta- and achiral pseudo-para-disubstituted [2.2]paracyclophanes are investigated in an approach suggested to be general for the synthesis of bis-bifunctional [2.2]paracyclophanes. The mono- and diacylation of chiral pseudo-meta-dihydroxy[2.2]paracyclophane 14 with acetylchloride occur ortho-regioselectively to produce tri- 22, 23 and symmetrically 21 tetrasubstituted acyl derivatives. The same reaction with benzoylchloride is neither regio-, nor chemoselective, and gives rise to a mixture of ortho-/para-, mono-/diacylated compounds 27-31. The double acylation of pseudo-meta-dimethoxy[2.2]paracyclophane 18 is completely para-regioselective. Electrophilic substitution of pseudo-meta-bis(methoxycarbonyl)[2.2]paracyclophane 20 regioselectively generates the pseudo-gem-substitution pattern. Formylation of this substrate produces the monocarbonyl derivatives 35 only, whereas the Fe-catalyzed bromination may be directed towards mono- 36 or disubstitution 37 products chemoselectively by varying the reactions conditions. The diacylation and dibromination reactions of the respective achiral diphenol 12 and bis(methoxycarbonyl) 40 derivatives of the pseudo-para-structure retain regioselectivities which are characteristic for their pseudo-meta-regioisomers. Imino ligands 26, 25, and 39, which were obtained from monoacyl- 22 and diacyldihydroxy[2.2]paracyclophanes 21, 38, are tested as chiral ligands in stereoselective Et(2)Zn addition to benzaldehyde producing 1-phenylpropanol with ee values up to 76 %.

  14. Synthesis of a new class of Betti bases by the Mannich-type reaction: efficient, facile, solvent-free and one-pot protocol.

    PubMed

    Shahrisa, Aziz; Teimuri-Mofrad, Reza; Gholamhosseini-Nazari, Mahdi

    2015-02-01

    A variety of organocatalysts has been screened for the synthesis of arylaminonaphthols. It has been shown that (N,N-dimethylethanolamine) is a highly efficient organocatalyst for the direct synthesis of a novel class of arylaminonaphthols via three-component condensation of 2-naphthol, aldehydes, and arylamines under solvent-free conditions. Mild, one-pot, and green reaction conditions, relatively short reaction times and good yields make this protocol highly significant. 25 new compounds have been synthesized by this method.

  15. An efficient synthesis of 1α,25-dihydroxyvitamin D3 LC-biotin.

    PubMed

    Kattner, Lars; Bernardi, Dan

    2017-10-01

    In recent years the apparent impact of vitamin D deficiency on human health has gained increased awareness. Consequently, the development of appropriate assays to measure the status of medicinally most relevant vitamin D metabolites in human blood, serum or relevant tissue is continuously being improved. Particularly, assaying of 1α,25-dihydroxyvitamin D 3 , in turn considered as the most active metabolite, is mainly indicated in disorders leading to calcaemia or those resulting from an impaired 1α-hydroxylation of 25-hydroxyvitamin D 3 . Thus, in some competitive protein binding and ELISA assays, biotin-linked 1α,25-dihydroxyvitamin D 3 (1α,25-dihydroxyvitamin D 3 LC-biotin) is employed for measurement of actual calicitriol concentration. A new efficient synthesis of 1α,25-dihydroxyvitamin D 3 LC-biotin is described, starting with readily available vitamin D 2 , and combining a classical approach to access 1α,25-dihydroxyvitamin D 3 , appropriate OH-protective group transformations, and a C-3-O-alkylation, suitable to connect the biotin-linker in a reliable, selective and high yielding strategy. The developed methodology is applicable to the synthesis of a wide variety of C-3-OH-linked vitamin D 3 and D 2 derivatives. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Design and efficient synthesis of novel GM2 analogues with respect to the elucidation of the function of GM2 activator.

    PubMed

    Komori, Tatsuya; Ando, Takayuki; Imamura, Akihiro; Li, Yu-Teh; Ishida, Hideharu; Kiso, Makoto

    2008-10-01

    To elucidate the mechanism underlying the hydrolysis of the GalNAcbeta1-->4Gal linkage in ganglioside GM2 [GalNAcbeta1-->4(NeuAcalpha2-->3)Galbeta1-->4Glcbeta1-->1' Cer] by beta-hexosaminidase A (Hex A) with GM2 activator protein, we designed and synthesized two kinds of GM2 linkage analogues-6'-NeuAc-GM2 and alpha-GalNAc-GM2. In this paper, the efficient and systematic synthesis of these GM2 analogues was described. The highlight of our synthesis process is that the key intermediates, newly developed sialyllactose derivatives, were efficiently prepared in sufficient quantities; these derivatives directly served as highly reactive glycosyl acceptors and coupled with GalNTroc donors to furnish the assembly of GM2 tetrasaccharides in large quantities.

  17. Microwave promoted simple, efficient and regioselective synthesis of trisubstituted imidazo[1,2-a]benzimidazoles on soluble support.

    PubMed

    Chen, Li-Hsun; Hsiao, Ya-Shan; Yellol, Gorakh S; Sun, Chung-Ming

    2011-03-14

    An efficient microwave-assisted and soluble polymer-supported synthesis of medicinally important imidazole-fused benzimidazoles has been developed. The protocol involves the rapid condensation of polymer-bound amino benzimidazoles with various α-bromoketones and subsequent in situ intramolecular cyclization under microwave irradiation resulting in a one pot synthesis of imidazole interlacing benzimidazole polymer conjugates. The condensed product was obtained with excellent regioselectivity. The biologically interesting imidazo[1,2-a]benzimidazoles was released from polymer support at ambient temperature. Diversity in the triheterocyclic nucleus was achieved by the different substitutions at its 2, 3, and 9 positions. The new protocol has the advantages of short reaction time, easy workup process, excellent yields, reduced environmental impact, wide substrate scope and convenient procedure.

  18. An Efficient Synthesis of 2-Substituted Benzimidazoles via Photocatalytic Condensation of o-Phenylenediamines and Aldehydes.

    PubMed

    Kovvuri, Jeshma; Nagaraju, Burri; Kamal, Ahmed; Srivastava, Ajay K

    2016-10-10

    A photocatalytic method has been developed for the efficient synthesis of functionalized benzimidazoles. This protocol involves photocatalytic condensation of o-phenylenediamines with various aldehydes using the Rose Bengal as photocatalyst. The method was found to be general and was successfully employed for accessing pharmaceutically important benzimidazoles by the condensation of aromatic, heteroaromatic and aliphatic aldehydes with o-phenylenediamines, in good-to-excellent yields. Notably, the method was found to be effective for the condensation of less reactive heterocyclic aldehydes with o-phenylenediamines.

  19. Efficient assessment of modified nucleoside stability under conditions of automated oligonucleotide synthesis: characterization of the oxidation and oxidative desulfurization of 2-thiouridine.

    PubMed

    Sochacka, E

    2001-01-01

    In order to efficiently assess the chemical stability of modified nucleosides to the reagents and conditions of automated oligonucleotide synthesis, we designed, developed and tested a scheme in which the modified nucleoside, directly attached to a solid support, is exposed to the cyclic chemistry of the instrument. Stability of 2-thiouridine against different oxidizers was investigated. Tertbutyl hydroperoxide (1 M) in anhydrous acetonitrile was a more effective oxidizer for the incorporation of 2-thiouridine into oligonucleotide chains than the same oxidizer in methylene chloride. Carbon tetrachloride/water in the presence of a basic catalyst was superior in maintaining the thiocarbonyl function, but its utility for RNA synthesis has yet to be fully tested, whereas 2-phenylsulfonyloxaziridine was a very efficient reagent for oxidative desulfurization of 2-thiouridine.

  20. A Catalytic Borylation/Dehalogenation Route to o-Fluoro Arylboronates

    PubMed Central

    2015-01-01

    A two-step Ir-catalyzed borylation/Pd-catalyzed dehalogenation sequence allows for the net synthesis of fluoroarenes where the boronic ester is ortho to fluorine. Key elements of this approach include the use of a halogen para to the fluorine to block meta Ir-catalyzed borylation and the chemoselective Pd-catalyzed dehalogenation by KF activated polymethylhydrosiloxane (PMHS). PMID:25418716

  1. A catalytic borylation/dehalogenation route to o-fluoro arylboronates.

    PubMed

    Jayasundara, Chathurika R K; Unold, Jason M; Oppenheimer, Jossian; Smith, Milton R; Maleczka, Robert E

    2014-12-05

    A two-step Ir-catalyzed borylation/Pd-catalyzed dehalogenation sequence allows for the net synthesis of fluoroarenes where the boronic ester is ortho to fluorine. Key elements of this approach include the use of a halogen para to the fluorine to block meta Ir-catalyzed borylation and the chemoselective Pd-catalyzed dehalogenation by KF activated polymethylhydrosiloxane (PMHS).

  2. Efficient Nazarov cyclization/Wagner-Meerwein rearrangement terminated by a Cu(II)-promoted oxidation: synthesis of 4-alkylidene cyclopentenones.

    PubMed

    Lebœuf, David; Theiste, Eric; Gandon, Vincent; Daifuku, Stephanie L; Neidig, Michael L; Frontier, Alison J

    2013-04-08

    The discovery and elucidation of a new Nazarov cyclization/Wagner-Meerwein rearrangement/oxidation sequence is described that constitutes an efficient strategy for the synthesis of 4-alkylidene cyclopentenones. DFT computations and EPR experiments were conducted to gain further mechanistic insight into the reaction pathways. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Synthesis of heteroglycoclusters by using orthogonal chemoselective ligations

    PubMed Central

    Thomas, Baptiste; Fiore, Michele; Bossu, Isabelle; Dumy, Pascal

    2012-01-01

    Summary Synthetic heteroglycoclusters are being subjected to increasing interest due to their potential to serve as selective ligands for carbohydrate-binding proteins. In this paper, we describe an expedient strategy to prepare cyclopeptides displaying well-defined distributions and combinations of carbohydrates. By using both oxime ligation and copper(I)-catalyzed alkyne–azide cycloaddition, two series of compounds bearing binary combinations of αMan, αFuc or βLac in an overall tetravalent presentation, and either 2:2 or 3:1 relative proportions, have been prepared. PMID:22509212

  4. Hydrothermal Synthesis of VO2 Polymorphs: Advantages, Challenges and Prospects for the Application of Energy Efficient Smart Windows.

    PubMed

    Li, Ming; Magdassi, Shlomo; Gao, Yanfeng; Long, Yi

    2017-09-01

    Vanadium dioxide (VO 2 ) is a widely studied inorganic phase change material, which has a reversible phase transition from semiconducting monoclinic to metallic rutile phase at a critical temperature of τ c ≈ 68 °C. The abrupt decrease of infrared transmittance in the metallic phase makes VO 2 a potential candidate for thermochromic energy efficient windows to cut down building energy consumption. However, there are three long-standing issues that hindered its application in energy efficient windows: high τ c , low luminous transmittance (T lum ), and undesirable solar modulation ability (ΔT sol ). Many approaches, including nano-thermochromism, porous films, biomimetic surface reconstruction, gridded structures, antireflective overcoatings, etc, have been proposed to tackle these issues. The first approach-nano-thermochromism-which is to integrate VO 2 nanoparticles in a transparent matrix, outperforms the rest; while the thermochromic performance is determined by particle size, stoichiometry, and crystallinity. A hydrothermal method is the most common method to fabricate high-quality VO 2 nanoparticles, and has its own advantages of large-scale synthesis and precise phase control of VO 2 . This Review focuses on hydrothermal synthesis, physical properties of VO 2 polymorphs, and their transformation to thermochromic VO 2 (M), and discusses the advantages, challenges, and prospects of VO 2 (M) in energy-efficient smart windows application. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 1,2-Dicyclopropylethyne and (Cyclopropylethynyl)cyclobutane from an Efficient Synthesis of 1,2-(omega-Haloalkyl)ethynes and 1-Cycloalkyl-2-(omega-haloalkyl)ethynes (Pre Print)

    DTIC Science & Technology

    2012-02-09

    Efficient Synthesis of 1,2-(ω-Haloalkyl0ethynes and 1 -Cycloalkyl-2-(ω-haloalkyl)ethynes 5b. GRANT NUMBER (Pre Print) 5c. PROGRAM ELEMENT NUMBER...suffers from low yield as is evi- dent from the reported synthesis of 5-chloropent- 1 -yne (5, 57%)9 and 1,8-dichlorooct- 1 -yne (9, 36%).8 The synthesis ... chloropropane / 1 -bromo-4-chlorobutane is very sluggish and incomplete in THF. However, the reaction in the presence of 10 mol % Bu4NI results in an

  6. RNA turnover and protein synthesis in fish cells.

    PubMed

    Smith, R W; Palmer, R M; Houlihan, D F

    2000-03-01

    Protein synthesis in fish has been previously correlated with RNA content. The present study investigates whether protein and RNA synthesis rates are similarly related. Protein and RNA synthesis rates were determined from 3H-phenylalanine and 3H-uridine incorporation, respectively, and expressed as % x day(-1) and half-lives, respectively. Three fibroblast cell lines were used: BF-2, RTP, CHSE 214, which are derived from the bluegill, rainbow trout and Chinook salmon, respectively. These cells contained similar RNA concentrations (approximately 175 microg RNA x mg(-1) cell protein). Therefore differences in protein synthesis rates, BF-2 (31.3 +/- 1.8)>RTP (25.1 +/- 1.7)>CHSE 214 (17.6 +/-1.1), were attributable to RNA translational efficiency. The most translationally efficient RNA (BF-2 cells), 1.8 mg protein synthesised x microg(-1) RNA x day(-1), corresponded to the lowest RNA half-life, 75.4 +/- 6.4 h. Translationally efficient RNA was also energetically efficient with BF-2 cells exploiting the least costly route of nucleotide supply (i.e. exogenous salvage) 3.5-6.0 times more than the least translationally efficient RNA (CHSE 214 cells). These data suggest that differential nucleotide supply, between intracellular synthesis and exogenous salvage, constitutes the area of pre-translational flexibility exploited to maintain RNA synthesis as a fixed energetic cost component of protein synthesis.

  7. Green chemistry for nanoparticle synthesis.

    PubMed

    Duan, Haohong; Wang, Dingsheng; Li, Yadong

    2015-08-21

    The application of the twelve principles of green chemistry in nanoparticle synthesis is a relatively new emerging issue concerning the sustainability. This field has received great attention in recent years due to its capability to design alternative, safer, energy efficient, and less toxic routes towards synthesis. These routes have been associated with the rational utilization of various substances in the nanoparticle preparations and synthetic methods, which have been broadly discussed in this tutorial review. This article is not meant to provide an exhaustive overview of green synthesis of nanoparticles, but to present several pivotal aspects of synthesis with environmental concerns, involving the selection and evaluation of nontoxic capping and reducing agents, the choice of innocuous solvents and the development of energy-efficient synthetic methods.

  8. Parallelizing quantum circuit synthesis

    NASA Astrophysics Data System (ADS)

    Di Matteo, Olivia; Mosca, Michele

    2016-03-01

    Quantum circuit synthesis is the process in which an arbitrary unitary operation is decomposed into a sequence of gates from a universal set, typically one which a quantum computer can implement both efficiently and fault-tolerantly. As physical implementations of quantum computers improve, the need is growing for tools that can effectively synthesize components of the circuits and algorithms they will run. Existing algorithms for exact, multi-qubit circuit synthesis scale exponentially in the number of qubits and circuit depth, leaving synthesis intractable for circuits on more than a handful of qubits. Even modest improvements in circuit synthesis procedures may lead to significant advances, pushing forward the boundaries of not only the size of solvable circuit synthesis problems, but also in what can be realized physically as a result of having more efficient circuits. We present a method for quantum circuit synthesis using deterministic walks. Also termed pseudorandom walks, these are walks in which once a starting point is chosen, its path is completely determined. We apply our method to construct a parallel framework for circuit synthesis, and implement one such version performing optimal T-count synthesis over the Clifford+T gate set. We use our software to present examples where parallelization offers a significant speedup on the runtime, as well as directly confirm that the 4-qubit 1-bit full adder has optimal T-count 7 and T-depth 3.

  9. Complete, Programmable Decoding of Oxidized 5-Methylcytosine Nucleobases in DNA by Chemoselective Blockage of Universal Transcription-Activator-Like Effector Repeats.

    PubMed

    Gieß, Mario; Witte, Anna; Jasper, Julia; Koch, Oliver; Summerer, Daniel

    2018-05-09

    5-Methylcytosine (5mC) and its oxidized derivatives are regulatory elements of mammalian genomes involved in development and disease. These nucleobases do not selectively modulate Watson-Crick pairing, preventing their programmable targeting and analysis by traditional hybridization probes. Transcription-activator-like effectors (TALEs) can be engineered for use as programmable probes with epigenetic nucleobase selectivity. However, only partial selectivities for oxidized 5mC have been achieved so far, preventing unambiguous target binding. We overcome this limitation by destroying and re-inducing nucleobase selectivity in TALEs via protein engineering and chemoselective nucleobase blocking. We engineer cavities in TALE repeats and identify a cavity that accommodates all eight human DNA nucleobases. We then introduce substituents with varying size, flexibility, and branching degree at each oxidized 5mC. Depending on the nucleobase, substituents with distinct properties effectively block TALE-binding and induce full nucleobase selectivity in the universal repeat. Successful transfer to affinity enrichment in a human genome background indicates that this approach enables the fully selective detection of each oxidized 5mC in complex DNA by programmable probes.

  10. Efficient synthesis of anacardic acid analogues and their antibacterial activities.

    PubMed

    Mamidyala, Sreeman K; Ramu, Soumya; Huang, Johnny X; Robertson, Avril A B; Cooper, Matthew A

    2013-03-15

    Anacardic acid derivatives exhibit a broad range of biological activities. In this report, an efficient method for the synthesis of anacardic acid derivatives was explored, and a small set of salicylic acid variants synthesised retaining a constant hydrophobic element (a naphthyl tail). The naphthyl side chain was introduced via Wittig reaction and the aldehyde installed using directed ortho-metalation reaction of the substituted o-anisic acids. The failure of ortho-metalation using unprotected carboxylic acid group compelled us to use directed ortho-metalation in which a tertiary amide was used as a strong ortho-directing group. In the initial route, tertiary amide cleavage during final step was challenging, but cleaving the tertiary amide before Wittig reaction was beneficial. The Wittig reaction with protected carboxylic group (methyl ester) resulted in side-products whereas using sodium salt resulted in higher yields. The novel compounds were screened for antibacterial activity and cytotoxicity. Although substitution on the salicylic head group enhanced antibacterial activities they also enhanced cytotoxicity. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. Facile synthesis of semi-library of low charge density cationic polyesters from poly(alkylene maleate)s for efficient local gene delivery.

    PubMed

    Yan, Huijie; Zhu, Dingcheng; Zhou, Zhuxian; Liu, Xin; Piao, Ying; Zhang, Zhen; Liu, Xiangrui; Tang, Jianbin; Shen, Youqing

    2018-03-30

    Cationic polymers are one of the main non-viral vectors for gene therapy, but their applications are hindered by the toxicity and inefficient transfection, particularly in the presence of serum or other biological fluids. While rational design based on the current understanding of gene delivery process has produced various cationic polymers with improved overall transfection, high-throughput parallel synthesis of libraries of cationic polymers seems a more effective strategy to screen out efficacious polymers. Herein, we demonstrate a novel platform for parallel synthesis of low cationic charge-density polyesters for efficient gene delivery. Unsaturated polyester poly(alkylene maleate) (PAM) readily underwent Michael-addition reactions with various mercaptamines to produce polyester backbones with pendant amine groups, poly(alkylene maleate mercaptamine)s (PAMAs). Variations of the alkylenes in the backbone and the mercaptamines on the side chain produced PAMAs with tunable hydrophobicity and DNA-condensation ability, the key parameters dominating transfection efficiency of the resulting polymer/DNA complexes (polyplexes). A semi-library of such PAMAs was exampled from 7 alkylenes and 18 mercaptamines, from which a lead PAMA, G-1, synthesized from poly(1,4-phenylene bis(methylene) maleate) and N,N-dimethylcysteamine, showed remarkable transfection efficiency even in the presence of serum, owing to its efficient lysosome-circumventing cellular uptake. Furthermore, G-1 polyplexes efficiently delivered the suicide gene pTRAIL to intraperitoneal tumors and elicited effective anticancer activity. Copyright © 2018 Elsevier Ltd. All rights reserved.

  12. Protecting‐Group‐Free Amidation of Amino Acids using Lewis Acid Catalysts

    PubMed Central

    Sabatini, Marco T.; Karaluka, Valerija; Lanigan, Rachel M.; Boulton, Lee T.; Badland, Matthew

    2018-01-01

    Abstract Amidation of unprotected amino acids has been investigated using a variety of ‘classical“ coupling reagents, stoichiometric or catalytic group(IV) metal salts, and boron Lewis acids. The scope of the reaction was explored through the attempted synthesis of amides derived from twenty natural, and several unnatural, amino acids, as well as a wide selection of primary and secondary amines. The study also examines the synthesis of medicinally relevant compounds, and the scalability of this direct amidation approach. Finally, we provide insight into the chemoselectivity observed in these reactions. PMID:29505683

  13. An efficient and highly stereoselective synthesis of new P-chiral 1,5-diphosphanylferrocene ligands and their use in enantioselective hydrogenation.

    PubMed

    Chen, Weiping; Roberts, J Stanley M; Whittall, John; Steiner, Alexander

    2006-07-21

    An efficient and highly stereoselective synthesis of P-chiral 1,5-diphosphanylferrocene ligands has been developed, and the introduction of P-chirality in ferrocene-based phosphine ligands enhances the enantioselective discrimination produced by the corresponding catalyst when matching of the planar chirality, the chirality at carbon and the chirality at phosphorus occurs.

  14. Precursor-Based Synthesis of Porous Colloidal Particles towards Highly Efficient Catalysts.

    PubMed

    Zheng, Yun; Geng, Hongbo; Zhang, Yufei; Chen, Libao; Li, Cheng Chao

    2018-04-02

    In recent years, porous colloidal particles have found promising applications in catalytic fields, such as photocatalysis, electrocatalysis, industrial and automotive byproducts removal, as well as biomass upgrading. These applications are critical for alleviating the energy crisis and environmental pollution. Porous colloidal particles have remarkable specific areas and abundant reactive sites, which can significantly improve the mass/charge transport and reaction rate in catalysis. Precursor-based synthesis is among the most facile and widely-adopted methods to achieve monodisperse and homogeneous porous colloidal particles. In the current review, we briefly introduce the general catalytic applications of porous colloidal particles. The conventional precursor-based methods are reviewed to design state-of-the-art porous colloidal particles as highly efficient catalysts. The recent development of porous colloidal particles derived from metal-organic frameworks (MOFs), glycerates, carbonate precursors, and ion exchange methods are reviewed. In the end, the current concerns and future development of porous colloidal particles are outlined. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Gold nanoparticles supported on titanium dioxide: an efficient catalyst for highly selective synthesis of benzoxazoles and benzimidazoles.

    PubMed

    Tang, Lin; Guo, Xuefeng; Yang, Yu; Zha, Zhenggen; Wang, Zhiyong

    2014-06-11

    A highly efficient and selective reaction for the synthesis of 2-substituted benzoxazoles and benzimidazoles catalyzed by Au/TiO2 has been developed via two hydrogen-transfer processes. This reaction has a good tolerance to air and water, a wide substrate scope, and represents a new avenue for practical C-N and C-O bond formation. More importantly, no additional additives, oxidants and reductants are required for the reaction and the catalyst can be recovered and reused readily.

  16. Iron- and cobalt-catalyzed arylation of azetidines, pyrrolidines, and piperidines with Grignard reagents.

    PubMed

    Barré, Baptiste; Gonnard, Laurine; Campagne, Rémy; Reymond, Sébastien; Marin, Julien; Ciapetti, Paola; Brellier, Marie; Guérinot, Amandine; Cossy, Janine

    2014-12-05

    Iron- and cobalt-catalyzed cross-couplings between iodo-azetidines, -pyrrolidines, -piperidines, and Grignard reagents are disclosed. The reaction is efficient, cheap, chemoselective and tolerates a large variety of (hetero)aryl Grignard reagents.

  17. A Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols

    PubMed Central

    Hoover, Jessica M.; Stahl, Shannon S.

    2011-01-01

    Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O2 as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)CuI/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups. PMID:21861488

  18. Efficient Extracellular Expression of Metalloprotease for Z-Aspartame Synthesis.

    PubMed

    Zhu, Fucheng; Liu, Feng; Wu, Bin; He, Bingfang

    2016-12-28

    Metalloprotease PT121 and its mutant Y114S (Tyr114 was substituted to Ser) are effective catalysts for the synthesis of Z-aspartame (Z-APM). This study presents the selection of a suitable signal peptide for improving expression and extracellular secretion of proteases PT121 and Y114S by Escherichia coli. Co-inducers containing IPTG and arabinose were used to promote protease production and cell growth. Under optimal conditions, the expression levels of PT121 and Y114S reached >500 mg/L, and the extracellular activity of PT121/Y114S accounted for 87/82% of the total activity of proteases. Surprisingly, purer protein was obtained in the supernatant, because arabinose reduced cell membrane permeability, avoiding cell lysis. Comparison of Z-APM synthesis and caseinolysis between proteases PT121 and Y114S showed that mutant Y114S presented remarkably higher activity of Z-APM synthesis and considerably lower activity of caseinolysis. The significant difference in substrate specificity renders these enzymes promising biocatalysts.

  19. Copper-catalyzed transformation of ketones to amides via C(CO)-C(alkyl) bond cleavage directed by picolinamide.

    PubMed

    Ma, Haojie; Zhou, Xiaoqiang; Zhan, Zhenzhen; Wei, Daidong; Shi, Chong; Liu, Xingxing; Huang, Guosheng

    2017-09-13

    Copper catalyzed chemoselective cleavage of the C(CO)-C(alkyl) bond leading to C-N bond formation with chelation assistance of N-containing directing groups is described. Inexpensive Cu(ii)-acetate serves as a convenient catalyst for this transformation. This method highlights the emerging strategy to transform unactivated alkyl ketones into amides in organic synthesis and provides a new strategy for C-C bond cleavage.

  20. Chemo- and Diastereoselective N-Heterocyclic Carbene-Catalyzed Cross-Benzoin Reactions Using N-Boc-α-amino Aldehydes.

    PubMed

    Haghshenas, Pouyan; Gravel, Michel

    2016-09-16

    N-Boc-α-amino aldehydes are shown to be excellent partners in cross-benzoin reactions with aliphatic or heteroaromatic aldehydes. The chemoselectivity of the reaction and the facial selectivity on the amino aldehyde allow cross-benzoin products to be obtained in good yields and good diastereomeric ratios. The developed method is utilized as the key step in a concise total synthesis of d-arabino-phytosphingosine.

  1. Formation of benzo[f]-1-indanone frameworks by regulable intramolecular annulations of gem-dialkylthio trienynes.

    PubMed

    Fang, Zhongxue; Liu, Ying; Barry, Badru-Deen; Liao, Peiqiu; Bi, Xihe

    2015-02-20

    An atom-economic route to benzo[f]-1-indanone frameworks has been developed starting from the readily available gem-dialkylthio trienynes by intramolecular annulations. The chemoselectivity of the intramolecular cyclizations can be regulated by both the base and the type of gas atmosphere used in the reaction, thus allowing the divergent synthesis of the corresponding functionalized benzo[f]-1-indanones in good to excellent yields.

  2. (18)F-Fluoroglucosylation of peptides, exemplified on cyclo(RGDfK).

    PubMed

    Hultsch, Christina; Schottelius, Margret; Auernheimer, Jörg; Alke, Andrea; Wester, Hans-Jürgen

    2009-09-01

    Oxime formation between an aminooxy-functionalized peptide and an (18)F-labelled aldehyde has recently been introduced as a powerful method for the rapid one-step chemoselective synthesis of radiofluorinated peptides. Here, the potential of using routinely produced and thus readily available [(18)F]fluorodeoxyglucose ([(18)F]FDG) as the aldehydic prosthetic group was investigated using an aminooxyacetyl-conjugated cyclic RGD peptide (cyclo(RGDfK(Aoa-(Boc)) as a model peptide. The use of [(18)F]FDG from routine production ([(18)F]FDGTUM) containing an excess of D: -glucose did not allow the radiosynthesis of [(18)F]FDG-RGD in activities >37 MBq in reasonable yield, rendering the direct use of clinical grade [(18)F]FDG for the routine clinical synthesis of (18)F-labelled peptides impossible. Using no-carrier-added (n.c.a.) [(18)F]FDG obtained via HPLC separation of [(18)F]FDGTUM from excess glucose, however, afforded [(18)F]FDG-RGD in yields of 56-93% (decay corrected) and activities up to 37 MBq. Suitable reaction conditions were 20 min at 120 degrees C and pH 2.5, and a peptide concentration of 5 mM. In a preliminary in vivo biodistribution study in M21 melanoma-bearing nude mice, [(18)F]FDG-RGD showed increased tumour accumulation compared to the "gold standard" [(18)F]galacto-RGD (2.18 vs 1.49 %iD/g, respectively, at 120 min after injection), but also slightly increased uptake in non-target organs, leading to comparable tumour/organ ratios for both compounds. These data demonstrate that chemoselective (18)F-labelling of aminooxy-functionalized peptides using n.c.a. [(18)F]FDG represents a radiofluorination/glycosylation strategy that allows preparation of (18)F-labelled peptides in high yield with suitable pharmacokinetics. As soon as the necessary n.c.a. preparation of [(18)F]FDG prior to reaction with the Aoa-peptide can be implemented in a fully automated [(18)F]FDG-synthesis, [(18)F]fluoroglucosylation of peptides may represent a promising alternative to

  3. Synthesis of mimics of pramanicin from pyroglutamic acid and their antibacterial activity.

    PubMed

    Tan, Song Wei Benjamin; Chai, Christina L L; Moloney, Mark G; Thompson, Amber L

    2015-03-06

    Epoxypyrrolidinones are available by epoxidation of carboxamide-activated bicyclic lactam substrates derived from pyroglutamate using aqueous hydrogen peroxide and tertiary amine catalysis. In the case of an activating Weinreb carboxamide, further chemoselective elaboration leads to the efficient formation of libraries of epoxyketones. Deprotection may be achieved under acidic conditions to give epoxypyroglutaminols, although the ease of this process can be ameliorated by the presence of internal hydrogen bonding. Bioassay against S. aureus and E. coli indicated that some compounds exhibit antibacterial activity. These libraries may be considered to be structural mimics of the natural products pramanicin and epolactaene. More generally, this outcome suggests that interrogation of bioactive natural products is likely to permit the identification of "privileged" structural scaffolds, providing frameworks suitable for optimization in a short series of chemical steps that may accelerate the discovery of new antibiotic chemotypes. Further optimization of such systems may permit the rapid identification of novel systems suitable for antibacterial drug development.

  4. Multiple epitope presentation and surface density control enabled by chemoselective immobilization lead to enhanced performance in IgE-binding fingerprinting on peptide microarrays.

    PubMed

    Gori, Alessandro; Cretich, Marina; Vanna, Renzo; Sola, Laura; Gagni, Paola; Bruni, Giulia; Liprino, Marta; Gramatica, Furio; Burastero, Samuele; Chiari, Marcella

    2017-08-29

    Multiple ligand presentation is a powerful strategy to enhance the affinity of a probe for its corresponding target. A promising application of this concept lies in the analytical field, where surface immobilized probes interact with their corresponding targets in the context of complex biological samples. Here we investigate the effect of multiple epitope presentation (MEP) in the challenging context of IgE-detection in serum samples using peptide microarrays, and evaluate the influence of probes surface density on the assay results. Using the milk allergen alpha-lactalbumin as a model, we have synthesized three immunoreactive epitope sequences in a linear, branched and tandem form and exploited a chemoselective click strategy (CuAAC) for their immobilization on the surface of two biosensors, a microarray and an SPR chip both modified with the same clickable polymeric coating. We first demonstrated that a fine tuning of the surface peptide density plays a crucial role to fully exploit the potential of oriented and multiple peptide display. We then compared the three multiple epitope presentations in a microarray assay using sera samples from milk allergic patients, confirming that a multiple presentation, in particular that of the tandem construct, allows for a more efficient characterization of IgE-binding fingerprints at a statistically significant level. To gain insights on the binding parameters that characterize antibody/epitopes affinity, we selected the most reactive epitope of the series (LAC1) and performed a Surface Plasmon Resonance Imaging (SPRi) analysis comparing different epitope architectures (linear versus branched versus tandem). We demonstrated that the tandem peptide provides an approximately twofold increased binding capacity with respect to the linear and branched peptides, that could be attributed to a lower rate of dissociation (K d ). Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Synthesis of Colloidal Nanocrystal Heterostructures for High-Efficiency Light Emission

    NASA Astrophysics Data System (ADS)

    Lu, Yifei

    Group II-VI semiconductor nanocrystals, particularly those based on ZnCdS(Se), can be synthesized using well established chemical colloidal processes, and have been a subject of extensive research over the past decade. Their optical properties can be easily tuned through size and composition variations, making them very attractive for many optoelectronic applications including light-emitting diodes (LEDs) and solar cells. Incorporation of diverse internal heterostructures provides an additional means for tuning the optical and electronic properties of conventional ZnCdS(Se) nanocrystals. Extensive bandgap and strain engineering may be applied to the resultant nanocrystal heterostructures to achieve desirable properties and enhanced performance. Despite the high scientific and practical interests of this unique class of nanomaterials, limited efforts have been made to explore their synthesis and potential device applications. This thesis focuses on the synthesis, engineering, characterization, and device demonstration of two types of CdSe-based nanocrystal heterostructures: core/multishell quantum dots (QDs) and QD quantum wells (QDQWs). Their optical properties have been tuned by bandgap and strain engineering to achieve efficient photoluminescence (PL) and electroluminescence (EL).Firstly, yellow light-emitting CdSe QDs with a strain-compensated ZnS/ZnCdS bilayer shell were synthesized using the successive ion layer adsorption and reaction technique and the effects of the shell on the luminescent properties were investigated. The core/shell/shell QDs enjoyed the benefits of excellent exciton confinement by the ZnS intermediate shell and strain compensation by the ZnCdS outer shell, and exhibited 40% stronger PL and a smaller peak redshift upon shell growth compared to conventional CdSe/ZnCdS/ZnS core/shell/shell QDs with an intermediate lattice adaptor. CdSe/ZnS/ZnCdS QD-LEDs had a luminance of 558 cd/m2 at 20 mA/cm 2, 28% higher than that of CdSe/ZnCdS/ZnS QD

  6. Electron-transfer-initiated benzoin- and Stetter-like reactions in packed-bed reactors for process intensification.

    PubMed

    Zaghi, Anna; Ragno, Daniele; Di Carmine, Graziano; De Risi, Carmela; Bortolini, Olga; Giovannini, Pier Paolo; Fantin, Giancarlo; Massi, Alessandro

    2016-01-01

    A convenient heterogeneous continuous-flow procedure for the polarity reversal of aromatic α-diketones is presented. Propaedeutic batch experiments have been initially performed to select the optimal supported base capable to initiate the two electron-transfer process from the carbamoyl anion of the N , N -dimethylformamide (DMF) solvent to the α-diketone and generate the corresponding enediolate active species. After having identified the 2- tert -butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine on polystyrene (PS-BEMP) as the suitable base, packed-bed microreactors (pressure-resistant stainless-steel columns) have been fabricated and operated to accomplish the chemoselective synthesis of aroylated α-hydroxy ketones and 2-benzoyl-1,4-diones (benzoin- and Stetter-like products, respectively) with a good level of efficiency and with a long-term stability of the packing material (up to five days).

  7. Electron-transfer-initiated benzoin- and Stetter-like reactions in packed-bed reactors for process intensification

    PubMed Central

    Zaghi, Anna; Ragno, Daniele; Di Carmine, Graziano; De Risi, Carmela; Bortolini, Olga; Giovannini, Pier Paolo; Fantin, Giancarlo

    2016-01-01

    A convenient heterogeneous continuous-flow procedure for the polarity reversal of aromatic α-diketones is presented. Propaedeutic batch experiments have been initially performed to select the optimal supported base capable to initiate the two electron-transfer process from the carbamoyl anion of the N,N-dimethylformamide (DMF) solvent to the α-diketone and generate the corresponding enediolate active species. After having identified the 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine on polystyrene (PS-BEMP) as the suitable base, packed-bed microreactors (pressure-resistant stainless-steel columns) have been fabricated and operated to accomplish the chemoselective synthesis of aroylated α-hydroxy ketones and 2-benzoyl-1,4-diones (benzoin- and Stetter-like products, respectively) with a good level of efficiency and with a long-term stability of the packing material (up to five days). PMID:28144342

  8. Chemoselective Deprotection of Triethylsilyl Ethers

    PubMed Central

    Chandra, Tilak; Broderick, William E.; Broderick, Joan B.

    2009-01-01

    An efficient and selective method was developed for the deprotection of triethylsilyl (TES) ethers using formic acid in methanol (5–10%) or in methylene chloride 2–5%) with excellent yields. TES ethers are selectively deprotected to the corresponding alcohols in high yields using formic acid in methanol under mild reaction conditions. Other hydroxyl protecting groups like t-butyldimethylsilyl (TBDMS) remain unaffected. PMID:20183570

  9. Flow “Fine” Synthesis: High Yielding and Selective Organic Synthesis by Flow Methods

    PubMed Central

    2015-01-01

    Abstract The concept of flow “fine” synthesis, that is, high yielding and selective organic synthesis by flow methods, is described. Some examples of flow “fine” synthesis of natural products and APIs are discussed. Flow methods have several advantages over batch methods in terms of environmental compatibility, efficiency, and safety. However, synthesis by flow methods is more difficult than synthesis by batch methods. Indeed, it has been considered that synthesis by flow methods can be applicable for the production of simple gasses but that it is difficult to apply to the synthesis of complex molecules such as natural products and APIs. Therefore, organic synthesis of such complex molecules has been conducted by batch methods. On the other hand, syntheses and reactions that attain high yields and high selectivities by flow methods are increasingly reported. Flow methods are leading candidates for the next generation of manufacturing methods that can mitigate environmental concerns toward sustainable society. PMID:26337828

  10. “Click, Click, Cyclize”: A DOS Approach to Sultams Utilizing Vinyl Sulfonamide Linchpins

    PubMed Central

    Zhou, Aihua; Rayabarapu, Dinesh; Hanson, Paul R.

    2009-01-01

    A diversity-oriented synthesis (DOS) strategy termed “Click, Click, Cyclize” is reported. This approach relies on functional group (FG) pairing between a vinyl sulfonamide and an array of functional groups to synthesize skeletally diverse sultams. Several FG pairing pathways on central tertiary vinyl sulfonamide linchpins have been developed including intramolecular Heck, aza-Michael, ring-closing enyne metathesis, Pauson—Khand, and chemoselective oxidation/Baylis—Hillman reactions. PMID:19115841

  11. Institute for Atom-Efficient Chemical Transformations Energy Frontier

    Science.gov Websites

    Synthesis Search Argonne ... Search Argonne Home > Institute for Atom-Efficient Chemical Transformations Synthesis Characterization Computational Studies Evaluation and Mechanisms/Catalytic Experimentation Using

  12. A Facile Synthesis of Nitrogen-Doped Highly Porous Carbon Nanoplatelets: Efficient Catalysts for Oxygen Electroreduction

    NASA Astrophysics Data System (ADS)

    Zhang, Yaqing; Zhang, Xianlei; Ma, Xiuxiu; Guo, Wenhui; Wang, Chunchi; Asefa, Tewodros; He, Xingquan

    2017-02-01

    The oxygen reduction reaction (ORR) is of great importance for various renewable energy conversion technologies such as fuel cells and metal-air batteries. Heteroatom-doped carbon nanomaterials have proven to be robust metal-free electrocatalysts for ORR in the above-mentioned energy devices. Herein, we demonstrate the synthesis of novel highly porous N-doped carbon nanoplatelets (N-HPCNPs) derived from oatmeal (or a biological material) and we show the materials’ high-efficiency as electrocatalyst for ORR. The obtained N-HPCNPs hybrid materials exhibit superior electrocatalytic activities towards ORR, besides excellent stability and good methanol tolerance in both basic and acidic electrolytes. The unique nanoarchitectures with rich micropores and mesopores, as well as the high surface area-to-volume ratios, present in the materials significantly increase the density of accessible catalytically active sites in them and facilitate the transport of electrons and electrolyte within the materials. Consequently, the N-HPCNPs catalysts hold a great potential to serve as low-cost and highly efficient cathode materials in direct methanol fuel cells (DMFCs).

  13. Efficient synthesis and evaluation of bis-pyridinium/bis-quinolinium metallosalophens as antibiotic and antitumor candidates

    NASA Astrophysics Data System (ADS)

    Elshaarawy, Reda F. M.; Eldeen, Ibrahim M.; Hassan, Eman M.

    2017-01-01

    Inspired with the pharmacological diversity of salophens and in our endeavor to explore a new strategy which may conflict the invasion of drug resistance, we report herein efficient synthetic routes for the synthesis of new RO-salophen(Cl), pyridinium/quinolinium-based salophens (3a-e) and metallosalophens (4a-j). These new architectures have been structurally characterized by elemental and spectral analysis as well pharmacologically evaluated for their in vitro antimicrobial, against a common panel of pathogenic bacterial and fungal strains, and anticancer activities against human colon carcinoma (HCT-116) cell lines. Antimicrobial assay results revealed that all tested compounds exhibited moderate to superb broad-spectrum efficacy in comparison to the standard antibiotic with a preferential ability to perform as a fungicides than to act as bactericides. Noteworthy, VO(II)-salophens are more effective in reduction HCT-116 cell viability than Cu(II)-salophens. For example, VO(II)-salophen3 (4f) (IC50 = 2.13 μg/mL) was ca. 10-fold more efficient than Cu(II)-salophen3 (4e) (IC50 = 20.30 μg/mL).

  14. Enantioselective syntheses of lignin models: an efficient synthesis of B-O-4 dimers and trimers by using the Evans chiral auxiliary

    Treesearch

    Costyl N. Njiojob; Joseph J. Bozell; Brian K. Long; Thomas Elder; Rebecca E. Key; William T. Hartwig

    2016-01-01

    We describe an efficient five-step, enantioselective synthesis of (R,R)- and (S,S)-lignin dimer models possessing a B-O-4 linkage, by using the Evans chiral aldol reaction as a key step. Mitsunobu inversion of the (R,R)- or (S,S)-isomers generates the corresponding (R,S)- and (S,R)-diastereomers. We further extend this approach to the...

  15. Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: optimum catalyst combinations and their substrate scope.

    PubMed

    Sasano, Yusuke; Kogure, Naoki; Nishiyama, Tomohiro; Nagasawa, Shota; Iwabuchi, Yoshiharu

    2015-04-01

    The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis.

    PubMed

    Nguyen, Thach T; Koh, Ming Joo; Mann, Tyler J; Schrock, Richard R; Hoveyda, Amir H

    2017-12-20

    Catalytic cross-metathesis is a central transformation in chemistry, yet corresponding methods for the stereoselective generation of acyclic trisubstituted alkenes in either the E or the Z isomeric forms are not known. The key problems are a lack of chemoselectivity-namely, the preponderance of side reactions involving only the less hindered starting alkene, resulting in homo-metathesis by-products-and the formation of short-lived methylidene complexes. By contrast, in catalytic cross-coupling, substrates are more distinct and homocoupling is less of a problem. Here we show that through cross-metathesis reactions involving E- or Z-trisubstituted alkenes, which are easily prepared from commercially available starting materials by cross-coupling reactions, many desirable and otherwise difficult-to-access linear E- or Z-trisubstituted alkenes can be synthesized efficiently and in exceptional stereoisomeric purity (up to 98 per cent E or 95 per cent Z). The utility of the strategy is demonstrated by the concise stereoselective syntheses of biologically active compounds, such as the antifungal indiacen B and the anti-inflammatory coibacin D.

  17. Efficient synthesis of highly fluorescent carbon dots by microreactor method and their application in Fe3+ ion detection.

    PubMed

    Rao, Longshi; Tang, Yong; Li, Zongtao; Ding, Xinrui; Liang, Guanwei; Lu, Hanguang; Yan, Caiman; Tang, Kairui; Yu, Binhai

    2017-12-01

    Rapidly obtaining strong photoluminescence (PL) of carbon dots with high stability is crucial in all practical applications of carbon dots, such as cell imaging and biological detection. In this study, we proposed a rapid, continuous carbon dots synthesis technique by using a microreactor method. By taking advantage of the microreactor, we were able to rapidly synthesized CDs at a large scale in less than 5min, and a high quantum yield of 60.1% was achieved. This method is faster and more efficient than most of the previously reported methods. To explore the relationship between the microreactor structure and CDs PL properties, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were carried out. The results show the surface functional groups and element contents influence the PL emission. Subsequent ion detection experiments indicated that CDs are very suitable for use as nanoprobes for Fe 3+ ion detection, and the lowest detection limit for Fe 3+ is 0.239μM, which is superior to many other research studies. This rapid and simple synthesis method will not only aid the development of the quantum dots industrialization but also provide a powerful and portable tool for the rapid and continuous online synthesis of quantum dots supporting their application in cell imaging and safety detection. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Selective synthesis of vitamin K3 over mesoporous NbSBA-15 catalysts synthesized by an efficient hydrothermal method.

    PubMed

    Selvaraj, M; Park, D-W; Kim, I; Kawi, S; Ha, C S

    2012-08-28

    Well hexagonally ordered NbSBA-15 catalysts synthesized by an efficient hydrothermal method were used, for the first time, for the selective synthesis of vitamin K(3) by liquid-phase oxidation of 2-methyl-1-naphthol (2MN1-OH) under various reaction conditions. The recyclable NbSBA-15 catalysts were also reused to find their catalytic activities. To investigate the leaching of non-framework niobium species on the surface of silica networks, the results of original and recyclable NbSBA-15 catalysts were correlated and compared. To find an optimum condition for the selective synthesis of vitamin K(3), the washed NbSBA-15(2.2pH) was extensively used in this reaction with various reaction parameters such as temperature, time and ratios of reactant (2M1N-OH to H(2)O(2)), and the obtained results were also demonstrated. Additionally, the liquid-phase oxidation of 2M1N-OH was carried out with different solvents to find the best solvent with a good catalytic activity. Based on the all catalytic studies, the vitamin K(3) selectivity (97.3%) is higher in NbSBA-15(2.2pH) than that of other NbSBA-15 catalysts, and the NbSBA-15(2.2pH) is found to be a highly active and eco-friendly heterogeneous catalyst for the selective synthesis of vitamin K(3).

  19. Substitution of the nitro group with Grignard reagents: facile arylation and alkenylation of pyridine N-oxides.

    PubMed

    Zhang, Fang; Zhang, Song; Duan, Xin-Fang

    2012-11-02

    The unprecedented substitution of a nitro group with aryl or alkenyl groups of Grignard reagents affords 2-aryl or alkenylpyridine N-oxides in modest to high yields with high chemoselectivity. This protocol allows a simple and clean synthesis of various 2-substituted pyridine N-oxides and the corresponding pyridine derivatives. Furthermore, straightforward one-pot iterative functionality of pyridine N-oxides could also be achieved simply by successive applications of two Grignard reagents.

  20. Complete regioselective addition of grignard reagents to pyrazine N-oxides, toward an efficient enantioselective synthesis of substituted piperazines.

    PubMed

    Andersson, Hans; Banchelin, Thomas Sainte-Luce; Das, Sajal; Gustafsson, Magnus; Olsson, Roger; Almqvist, Fredrik

    2010-01-15

    A conceptually new one-pot strategy for the synthesis of protected substituted piperazines via the addition of Grignard reagents to pyrazine N-oxides is presented. This strategy is high yielding (33-91% over three steps), step-efficient, and fast. The synthesized N,N-diprotected piperazines are convenient to handle and allow for orthogonal deprotection at either nitrogen for selective transformations. In addition, this is a synthetic route to enantiomerically enriched piperazines by using a combination of phenyl magnesium chloride and (-)-sparteine, which resulted in enantiomeric excesses up to 83%.

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

    PubMed

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

    2014-02-24

    An efficient synthesis of N-substituted indole derivatives was realized by combining the Pd-catalyzed one-pot multicomponent coupling approach with cleavage of the C(sp(3))-N bonds. Three or four components of aryl iodides, alkynes, and amines were involved in this coupling process. The cyclopentadiene-phosphine ligand showed high efficiency. A variety of aryl iodides, including cyclic and acyclic tertiary amino aryl iodides, and substituted 1-bromo-2-iodobenzene derivatives could be used. Both symmetric and unsymmetric alkynes substituted with alkyl, aryl, or trimethylsilyl groups could be applied. Cyclic secondary amines such as piperidine, morpholine, 4-methylpiperidine, 1-methylpiperazine, 2-methylpiperidine, and acyclic amines including secondary and primary amines all showed good reactivity. Further application of the resulting indole derivatives was demonstrated by the synthesis of benzosilolo[2,3-b]indole. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis of amino-rich silica-coated magnetic nanoparticles for the efficient capture of DNA for PCR.

    PubMed

    Bai, Yalong; Cui, Yan; Paoli, George C; Shi, Chunlei; Wang, Dapeng; Zhou, Min; Zhang, Lida; Shi, Xianming

    2016-09-01

    Magnetic separation has great advantages over traditional bio-separation methods and has become popular in the development of methods for the detection of bacterial pathogens, viruses, and transgenic crops. Functionalization of magnetic nanoparticles is a key factor for efficient capture of the target analytes. In this paper, we report the synthesis of amino-rich silica-coated magnetic nanoparticles using a one-pot method. This type of magnetic nanoparticle has a rough surface and a higher density of amino groups than the nanoparticles prepared by a post-modification method. Furthermore, the results of hydrochloric acid treatment indicated that the magnetic nanoparticles were stably coated. The developed amino-rich silica-coated magnetic nanoparticles were used to directly adsorb DNA. After magnetic separation and blocking, the magnetic nanoparticles and DNA complexes were used directly for the polymerase chain reaction (PCR), without onerous and time-consuming purification and elution steps. The results of real-time quantitative PCR showed that the nanoparticles with higher amino group density resulted in improved DNA capture efficiency. The results suggest that amino-rich silica-coated magnetic nanoparticles are of great potential for efficient bio-separation of DNA prior to detection by PCR. Copyright © 2016. Published by Elsevier B.V.

  3. Highly regioselective Lewis acid-catalyzed [3+2] cycloaddition of alkynes with donor-acceptor oxiranes by selective carbon-carbon bond cleavage of epoxides.

    PubMed

    Liu, Renrong; Zhang, Mei; Zhang, Junliang

    2011-12-28

    A novel, efficient, highly regioselective Sc(OTf)(3)-catalyzed [3+2] cycloaddition of electron-rich alkynes with donor-acceptor oxiranes via highly chemoselective C-C bond cleavage under mild conditions was developed. This journal is © The Royal Society of Chemistry 2011

  4. Bi-template assisted synthesis of mesoporous manganese oxide nanostructures: Tuning properties for efficient CO oxidation.

    PubMed

    Roy, Mouni; Basak, Somjyoti; Naskar, Milan Kanti

    2016-02-21

    A simple soft bi-templating process was used for the synthesis of mesoporous manganese oxide nanostructures using KMnO4 as a precursor and polyethylene glycol and cetyltrimethylammonium bromide as templates in the presence of benzaldehyde as an organic additive in alkaline media, followed by calcination at 400 °C. X-ray diffraction and Raman spectroscopic analysis of the calcined products confirmed the existence of stoichiometric (MnO2 and Mn5O8) and non-stoichiometric mixed phases (MnO2 + Mn5O8) of Mn oxides obtained by tuning the concentration of the additive and the synthesis time. The surface properties of the prepared Mn oxides were determined by X-ray photoelectron spectroscopy. The mesoporosity of the samples was confirmed by N2 adsorption-desorption. Different synthetic conditions resulted in the formation of different morphologies of the Mn oxides (α-MnO2, Mn5O8, and α-MnO2 + Mn5O8), such as nanoparticles, nanorods, and nanowires. The synthesized mesoporous Mn oxide nanostructures were used for the catalytic oxidation of the harmful air pollutant carbon monoxide. The Mn5O8 nanoparticles with the highest Brunauer-Emmett-Teller surface area and the non-stoichiometric manganese oxide (α-MnO2 + Mn5O8) nanorods with a higher Mn(3+) concentration had the best catalytic efficiency.

  5. Nitric Oxide Regulates Skeletal Muscle Fatigue, Fiber Type, Microtubule Organization, and Mitochondrial ATP Synthesis Efficiency Through cGMP-Dependent Mechanisms.

    PubMed

    Moon, Younghye; Balke, Jordan E; Madorma, Derik; Siegel, Michael P; Knowels, Gary; Brouckaert, Peter; Buys, Emmanuel S; Marcinek, David J; Percival, Justin M

    2017-06-10

    Skeletal muscle nitric oxide-cyclic guanosine monophosphate (NO-cGMP) pathways are impaired in Duchenne and Becker muscular dystrophy partly because of reduced nNOSμ and soluble guanylate cyclase (GC) activity. However, GC function and the consequences of reduced GC activity in skeletal muscle are unknown. In this study, we explore the functions of GC and NO-cGMP signaling in skeletal muscle. GC1, but not GC2, expression was higher in oxidative than glycolytic muscles. GC1 was found in a complex with nNOSμ and targeted to nNOS compartments at the Golgi complex and neuromuscular junction. Baseline GC activity and GC agonist responsiveness was reduced in the absence of nNOS. Structural analyses revealed aberrant microtubule directionality in GC1 -/- muscle. Functional analyses of GC1 -/- muscles revealed reduced fatigue resistance and postexercise force recovery that were not due to shifts in type IIA-IIX fiber balance. Force deficits in GC1 -/- muscles were also not driven by defects in resting mitochondrial adenosine triphosphate (ATP) synthesis. However, increasing muscle cGMP with sildenafil decreased ATP synthesis efficiency and capacity, without impacting mitochondrial content or ultrastructure. GC may represent a new target for alleviating muscle fatigue and that NO-cGMP signaling may play important roles in muscle structure, contractility, and bioenergetics. These findings suggest that GC activity is nNOS dependent and that muscle-specific control of GC expression and differential GC targeting may facilitate NO-cGMP signaling diversity. They suggest that nNOS regulates muscle fiber type, microtubule organization, fatigability, and postexercise force recovery partly through GC1 and suggest that NO-cGMP pathways may modulate mitochondrial ATP synthesis efficiency. Antioxid. Redox Signal. 26, 966-985.

  6. Biomimetically inspired asymmetric total synthesis of (+)-19-dehydroxyl arisandilactone A

    NASA Astrophysics Data System (ADS)

    Han, Yi-Xin; Jiang, Yan-Long; Li, Yong; Yu, Hai-Xin; Tong, Bing-Qi; Niu, Zhe; Zhou, Shi-Jie; Liu, Song; Lan, Yu; Chen, Jia-Hua; Yang, Zhen

    2017-01-01

    Complex natural products are a proven and rich source of disease-modulating drugs and of efficient tools for the study of chemical biology and drug discovery. The architectures of complex natural products are generally considered to represent significant barriers to efficient chemical synthesis. Here we describe a concise and efficient asymmetric synthesis of 19-dehydroxyl arisandilactone A--which belongs to a family of architecturally unique, highly oxygenated nortriterpenoids isolated from the medicinal plant Schisandra arisanensis. This synthesis takes place by means of a homo-Michael reaction, a tandem retro-Michael/Michael reaction, and Cu-catalysed intramolecular cyclopropanation as key steps. The proposed mechanisms for the homo-Michael and tandem retro-Michael/Michael reactions are supported by density functional theory (DFT) calculation. The developed chemistry may find application for the synthesis of its other family members of Schisandraceae nortriterpenoids.

  7. Combining Chemoselective Ligation with Polyhistidine-Driven Self-Assembly for the Modular Display of Biomolecules on Quantum Dots

    PubMed Central

    Prasuhn, Duane E.; Blanco-Canosa, Juan B.; Vora, Gary J.; Delehanty, James B.; Susumu, Kimihiro; Mei, Bing C.; Dawson, Philip E.; Medintz, Igor L.

    2015-01-01

    One of the principle hurdles to wider incorporation of semiconductor quantum dots (QDs) in biology is the lack of facile linkage chemistries to create different types of functional QD-bioconjugates. A two-step modular strategy for the presentation of biomolecules on CdSe/ZnS core/shell QDs is described here which utilizes a chemoselective, aniline-catalyzed hydrazone coupling chemistry to append hexahistidine sequences onto peptides and DNA. This specifically provides them the ability to ratiometrically self-assemble to hydrophilic QDs. The versatility of this labeling approach was highlighted by ligating proteolytic substrate peptides, an oligoarginine cell-penetrating peptide, or a DNA-probe to cognate hexahistidine peptidyl sequences. The modularity allowed subsequently self-assembled QD constructs to engage in different types of targeted bioassays. The self-assembly and photophysical properties of individual QD conjugates were first confirmed by gel electrophoresis and Förster resonance energy transfer analysis. QD-dye-labeled peptide conjugates were then used as biosensors to quantitatively monitor the proteolytic activity of caspase-3 or elastase enzymes from different species. These sensors allowed the determination of the corresponding kinetic parameters, including the Michaelis constant (KM) and the maximum proteolytic activity (Vmax). QDs decorated with cell-penetrating peptides were shown to be successfully internalized by HEK 293T/17 cells, while nanocrystals displaying peptide-DNA conjugates were utilized as fluorescent probes in hybridization microarray assays. This modular approach for displaying peptides or DNA on QDs may be extended to other more complex biomolecules such as proteins or utilized with different types of nanoparticle materials. PMID:20099912

  8. Efficient synthesis of gamma-lactams by a tandem reductive amination/lactamization sequence.

    PubMed

    Nöth, Julica; Frankowski, Kevin J; Neuenswander, Benjamin; Aubé, Jeffrey; Reiser, Oliver

    2008-01-01

    A three-component method for the synthesis of highly substituted gamma-lactams from readily available maleimides, aldehydes, and amines is described. A new reductive amination/intramolecular lactamization sequence provides a straightforward route to the lactam products in a single manipulation. The general utility of this method is demonstrated by the parallel synthesis of a gamma-lactam library.

  9. Simple and Efficient Generation of Aryl Radicals from Aryl Triflates: Synthesis of Aryl Boronates and Aryl Iodides at Room Temperature.

    PubMed

    Liu, Wenbo; Yang, Xiaobo; Gao, Yang; Li, Chao-Jun

    2017-06-28

    Despite the wide use of aryl radicals in organic synthesis, current methods to prepare them from aryl halides, carboxylic acids, boronic acids, and diazonium salts suffer from limitations. Aryl triflates, easily obtained from phenols, are promising aryl radical progenitors but remain elusive in this regard. Inspired by the single electron transfer process for aryl halides to access aryl radicals, we developed a simple and efficient protocol to convert aryl triflates to aryl radicals. Our success lies in exploiting sodium iodide as the soft electron donor assisted by light. This strategy enables the scalable synthesis of two types of important organic molecules, i.e., aryl boronates and aryl iodides, in good to high yields, with broad functional group compatibility in a transition-metal-free manner at room temperature. This protocol is anticipated to find potential applications in other aryl-radical-involved reactions by using aryl triflates as aryl radical precursors.

  10. Rate in template-directed polymer synthesis.

    PubMed

    Saito, Takuya

    2014-06-01

    We discuss the temporal efficiency of template-directed polymer synthesis, such as DNA replication and transcription, under a given template string. To weigh the synthesis speed and accuracy on the same scale, we propose a template-directed synthesis (TDS) rate, which contains an expression analogous to that for the Shannon entropy. Increasing the synthesis speed accelerates the TDS rate, but the TDS rate is lowered if the produced sequences are diversified. We apply the TDS rate to some production system models and investigate how the balance between the speed and the accuracy is affected by changes in the system conditions.

  11. Highly efficient solid phase synthesis of oligonucleotide analogs containing phosphorodithioate linkages

    PubMed Central

    Capaldi, Daniel C.; Cole, Douglas L.; Ravikumar, Vasulinga T.

    2000-01-01

    A triester method for the synthesis of deoxynucleoside phosphorodithioate dimers is described. The phosphorodithioate linkage is introduced using a new dithiophosphorylating reagent DPSE-SP(S)Cl2 where DPSE = 2-diphenylmethylsilylethyl. This group is removed quickly using tetra-butylammonium fluoride leading to the quantitative formation of phosphorodithioate diesters uncontaminated with the corresponding phosphorothioates. The utility of this group is demonstrated by the synthesis of a pentadecathymidylic acid, [T(PS2)T(PO2)]7T, which contains alternating phosphorodithioate/phosphate diester internucleotide linkages. PMID:10756207

  12. Highly efficient solid phase synthesis of oligonucleotide analogs containing phosphorodithioate linkages.

    PubMed

    Capaldi, D C; Cole, D L; Ravikumar, V T

    2000-05-01

    A triester method for the synthesis of deoxynucleoside phosphorodithioate dimers is described. The phosphorodithioate linkage is introduced using a new dithiophosphorylating reagent DPSE-SP(S)Cl(2)where DPSE = 2-diphenylmethylsilylethyl. This group is removed quickly using tetra-butylammonium fluoride leading to the quantitative formation of phosphorodithioate diesters uncontaminated with the corresponding phosphorothioates. The utility of this group is demonstrated by the synthesis of a penta-decathymidylic acid, [T(PS(2))T(PO(2))](7)T, which contains alternating phosphorodithioate/phosphate diester internucleotide linkages.

  13. LOGIC NETS, THEIR CHARACTERIZATION, RELIABILITY, AND EFFICIENT SYNTHESIS.

    DTIC Science & Technology

    The report consists of two parts. The first discusses a problem in the dual-support approach to network synthesis using threshold gates, gives new...asymptotic results on the number of threshold gates and the size of threshold gate networks, and summarizes the work in threshold logic supported by...this contract, including programs to facilitate experimentation in the design of networks of threshold gates. The second summarizes CDL1 - Computer

  14. Synthesis of palladium nanoparticles with leaf extract of Chrysophyllum cainito (Star apple) and their applications as efficient catalyst for C-C coupling and reduction reactions

    NASA Astrophysics Data System (ADS)

    Majumdar, Rakhi; Tantayanon, Supawan; Bag, Braja Gopal

    2017-10-01

    A simple green chemical method for the one-step synthesis of palladium nanoparticles (PdNPs) has been described by reducing palladium (II) chloride with the leaf extract of Chrysophyllum cainito in aqueous medium. The synthesis of the palladium nanoparticles completed within 2-3 h at room temperature, whereas on heat treatment (70-80 °C), the synthesis of colloidal PdNPs completed almost instantly. The stabilized PdNPs have been characterized in detail by spectroscopic, electron microscopic and light scattering measurements. The synthesized PdNPs have been utilized as a green catalyst for C-C coupling reactions under aerobic and phosphine-free conditions in aqueous medium. In addition, the synthesized PdNPs have also been utilized as a catalyst for a very efficient sodium borohydride reduction of 3- and 4-nitrophenols. The synthesized PdNPs can retain their catalytic activity for several months.

  15. Reaction of Diazo Compounds with Difluorocarbene: An Efficient Approach towards 1,1-Difluoroolefins.

    PubMed

    Zhang, Zhikun; Yu, Weizhi; Wu, Chenggui; Wang, Chengpeng; Zhang, Yan; Wang, Jianbo

    2016-01-04

    A transition-metal-free difluoromethylenation of diazo compounds that proceeds under mild conditions has been developed and is based on the use of TMSCF2 Br as the difluoromethylene source and tetrabutylammonium bromide (TBAB) as the promoter. The chemoselective formal carbene dimerization reaction is achieved owing to the electronic properties and the relative stability of the difluorocarbene intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. An efficient coupling of N-tosylhydrazones with 2-halopyridines: synthesis of 2-α-styrylpyridines endowed with antitumor activity.

    PubMed

    Lawson, Marie; Hamze, Abdallah; Peyrat, Jean-François; Bignon, Jérôme; Dubois, Joelle; Brion, Jean-Daniel; Alami, Mouad

    2013-06-14

    The synthesis of 2-α-styrylpyridines has been carried out by using the coupling of polyoxygenated N-tosylhydrazones with various 2-halopyridines. We demonstrated that the use of a catalytic amount of PdCl2(MeCN)2 in combination with a bidentate ferrocene DPPF or a monodentate alkyl phosphine (t)Bu2MeP-HBF4 constitutes an efficient protocol for this coupling, providing 2-α-styrylpyridines 2 in satisfactory to good yields. Among several polyoxygenated derivatives 2 evaluated, compound 2aa was found to exhibit excellent antiproliferative and antimitotic activities comparable to that of the reference compound isoCA-4.

  17. Synthesis of a Monophosphoryl Derivative of Escherichia coli Lipid A and Its Efficient Coupling to a Tumor-Associated Carbohydrate Antigen

    PubMed Central

    Tang, Shouchu; Wang, Qianli

    2010-01-01

    Monophosphoryl lipid A is a safe and potent immunostimulant and vaccine adjuvant, which is potentially useful for the development of effective carbohydrate-based conjugate vaccines. This paper presented a convergent and efficient synthesis of a monophosphoryl derivative of E. coli lipid A having an alkyne functionality at the reducing end, which is suitable for the coupling with various molecules. The coupling of this derivative to an N-modified analog of tumor-associated antigen GM3 by click chemistry is also presented. PMID:19943286

  18. Efficient and Selective N-Methylation of Nitroarenes under Mild Reaction Conditions.

    PubMed

    Pedrajas, Elena; Sorribes, Iván; Guillamón, Eva; Junge, Kathrin; Beller, Matthias; Llusar, Rosa

    2017-09-21

    Herein, we report a straightforward protocol for the preparation of N,N-dimethylated amines from readily available nitro starting materials using formic acid as a renewable C 1 source and silanes as reducing agents. This tandem process is efficiently accomplished in the presence of a cubane-type Mo 3 PtS 4 catalyst. For the preparation of the novel [Mo 3 Pt(PPh 3 )S 4 Cl 3 (dmen) 3 ] + (3 + ) (dmen: N,N'-dimethylethylenediamine) compound we have followed a [3+1] building block strategy starting from the trinuclear [Mo 3 S 4 Cl 3 (dmen) 3 ] + (1 + ) and Pt(PPh 3 ) 4 (2) complexes. The heterobimetallic 3 + cation preserves the main structural features of its 1 + cluster precursor. Interestingly, this catalytic protocol operates at room temperature with high chemoselectivity when the 3 + catalyst co-exists with its trinuclear 1 + precursor. N-heterocyclic arenes, double bonds, ketones, cyanides and ester functional groups are well retained after N-methylation of the corresponding functionalized nitroarenes. In addition, benzylic-type as well as aliphatic nitro compounds can also be methylated following this protocol. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Chemoselective Reactions for the Synthesis of Glycoconjugates from Unprotected Carbohydrates.

    PubMed

    Villadsen, Klaus; Martos-Maldonado, Manuel C; Jensen, Knud J; Thygesen, Mikkel B

    2017-04-04

    Glycobiology is the comprehensive biological investigation of carbohydrates. The study of the role and function of complex carbohydrates often requires the attachment of carbohydrates to surfaces, their tagging with fluorophores, or their conversion into natural or non-natural glycoconjugates, such as glycopeptides or glycolipids. Glycobiology and its "omics", glycomics, require easy and robust chemical methods for the construction of these glycoconjugates. This review gives an overview of the rapidly expanding field of chemical reactions that selectively convert unprotected carbohydrates into glycoconjugates through the anomeric position. The discussion is divided in terms of the anomeric bond type of the newly formed glycoconjugates, including O-, N-, S-, and C-glycosides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Improving the time efficiency of the Fourier synthesis method for slice selection in magnetic resonance imaging.

    PubMed

    Tahayori, B; Khaneja, N; Johnston, L A; Farrell, P M; Mareels, I M Y

    2016-01-01

    The design of slice selective pulses for magnetic resonance imaging can be cast as an optimal control problem. The Fourier synthesis method is an existing approach to solve these optimal control problems. In this method the gradient field as well as the excitation field are switched rapidly and their amplitudes are calculated based on a Fourier series expansion. Here, we provide a novel insight into the Fourier synthesis method via representing the Bloch equation in spherical coordinates. Based on the spherical Bloch equation, we propose an alternative sequence of pulses that can be used for slice selection which is more time efficient compared to the original method. Simulation results demonstrate that while the performance of both methods is approximately the same, the required time for the proposed sequence of pulses is half of the original sequence of pulses. Furthermore, the slice selectivity of both sequences of pulses changes with radio frequency field inhomogeneities in a similar way. We also introduce a measure, referred to as gradient complexity, to compare the performance of both sequences of pulses. This measure indicates that for a desired level of uniformity in the excited slice, the gradient complexity for the proposed sequence of pulses is less than the original sequence. Copyright © 2015 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

  1. Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis.

    PubMed

    Li, Chun; Han, Xiaopeng; Cheng, Fangyi; Hu, Yuxiang; Chen, Chengcheng; Chen, Jun

    2015-06-04

    Spinel-type oxides are technologically important in many fields, including electronics, magnetism, catalysis and electrochemical energy storage and conversion. Typically, these materials are prepared by conventional ceramic routes that are energy consuming and offer limited control over shape and size. Moreover, for mixed-metal oxide spinels (for example, Co(x)Mn(3-x)O4), the crystallographic phase sensitively correlates with the metal ratio, posing great challenges to synthesize active product with simultaneously tuned phase and composition. Here we report a general synthesis of ultrasmall cobalt manganese spinels with tailored structural symmetry and composition through facile solution-based oxidation-precipitation and insertion-crystallization process at modest condition. As an example application, the nanocrystalline spinels catalyse the oxygen reduction/evolution reactions, showing phase and composition co-dependent performance. Furthermore, the mild synthetic strategy allows the formation of homogeneous and strongly coupled spinel/carbon nanocomposites, which exhibit comparable activity but superior durability to Pt/C and serve as efficient catalysts to build rechargeable Zn-air and Li-air batteries.

  2. Facile and easily popularized synthesis of L-cysteine-functionalized magnetic nanoparticles based on one-step functionalization for highly efficient enrichment of glycopeptides.

    PubMed

    Feng, Xiaoyan; Deng, Chunhui; Gao, Mingxia; Zhang, Xiangmin

    2018-01-01

    Protein glycosylation is one of the most important post-translational modifications. Also, efficient enrichment and separation of glycopeptides from complex samples are crucial for the thorough analysis of glycosylation. Developing novel hydrophilic materials with facile and easily popularized synthesis is an urgent need in large-scale glycoproteomics research. Herein, for the first time, a one-step functionalization strategy based on metal-organic coordination was proposed and Fe 3 O 4 nanoparticles were directly functionalized with zwitterionic hydrophilic L-cysteine (L-Cys), greatly simplifying the synthetic procedure. The easily synthesized Fe 3 O 4 /L-Cys possessed excellent hydrophilicity and brief composition, contributing to affinity for glycopeptides and reduction in nonspecific interaction. Thus, Fe 3 O 4 /L-Cys nanoparticles showed outstanding sensitivity (25 amol/μL), high selectivity (mixture of bovine serum albumin and horseradish peroxidase tryptic digests at a mass ratio of 100:1), good reusability (five repeated times), and stability (room temperature storage of 1 month). Encouragingly, in the glycosylation analysis of human serum, a total of 376 glycopeptides with 393 N-glycosylation sites corresponding to 118 glycoproteins were identified after enrichment with Fe 3 O 4 /L-Cys, which was superior to ever reported L-Cys modified magnetic materials. Furthermore, applying the one-step functionalization strategy, cysteamine and glutathione respectively direct-functionalized Fe 3 O 4 nanoparticles were successfully synthesized and also achieved efficient glycopeptide enrichment in human serum. The results indicated that we have presented an efficient and easily popularized strategy in glycoproteomics as well as in the synthesis of novel materials. Graphical abstract Fe 3 O 4 /L-Cys nanoparticles based on one-step functionalization for highly efficient enrichment of glycopeptides.

  3. Efficient synthesis of ammonia from N2 and H2 alone in a ferroelectric packed-bed DBD reactor

    NASA Astrophysics Data System (ADS)

    Gómez-Ramírez, A.; Cotrino, J.; Lambert, R. M.; González-Elipe, A. R.

    2015-12-01

    A detailed study of ammonia synthesis from hydrogen and nitrogen in a planar dielectric barrier discharge (DBD) reactor was carried out. Electrical parameters were systematically varied, including applied voltage and frequency, electrode gap, and type of ferroelectric material (BaTiO3 versus PZT). For selected operating conditions, power consumption and plasma electron density were estimated from Lissajous diagrams and by application of the Bolsig  +  model, respectively. Optical emission spectroscopy was used to follow the evolution of plasma species (\\text{N}{{\\text{H}}*},{{\\text{N}}*},~{N}2+~\\text{and} ~{N}2* ) as a function of applied voltage with both types of ferroelectric material. PZT gave both greater energy efficiency and higher ammonia yield than BaTiO3: 0.9 g NH3 kWh-1 and 2.7% single pass N2 conversion, respectively. This performance is substantially superior to previously published findings on DBD synthesis of NH3 from N2 and H2 alone. The influence of electrical working parameters, the beneficial effect of PZT and the importance of controlling reactant residence time are rationalized in a reaction model that takes account of the principal process variables

  4. Synthesis of Ureas from CO2.

    PubMed

    Wang, Hua; Xin, Zhuo; Li, Yuehui

    2017-04-01

    Ureas are an important class of bioactive organic compounds in organic chemistry and exist widely in natural products, agricultural pesticides, uron herbicides, pharmaceuticals. Even though urea itself has been synthesized from CO 2 and ammonia for a long time, the selective and efficient synthesis of substituted ureas is still challenging due to the difficulty of dehydration processes. Efficient and economic fixation of CO 2 is of great importance in solving the problems of resource shortages, environmental issues, global warming, etc. During recent decades, chemists have developed different catalytic systems to synthesize ureas from CO 2 and amines. Herein, we focus on catalytic synthesis of ureas using CO 2 and amines.

  5. Efficient reductive amination process for enantioselective synthesis of L-phosphinothricin applying engineered glutamate dehydrogenase.

    PubMed

    Yin, Xinjian; Wu, Jianping; Yang, Lirong

    2018-05-01

    The objective of this study was to identify and exploit a robust biocatalyst that can be applied in reductive amination for enantioselective synthesis of the competitive herbicide L-phosphinothricin. Applying a genome mining-based library construction strategy, eight NADPH-specific glutamate dehydrogenases (GluDHs) were identified for reductively aminating 2-oxo-4-[(hydroxy)(methyl)phosphinoyl]butyric acid (PPO) to L-phosphinothricin. Among them, the glutamate dehydrogenase cloned from Pseudomonas putida (PpGluDH) exhibited relatively high catalytic activity and favorable soluble expression. This enzyme was purified to homogeneity for further characterization. The specific activity of PpGluDH was 296.1 U/g-protein, which is significantly higher than the reported value for a GluDH. To the best of our knowledge, there has not been any report on protein engineering of GluDH for PPO-oriented activity. Taking full advantage of the available information and the diverse characteristics of the enzymes in the enzyme library, PpGluDH was engineered by site-directed mutation based on multiple sequence alignment. The mutant I170M, which had 2.1-fold enhanced activity, was successfully produced. When the I170M mutant was applied in the batch production of L-phosphinothricin, it showed markedly improved catalytic efficiency compared with the wild type enzyme. The conversion reached 99% (0.1 M PPO) with an L-phosphinothricin productivity of 1.35 g/h·L, which far surpassed the previously reported level. These results show that PpGluDH I170M is a promising biocatalyst for highly enantioselective synthesis of L-phosphinothricin by reductive amination.

  6. Effect of powder compaction on radiation-thermal synthesis of lithium-titanium ferrites

    NASA Astrophysics Data System (ADS)

    Surzhikov, A. P.; Lysenko, E. N.; Vlasov, V. A.; Malyshev, A. V.; Korobeynikov, M. V.; Mikhailenko, M. A.

    2017-01-01

    Effect of powder compaction on the efficiency of thermal and radiation-thermal synthesis of lithium-substituted ferrites was investigated by X-Ray diffraction and specific magnetization analysis. It was shown that the radiation-thermal heating of compacted powder reagents mixture leads to an increase in efficiency of lithium-titanium ferrites synthesis.

  7. Adapter reagents for protein site specific dye labeling.

    PubMed

    Thompson, Darren A; Evans, Eric G B; Kasza, Tomas; Millhauser, Glenn L; Dawson, Philip E

    2014-05-01

    Chemoselective protein labeling remains a significant challenge in chemical biology. Although many selective labeling chemistries have been reported, the practicalities of matching the reaction with appropriately functionalized proteins and labeling reagents is often a challenge. For example, we encountered the challenge of site specifically labeling the cellular form of the murine Prion protein with a fluorescent dye. To facilitate this labeling, a protein was expressed with site specific p-acetylphenylalanine. However, the utility of this acetophenone reactive group is hampered by the severe lack of commercially available aminooxy fluorophores. Here we outline a general strategy for the efficient solid phase synthesis of adapter reagents capable of converting maleimido-labels into aminooxy or azide functional groups that can be further tuned for desired length or solubility properties. The utility of the adapter strategy is demonstrated in the context of fluorescent labeling of the murine Prion protein through an adapted aminooxy-Alexa dye. © 2014 Wiley Periodicals, Inc.

  8. Adapter Reagents for Protein Site Specific Dye Labeling

    PubMed Central

    Thompson, Darren A.; Evans, Eric G. B.; Kasza, Tomas; Millhauser, Glenn L.; Dawson, Philip E.

    2016-01-01

    Chemoselective protein labeling remains a significant challenge in chemical biology. Although many selective labeling chemistries have been reported, the practicalities of matching the reaction with appropriately functionalized proteins and labeling reagents is often a challenge. For example, we encountered the challenge of site specifically labeling the cellular form of the murine Prion protein with a fluorescent dye. To facilitate this labeling, a protein was expressed with site specific p-acetylphenylalanine. However, the utility of this aceto-phenone reactive group is hampered by the severe lack of commercially available aminooxy fluorophores. Here we outline a general strategy for the efficient solid phase synthesis of adapter reagents capable of converting maleimido-labels into aminooxy or azide functional groups that can be further tuned for desired length or solubility properties. The utility of the adapter strategy is demonstrated in the context of fluorescent labeling of the murine Prion protein through an adapted aminooxy-Alexa dye. PMID:24599728

  9. Site-specific protein labeling with PRIME and chelation-assisted Click chemistry

    PubMed Central

    Uttamapinant, Chayasith; Sanchez, Mateo I.; Liu, Daniel S.; Yao, Jennifer Z.; White, Katharine A.; Grecian, Scott; Clarke, Scott; Gee, Kyle R.; Ting, Alice Y.

    2016-01-01

    This protocol describes an efficient method to site-specifically label cell-surface or purified proteins with chemical probes in two steps: PRobe Incorporation Mediated by Enzymes (PRIME) followed by chelation-assisted copper-catalyzed azide-alkyne cycloaddition (CuAAC). In the PRIME step, Escherichia coli lipoic acid ligase site-specifically attaches a picolyl azide derivative to a 13-amino acid recognition sequence that has been genetically fused onto the protein of interest. Proteins bearing picolyl azide are chemoselectively derivatized with an alkyne-probe conjugate by chelation-assisted CuAAC in the second step. We describe herein the optimized protocols to synthesize picolyl azide, perform PRIME labeling, and achieve CuAAC derivatization of picolyl azide on live cells, fixed cells, and purified proteins. Reagent preparations, including synthesis of picolyl azide probes and expression of lipoic acid ligase, take 12 d, while the procedure to perform site-specific picolyl azide ligation and CuAAC on cells or on purified proteins takes 40 min-3 h. PMID:23887180

  10. Towards efficient chemical synthesis via engineering enzyme catalysis in biomimetic nanoreactors.

    PubMed

    Liu, Jia; Yang, Qihua; Li, Can

    2015-09-18

    Biocatalysis with immobilized enzymes as catalysts holds enormous promise in developing more efficient and sustainable processes for the synthesis of fine chemicals, chiral pharmaceuticals and biomass feedstocks. Despite the appealing potentials, nowadays the industrial-scale application of biocatalysts is still quite modest in comparison with that of traditional chemical catalysts. A critical issue is that the catalytic performance of enzymes, the sophisticated and vulnerable catalytic machineries, strongly depends on their intracellular working environment; however the working circumstances provided by the support matrix are radically different from those in cells. This often leads to various adverse consequences on enzyme conformation and dynamic properties, consequently decreasing the overall performance of immobilized enzymes with regard to their activity, selectivity and stability. Engineering enzyme catalysis in support nanopores by mimicking the physiological milieu of enzymes in vivo and investigating how the interior microenvironment of nanopores imposes an influence on enzyme behaviors in vitro are of paramount significance to modify and improve the catalytic functions of immobilized enzymes. In this feature article, we have summarized the recent advances in mimicking the working environment and working patterns of intracellular enzymes in nanopores of mesoporous silica-based supports. Especially, we have demonstrated that incorporation of polymers into silica nanopores could be a valuable approach to create the biomimetic microenvironment for enzymes in the immobilized state.

  11. New Efficient Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones Catalyzed by Benzotriazolium-Based Ionic Liquids under Solvent-Free Conditions.

    PubMed

    Liu, Zhiqing; Ma, Rong; Cao, Dawei; Liu, Chenjiang

    2016-04-07

    An efficient synthesis of novel 3,4-dihydropyrimidin-2(1H)-ones (DHPMs) and their derivatives, using Brønsted acidic ionic liquid [C₂O₂BBTA][TFA] as a catalyst, from the condensation of aryl aldehyde, β-ketoester and urea was described. Reactions proceeded smoothly for 40 min under solvent-free conditions and gave the desirable products with good to excellent yields (up to 99%). The catalyst could be easily recycled and reused with similar efficacies for at least six cycles.

  12. Schwertmannite Synthesis through Ferrous Ion Chemical Oxidation under Different H2O2 Supply Rates and Its Removal Efficiency for Arsenic from Contaminated Groundwater.

    PubMed

    Liu, Fenwu; Zhou, Jun; Zhang, Shasha; Liu, Lanlan; Zhou, Lixiang; Fan, Wenhua

    2015-01-01

    Schwertmannite-mediated removal of arsenic from contaminated water has attracted increasing attention. However, schwertmannite chemical synthesis behavior under different H2O2 supply rates for ferrous ions oxidation is unclear. This study investigated pH, ferrous ions oxidation efficiency, and total iron precipitation efficiency during schwertmannite synthesis by adding H2O2 into FeSO4 · 7H2O solution at different supply rates. Specific surface area and arsenic (III) removal capacity of schwertmannite have also been studied. Results showed that pH decreased from ~3.48 to ~1.96, ~2.06, ~2.12, ~2.14, or ~2.17 after 60 h reaction when the ferrous ions solution received the following corresponding amounts of H2O2: 1.80 mL at 2 h (treatment 1); 0.90 mL at 2 h and 14 h (treatment 2); 0.60 mL at 2, 14, and 26 h (treatment 3); 0.45 mL at 2, 14, 26, and 38 h (treatment 4), or 0.36 mL at 2, 14, 26, 38, and 50 h (treatment 5). Slow H2O2 supply significantly inhibited the total iron precipitation efficiency but improved the specific surface area or arsenic (III) removal capacity of schwertmannite. For the initial 50.0 μg/L arsenic (III)-contaminated water under pH ~7.0 and using 0.25 g/L schwertmannite as an adsorbent, the total iron precipitation efficiency, specific surface area of the harvested schwertmannite, and schwertmannite arsenic(III) removal efficiency were 29.3%, 2.06 m2/g, and 81.1%, respectively, in treatment 1. However, the above parameters correspondingly changed to 17.3%, 16.30 m2/g, and 96.5%, respectively, in treatment 5.

  13. Rational Design, Development, and Stability Assessment of a Macrocyclic Four-Hydroxamate-Bearing Bifunctional Chelating Agent for 89 Zr.

    PubMed

    Seibold, Uwe; Wängler, Björn; Wängler, Carmen

    2017-09-21

    Zirconium-89 is a positron-emitting radionuclide of high interest for medical imaging applications with positron emission tomography (PET). For the introduction of this radiometal into biologically active targeting vectors, the chelating agent desferrioxamine B (DFO) is commonly applied. However, DFO is known to form 89 Zr complexes of limited in vivo stability. Herein we describe the rational design and chemical development of a new macrocyclic four-hydroxamate-bearing chelating agent-1,10,19,28-tetrahydroxy-1,5,10,14,19,23,28,32-octaazacyclohexatriacontan-2,6,11,15,20,24,29,33-octaone (CTH36)-for the stable complexation of Zr 4+ . For this purpose, we first performed computational studies to determine the optimal chelator geometry before we developed different synthesis pathways toward the target structures. The best results were obtained using an efficient solution-phase-based synthesis strategy toward the target chelating agent. To enable efficient and chemoselective conjugation to biomolecules, a tetrazine-modified variant of CTH36 was also developed. The excellent conjugation characteristics of the so-functionalized chelator were demonstrated on the example of the model peptide TCO-c(RGDfK). We determined the optimal 89 Zr radiolabeling parameters for CTH36 as well as its bioconjugate, and found that 89 Zr radiolabeling proceeds efficiently under very mild reaction conditions. Finally, we performed comparative complex stability tests for 89 Zr-CHT36-c(RGDfK) and 89 Zr-DFO-c(RGDfK), showing improved complex stability for the newly developed chelator CTH36. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Strategies to prepare and use functionalized organometallic reagents.

    PubMed

    Klatt, Thomas; Markiewicz, John T; Sämann, Christoph; Knochel, Paul

    2014-05-16

    Polyfunctional zinc and magnesium organometallic reagents occupy a central position in organic synthesis. Most organic functional groups are tolerated by zinc organometallic reagents, and Csp(2)-centered magnesium organometallic reagents are compatible with important functional groups, such as the ester, aryl ketone, nitro, cyano, and amide functions. This excellent chemoselectivity gives zinc- and magnesium-organometallic reagents a central position in modern organic synthesis. Efficient and general preparations of these organometallic reagents, as well as their most practical and useful reactions, are presented in this Perspective. As starting materials, a broad range of organic halides (iodides, bromides, and also to some extent chlorides) can be used for the direct insertion of magnesium or zinc powder; the presence of LiCl very efficiently promotes such insertions. Alternatively, aromatic or heterocyclic bromides also undergo a smooth bromine-magnesium exchange when treated with i-PrMgCl·LiCl. Alternative precursors of zinc and magnesium reagents are polyfunctionalized aryl and heteroaryl molecules, which undergo directed metalations with sterically hindered TMP bases (TMP = 2,2,6,6-tetramethylpiperide) of magnesium and zinc. This powerful C-H functionalization method gives access to polyfunctional heterocyclic zinc and magnesium reagents, which undergo efficient reactions with numerous electrophiles. The compatibility of the strong TMP-bases with BF3·OEt2 (formation of frustrated Lewis pairs) dramatically increases the scope of these metalations, giving for example, a practical access to magnesiated pyridines and pyrazines, which can be used as convenient building blocks for the preparation of biologically active molecules.

  15. Peptide synthesis on glass substrate using acoustic droplet ejector.

    PubMed

    Youngki Choe; Shih-Jui Chen; Eun Sok Kim

    2014-03-01

    This paper describes the synthesis of a 9-mers-long peptide ladder structure of glycine on a modified glass surface using a nanoliter droplet ejector. To synthesize peptide on a glass substrate, SPOT peptide synthesis protocol was followed with a nozzleless acoustic droplet ejector being used to eject about 300 droplets of preactivated amino acid solution to dispense 60 nL of the solution per mer. The coupling efficiency of each mer was measured with FITC fluorescent tag to be 96%, resulting in net 70% efficiency for the whole 9-mer-long peptide of glycine. Usage of a nanoliter droplet ejector for SPOT peptide synthesis increases the density of protein array on a chip.

  16. Bioorthogonal Diversification of Peptides through Selective Ruthenium(II)-Catalyzed C-H Activation.

    PubMed

    Schischko, Alexandra; Ren, Hongjun; Kaplaneris, Nikolaos; Ackermann, Lutz

    2017-02-01

    Methods for the chemoselective modification of amino acids and peptides are powerful techniques in biomolecular chemistry. Among other applications, they enable the total synthesis of artificial peptides. In recent years, significant momentum has been gained by exploiting palladium-catalyzed cross-coupling for peptide modification. Despite major advances, the prefunctionalization elements on the coupling partners translate into undesired byproduct formation and lengthy synthetic operations. In sharp contrast, we herein illustrate the unprecedented use of versatile ruthenium(II)carboxylate catalysis for the step-economical late-stage diversification of α- and β-amino acids, as well as peptides, through chemo-selective C-H arylation under racemization-free reaction conditions. The ligand-accelerated C-H activation strategy proved water-tolerant and set the stage for direct fluorescence labelling as well as various modes of peptide ligation with excellent levels of positional selectivity in a bioorthogonal fashion. The synthetic utility of our approach is further demonstrated by twofold C-H arylations for the complexity-increasing assembly of artificial peptides within a multicatalytic C-H activation manifold. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. A Novel Implementation of Efficient Algorithms for Quantum Circuit Synthesis

    NASA Astrophysics Data System (ADS)

    Zeller, Luke

    In this project, we design and develop a computer program to effectively approximate arbitrary quantum gates using the discrete set of Clifford Gates together with the T gate (π/8 gate). Employing recent results from Mosca et. al. and Giles and Selinger, we implement a decomposition scheme that outputs a sequence of Clifford, T, and Tt gates that approximate the input to within a specified error range ɛ. Specifically, the given gate is first rounded to an element of Z[1/2, i] with a precision determined by ɛ, and then exact synthesis is employed to produce the resulting gate. It is known that this procedure is optimal in approximating an arbitrary single qubit gate. Our program, written in Matlab and Python, can complete both approximate and exact synthesis of qubits. It can be used to assist in the experimental implementation of an arbitrary fault-tolerant single qubit gate, for which direct implementation isn't feasible.

  18. ZnO nanoparticles as an efficient, heterogeneous, reusable, and ecofriendly catalyst for four-component one-pot green synthesis of pyranopyrazole derivatives in water.

    PubMed

    Sachdeva, Harshita; Saroj, Rekha

    2013-01-01

    An extremely efficient catalytic protocol for the synthesis of a series of pyranopyrazole derivatives developed in a one-pot four-component approach in the presence of ZnO nanoparticles as heterogeneous catalyst using water as a green solvent is reported. Greenness of the process is well instituted as water is exploited both as reaction media and medium for synthesis of catalyst. The ZnO nanoparticles exhibited excellent catalytic activity, and the proposed methodology is capable of providing the desired products in good yield (85-90%) and short reaction time. After reaction course, ZnO nanoparticles can be recycled and reused without any apparent loss of activity which makes this process cost effective and hence ecofriendly. All the synthesized compounds have been characterized on the basis of elemental analysis, IR, ¹H NMR, and ¹³C NMR spectral studies.

  19. Flavivirus RNA Synthesis in vitro

    PubMed Central

    Padmanabhan, Radhakrishnan; Takhampunya, Ratree; Teramoto, Tadahisa; Choi, Kyung H.

    2015-01-01

    Summary Establishment of in vitro systems to study mechanisms of RNA synthesis for positive strand RNA viruses have been very useful in the past and have shed light on the composition of protein and RNA components, optimum conditions, the nature of the products formed, cis-acting RNA elements and trans-acting protein factors required for efficient synthesis. In this review, we summarize our current understanding regarding the requirements for flavivirus RNA synthesis in vitro. We describe details of reaction conditions, the specificity of template used by either the multi-component membrane-bound viral replicase complex or by purified, recombinant RNA-dependent RNA polymerase. We also discuss future perspectives to extend the boundaries of our knowledge. PMID:26272247

  20. Ligand-Free Pd-Catalyzed Double Carbonylation of Aryl Iodides with Amines to α-Ketoamides under Atmospheric Pressure of Carbon Monoxide and at Room Temperature.

    PubMed

    Du, Hongyan; Ruan, Qing; Qi, Minghao; Han, Wei

    2015-08-07

    A general Pd-catalyzed double carbonylation of aryl iodides with secondary or primary amines to produce α-ketoamides at atmospheric CO pressure has been developed. This transformation proceeds successfully even at room temperature and in the absence of any ligand and additive. A wide range of aryl iodides and amines can be coupled to the desired α-ketoamides in high yields with excellent chemoselectivities. Importantly, the current methodology has been demonstrated to be applied in the synthesis of bioactive molecules and chiral α-ketoamides.

  1. Shape-Controlled Synthesis of High-Quality Cu7 S4 Nanocrystals for Efficient Light-Induced Water Evaporation.

    PubMed

    Zhang, Changbo; Yan, Cong; Xue, Zhenjie; Yu, Wei; Xie, Yinde; Wang, Tie

    2016-10-01

    Copper sulfides (Cu 2-x S), are a novel kind of photothermal material exhibiting significant photothermal conversion efficiency, making them very attractive in various energy conversion related devices. Preparing high quality uniform Cu 2-x S nanocrystals (NCs) is a top priority for further energy-and sustainability relevant nanodevices. Here, a shape-controlled high quality Cu 7 S 4 NCs synthesis strategy is reported using sulfur in 1-octadecene as precursor by varying the heating temperature, as well as its forming mechanism. The performance of the Cu 7 S 4 NCs is further explored for light-driven water evaporation without the need of heating the bulk liquid to the boiling point, and the results suggest that as-synthesized highly monodisperse NCs perform higher evaporation rate than polydisperse NCs under the identical morphology. Furthermore, disk-like NCs exhibit higher water evaporation rate than spherical NCs. The water evaporation rate can be further enhanced by assembling the organic phase Cu 7 S 4 NCs into a dense film on the aqueous solution surface. The maximum photothermal conversion efficiency is as high as 77.1%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Advances in chemoselective intermolecular cross-benzoin-type condensation reactions.

    PubMed

    Gaggero, Nicoletta; Pandini, Stefano

    2017-08-23

    The intermolecular cross-benzoin and acyloin condensation reactions are powerful approaches to α-hydroxy carbonyls in a single step. However, their potentiality suffers from the occurrence of side reactions including self-condensation and the formation of the undesired cross-acyloin. The broad range of azolium salt precatalysts available confers high tunability to NHC mediated benzoin condensation, assuring a good level of selectivity to the direct coupling between two non-equivalent aldehydes. Many efforts have also been devoted to the design of strategies that expand the range of suitable reaction partners beyond the traditional aldehydes and to the discovery of novel umpolung catalytic systems. The synthesis of both racemic and enantiomerically enriched acyloins is reviewed.

  3. An efficient synthesis of the constrained peptidomimetic 2-oxo-3-(N-9-fluorenyloxycarbonylamino)-1-azabicyclo[4.3.0]nonane-9-carboxylic acid from pyroglutamic acid.

    PubMed

    Mandal, Pijus Kumar; Kaluarachchi, Kumar K; Ogrin, Douglas; Bott, Simon G; McMurray, John S

    2005-11-25

    [reaction: see text] Azabicyclo[X.Y.0]alkane amino acids are rigid dipeptide mimetics that are useful tools for structure-activity studies in peptide-based drug discovery. Herein, we report an efficient synthesis of three diastereomers of 9-tert-butoxycarbonyl-2-oxo-3-(N-tert-butoxycarbonylamino)-1-azabicyclo[4.3.0]nonane (3S,6S,9S, 3S,6R,9R, and 3S,6R,9S). Methyl N-Boc-pyroglutamate is cleaved with vinylmagnesium bromide to produce an acyclic gamma-vinyl ketone. Michael addition of N-diphenylmethyleneglycine tert-butyl ester produces the N-Boc-delta-oxo-alpha,omega-diaminoazelate intermediate, which, on hydrogenloysis, gives the fused ring system. Acidolytic deprotection followed by Fmoc-protection provided building blocks suitable for solid-phase synthesis.

  4. Efficient synthesis and physicochemical characterization of natural danshensu, its S isomer and intermediates thereof

    NASA Astrophysics Data System (ADS)

    Sidoryk, Katarzyna; Filip, Katarzyna; Cmoch, Piotr; Łaszcz, Marta; Cybulski, Marcin

    2018-02-01

    The synthesis and molecular structure details of R- 3,4-dihydroxyphenyl lactic acid (danshensu) and related compounds, i.e. S isomer and the key intermediates have been described. Danshensu is an important water soluble phenolic acid of Salvia miltiorrhiza herb (danshen or red sag) with numerous applications in traditional Chinese medicine (TCM). Our synthetic approach was based on the Knoevenagel condensation of the protected 3,4-dihydroxybenzaldehyd and Meldrum acid derivative, followed by asymmetric Sharples dihydroxylation, reductive mono dehydroxylation and final deprotection. All compounds were characterized by various spectroscopic techniques: 1H-, 13C- magnetic resonance (NMR); Fourier-transformed infrared (FTIR); Raman, HR mass spectroscopy. For the determination of compound optical purities original HPLC methods were developed which allowed for the efficient resolution of danshensu R and S enantiomers as well as its intermediate enantiomers, using commercially available chiral stationary phases. Furthermore, in order to better understand danshensu specificity as a potential API in drug formulation, the physicochemical properties of the compounds were studied by thermal analysis, including differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).

  5. Regulation of Staphylococcal Penicillinase Synthesis

    PubMed Central

    Imsande, John; Zyskind, Judith W.; Mile, Imre

    1972-01-01

    5-Methyl tryptophan was found to be an efficient inducer of penicillinase synthesis in Staphylococcus aureus. Addition of actinomycin D or tryptophan to the culture medium shuts off the 5-methyl tryptophan-induced synthesis of penicillinase with an apparent half-life of approximately 1 to 2 min, respectively. Hence, in the induction of penicillinase synthesis, 5-methyl tryptophan seems to function as a structural analogue of penicillin rather than by becoming incorporated in proteins and thereby creating faulty penicillinase repressor or antirepressor. This conclusion is supported by similarities in the structures of the two compounds as revealed by solid atomic models. The fact that S. aureus exposed to 14C-penicillin in the absence of protein synthesis failed to synthesize penicillinase at an increased level when cell growth was resumed strongly suggests that a protein involved in the regulation of penicillinase synthesis must be synthesized in the presence of the penicillinase inducer. In turn, this observation suggests that the penicillinase inducer promotes penicillinase synthesis by directing the penicillinase regulatory protein (i.e., the penicillinase antirepressor) to acquire a different conformation when it is synthesized in the presence of the penicillinase inducer. A working model for the regulation of penicillinase synthesis based on these and other data has been constructed and is presented. Images PMID:4333374

  6. Graphene Derivative in Magnetically Recoverable Catalyst Determines Catalytic Properties in Transfer Hydrogenation of Nitroarenes to Anilines with 2-Propanol.

    PubMed

    Das, Vijay Kumar; Mazhar, Sumaira; Gregor, Lennon; Stein, Barry D; Morgan, David Gene; Maciulis, Nicholas A; Pink, Maren; Losovyj, Yaroslav; Bronstein, Lyudmila M

    2018-06-14

    Here, we report transfer hydrogenation of nitroarenes to aminoarenes using 2-propanol as a hydrogen source and Ag-containing magnetically recoverable catalysts based on partially reduced graphene oxide (pRGO) sheets. X-ray diffraction and X-ray photoelectron spectroscopy data demonstrated that, during the one-pot catalyst synthesis, formation of magnetite nanoparticles (NPs) is accompanied by the reduction of graphene oxide (GO) to pRGO. The formation of Ag 0 NPs on top of magnetite nanoparticles does not change the pRGO structure. At the same time, the catalyst structure is further modified during the transfer hydrogenation, leading to a noticeable increase of sp 2 carbons. These carbons are responsible for the adsorption of substrate and intermediates, facilitating a hydrogen transfer from Ag NPs and creating synergy between the components of the catalyst. The nitroarenes with electron withdrawing and electron donating substituents allow for excellent yields of aniline derivatives with high regio and chemoselectivity, indicating that the reaction is not disfavored by these functionalities. The versatility of the catalyst synthetic protocol was demonstrated by a synthesis of an Ru-containing graphene derivative based catalyst, also allowing for efficient transfer hydrogenation. Easy magnetic separation and stable catalyst performance in the transfer hydrogenation make this catalyst promising for future applications.

  7. Peptide o-aminoanilides as crypto-thioesters for protein chemical synthesis.

    PubMed

    Wang, Jia-Xing; Fang, Ge-Min; He, Yao; Qu, Da-Liang; Yu, Min; Hong, Zhang-Yong; Liu, Lei

    2015-02-09

    Fully unprotected peptide o-aminoanilides can be efficiently activated by NaNO2 in aqueous solution to furnish peptide thioesters for use in native chemical ligation. This finding enables the convergent synthesis of proteins from readily synthesizable peptide o-aminoanilides as a new type of crypto-thioesters. The practicality of this approach is shown by the synthesis of histone H2B from five peptide segments. Purification or solubilization tags, which are sometimes needed to improve the efficiency of protein chemical synthesis, can be incorporated into the o-aminoanilide moiety, as demonstrated in the preparation of the cyclic protein lactocyclicin Q. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Using Decision Procedures to Build Domain-Specific Deductive Synthesis Systems

    NASA Technical Reports Server (NTRS)

    VanBaalen, Jeffrey; Roach, Steven; Lau, Sonie (Technical Monitor)

    1998-01-01

    This paper describes a class of decision procedures that we have found useful for efficient, domain-specific deductive synthesis. These procedures are called closure-based ground literal satisfiability procedures. We argue that this is a large and interesting class of procedures and show how to interface these procedures to a theorem prover for efficient deductive synthesis. Finally, we describe some results we have observed from our implementation. Amphion/NAIF is a domain-specific, high-assurance software synthesis system. It takes an abstract specification of a problem in solar system mechanics, such as 'when will a signal sent from the Cassini spacecraft to Earth be blocked by the planet Saturn?', and automatically synthesizes a FORTRAN program to solve it.

  9. Chemoenzymatic Synthesis and α-Glucosidase Inhibitory Activity of Dimeric Neolignans Inspired by Magnolol.

    PubMed

    Pulvirenti, Luana; Muccilli, Vera; Cardullo, Nunzio; Spatafora, Carmela; Tringali, Corrado

    2017-05-26

    A chemoenzymatic synthesis of a small library of dimeric neolignans inspired by magnolol (1) is reported. The 2-iodoxybenzoic acid (IBX)-mediated regioselective ortho-hydroxylation of magnolol is described, affording the bisphenols 6 and 7. Further magnolol analogues (12, 13, 15-17, 19-23) were obtained from eugenol (3), tyrosol (4), and homovanillic alcohol (5), through horseradish peroxidase (HRP)-mediated oxidative coupling and regioselective ortho-hydroxylation or ortho-demethylation in the presence of IBX, followed by reductive treatment with Na 2 S 2 O 4 . A chemoselective protection/deprotection of the alcoholic group of 4 and 5 was carried out by lipase-mediated acetylation/deacetylation. The dimeric neolignans, together with 1 and honokiol (2), were evaluated as inhibitors of yeast α-glucosidase, in view of their possible utilization and optimization as antidiabetic drugs. The synthetic analogues of magnolol showed a strong inhibitory activity with IC 50 values in the range 0.15-4.1 μM, much lower than those of honokiol and the reference compounds quercetin and acarbose. In particular, a very potent inhibitory activity, with an IC 50 of 0.15 μM, was observed for 1,1'-dityrosol-8,8'-diacetate (15), and comparable inhibitory activities were also shown by bisphenols 6 (0.49 μM), 13 (0.50 μM), and 22 (0.86 μM). A kinetic study showed that 15 acts as a competitive inhibitor, with a K i value of 0.86 μM.

  10. Multigram Synthesis of a Chiral Substituted Indoline Via Copper-Catalyzed Alkene Aminooxygenation.

    PubMed

    Sequeira, Fatima C; Bovino, Michael T; Chipre, Anthony J; Chemler, Sherry R

    2012-05-01

    (S)-5-Fluoro-2-(2,2,6,6-tetramethylpiperidin-1-yloxymethyl)-1-tosylindoline, a 2-methyleneoxy-substituted chiral indoline, was synthesized on multigram scale using an efficient copper-catalyzed enantioselective intramolecular alkene aminooxygenation. The synthesis is accomplished in four steps and the indoline is obtained in 89% ee (>98% after one recrystallization). Other highlights include efficient gram-scale synthesis of the (4R,5S)-di-Ph-box ligand and efficient separation of a monoallylaniline from its bis(allyl)aniline by-product by distillation under reduced pressure.

  11. Anchoring of Cu(II) onto surface of porous metal-organic framework through post-synthesis modification for the synthesis of benzimidazoles and benzothiazoles

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kardanpour, Reihaneh; Tangestaninejad, Shahram, E-mail: stanges@sci.ui.ac.ir; Mirkhani, Valiollah, E-mail: mirkhani@sci.ui.ac.ir

    2016-03-15

    Efficient synthesis of various benzimidazoles and benzothiazoles under mild conditions catalyzed by Cu(II) anchored onto UiO-66–NH{sub 2} metal organic framework is reported. In this manner, first, the aminated UiO-66 was modified with thiophene-2-carbaldehyde and then the prepared Schiff base was reacted with CuCl{sub 2}. The prepared catalyst was characterized by FT-IR, UV–vis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N{sub 2} adsorption, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). The UiO-66–NH{sub 2}–TC–Cu was applied as a highly efficient catalyst for synthesis of benzimidazole and benzothiazole derivatives by the reaction of aldehydes with 1,2-diaminobenzenemore » or 2-aminothiophenol. The Cu(II)-containing MOF was reused several times without any appreciable loss of its efficiency. - Graphical abstract: Efficient synthesis of benzimidazoles and benzothiazoles catalyzed by Cu(II) anchored onto UiO-66–NH{sub 2} metal organic framework is reported. - Highlights: • A copper Schiff base was immobilized on UiO-66 via postsynthetic modification. • The modified MOFs were fully characterized by a variety of methods. • The catalyst was used for the preparation of benzimidazoles and benzothiazoles. • In comparison of other catalysts, our catalyst was more efficient and forceful.« less

  12. Catalytic chemical amide synthesis at room temperature: one more step toward peptide synthesis.

    PubMed

    Mohy El Dine, Tharwat; Erb, William; Berhault, Yohann; Rouden, Jacques; Blanchet, Jérôme

    2015-05-01

    An efficient method has been developed for direct amide bond synthesis between carboxylic acids and amines via (2-(thiophen-2-ylmethyl)phenyl)boronic acid as a highly active bench-stable catalyst. This catalyst was found to be very effective at room temperature for a large range of substrates with slightly higher temperatures required for challenging ones. This methodology can be applied to aliphatic, α-hydroxyl, aromatic, and heteroaromatic acids as well as primary, secondary, heterocyclic, and even functionalized amines. Notably, N-Boc-protected amino acids were successfully coupled in good yields with very little racemization. An example of catalytic dipeptide synthesis is reported.

  13. 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.

    PubMed

    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

    2014-05-16

    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.

  14. Efficient synthesis and antimicrobial evaluation of some Mannich bases from 2-arylidine-1-thia-4-azaspiro[4.5]decan-3-ones.

    PubMed

    Hussein, Essam M; Masaret, Ghada S; Khairou, Khalid S

    2015-01-01

    Thiazolidinone, has been employed in the preparation of different important drugs required for treatment of inflammations, bacterial infections, and hypertension. Mannich bases have been shown to exhibit diverse biological activities, such as antibacterial, and antifungal activities. Spiroheterocycles including thiazolidine moiety have antimicrobial activity. In this study, a novel, rapid, and efficient protocol is developed for the synthesis of various 2-arylidine-1-thia-4-azaspiro[4.5]decan-3-ones using sodium dodecylbenzene sulfonate (DBSNa) as an inexpensive and readily available reagent in acetic acid at room temperature. High yields, easy work-up, and short reaction times are advantages of this procedure. The synthesized arylidines were undergone Mannich reaction with formaldehyde and secondary amines in absolute ethanol at room temperature to afford the corresponding N-Mannich bases. All prepared Mannich bases were evaluated for their antimicrobial activity. Good activity was noted for Mannich bases from 2-arylidine-1-thia-4-azaspiro[4.5]decan-3-ones, with some members recorded higher antimicrobial activity. Graphical abstractSynthesis of Mannich bases of 2-arylidine-1-thia-4-azaspiro[4.5]decan-3-ones.

  15. Highly efficient enzymatic synthesis of tert-butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate with a mutant alcohol dehydrogenase of Lactobacillus kefir.

    PubMed

    He, Xiu-Juan; Chen, Shao-Yun; Wu, Jian-Ping; Yang, Li-Rong; Xu, Gang

    2015-11-01

    tert-Butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate ((S)-CHOH) is a valuable chiral synthon, which is used for the synthesis of the cholesterol-lowering drugs atorvastatin and rosuvastatin. To date, only the alcohol dehydrogenases from Lactobacillus brevis (LbADH) and Lactobacillus kefir (LkADH) have demonstrated catalytic activity toward the asymmetric reduction of tert-butyl 6-chloro-3,5-dioxohexanoate (CDOH) to (S)-CHOH. Herein, a tetrad mutant of LkADH (LkTADH), A94T/F147L/L199H/A202L, was screened to be more efficient in this bioreduction process, exhibiting a 3.7- and 42-fold improvement in specific activity toward CDOH (1.27 U/mg) over LbADH (0.34 U/mg) and wild-type LkADH (0.03 U/mg), respectively. The molecular basis for the improved catalytic activity of LkTADH toward CDOH was investigated using homology modeling and docking analysis. Two major issues had a significant impact on the biocatalytic efficiency of this process, including (i) the poor aqueous stability of the substrate and (ii) partial substrate inhibition. A fed-batch strategy was successfully developed to address these issues and maintain a suitably low substrate concentration throughout the entire process. Several other parameters were also optimized, including the pH, temperature, NADP(+) concentration and cell loading. A final CDOH concentration of 427 mM (100 g/L) gave (S)-CHOH in 94 % yield and 99.5 % e.e. after a reaction time of 38 h with whole cells expressing LkTADH. The space-time yield and turnover number of NADP(+) in this process were 10.6 mmol/L/h and 16,060 mol/mol, respectively, which were the highest values ever reported. This new approach therefore represents a promising alternative for the efficient synthesis of (S)-CHOH.

  16. Orthogonal Discrimination among Functional Groups in Ullmann-Type C-O and C-N Couplings.

    PubMed

    Rovira, Mireia; Soler, Marta; Güell, Imma; Wang, Ming-Zheng; Gómez, Laura; Ribas, Xavi

    2016-09-02

    The copper-catalyzed arylation of nucleophiles has been established as an efficient methodology for the formation of C-C and C-heteroatom bonds. Considering the advances during the last two decades, the ligand choice plays a key role in such transformations and can strongly influence the catalytic efficiency. The applicability of these Ullmann-type coupling reactions regarding the orthogonal selectivity of different functional groups constitutes a challenging subject for current synthetic strategies. Herein, we report a useful toolkit of Cu-based catalysts for the chemoselective arylation of a wide-range of nucleophiles in competitive reactions using aryl iodides and bromides. We show in this work that the arylation of all kinds of amides can be orthogonal to that of amines (aliphatic or aromatic) and phenol derivatives. This high chemoselectivity can be governed by the use of different ligands, yielding the desired coupling products under mild conditions. The selectivity trends are maintained for electronically biased iodobenzene and bromobenzene electrophiles. Radical clock experiments discard the occurrence of radical-based mechanisms.

  17. Liposome-chaperoned cell-free synthesis for the design of proteoliposomes: Implications for therapeutic delivery.

    PubMed

    Lu, Mei; Zhao, Xiaoyun; Xing, Haonan; Xun, Zhe; Yang, Tianzhi; Cai, Cuifang; Wang, Dongkai; Ding, Pingtian

    2018-04-03

    Cell-free (CF) protein synthesis has emerged as a powerful technique platform for efficient protein production in vitro. Liposomes have been widely studied as therapeutic carriers due to their biocompatibility, biodegradability, low toxicity, flexible surface manipulation, easy preparation, and higher cargo encapsulation capability. However, rapid immune clearance, insufficient targeting capacity, and poor cytoplasmic delivery efficiency substantially restrict their clinical application. The incorporation of functional membrane proteins (MPs) or peptides allows the transfer of biological properties to liposomes and imparts them with improved circulation, increased targeting, and efficient intracellular delivery. Liposome-chaperoned CF synthesis enables production of proteoliposomes in one-step reaction, which not only substantially simplifies the production procedure but also keeps protein functionality intact. Building off these observations, proteoliposomes with integrated MPs represent an excellent candidate for therapeutic delivery. In this review, we describe recent advances in CF synthesis with emphasis on detailing key factors for improving CF expression efficiency. Furthermore, we provide insights into strategies for rational design of proteoliposomal nanodelivery systems via CF synthesis. Liposome-chaperoned CF synthesis has emerged as a powerful approach for the design of recombinant proteoliposomes in one-step reaction. The incorporation of bioactive MPs or peptides into liposomes via CF synthesis can facilitate the development of proteoliposomal nanodelivery systems with improved circulation, increased targeting, and enhanced cellular delivery capacity. Moreover, by adapting lessons learned from natural delivery vehicles, novel bio-inspired proteoliposomes with enhanced delivery properties could be produced in CF systems. In this review, we first give an overview of CF synthesis with focus on enhancing protein expression in liposome-chaperoned CF

  18. Flow microreactor synthesis in organo-fluorine chemistry.

    PubMed

    Amii, Hideki; Nagaki, Aiichiro; Yoshida, Jun-Ichi

    2013-12-05

    Organo-fluorine compounds are the substances of considerable interest in various industrial fields due to their unique physical and chemical properties. Despite increased demand in wide fields of science, synthesis of fluoro-organic compounds is still often faced with problems such as the difficulties in handling of fluorinating reagents and in controlling of chemical reactions. Recently, flow microreactor synthesis has emerged as a new methodology for producing chemical substances with high efficiency. This review outlines the successful examples of synthesis and reactions of fluorine-containing molecules by the use of flow microreactor systems to overcome long-standing problems in fluorine chemistry.

  19. An efficient synthesis strategy for metal-organic frameworks: Dry-gel synthesis of MOF-74 framework with high yield and improved performance

    DOE PAGES

    Das, Atanu Kumar; Vemuri, Rama Sesha; Kutnyakov, Igor; ...

    2016-06-16

    Here, vapor-assisted dry-gel synthesis of MOF-74 structure, specifically NiMOF-74 from its synthetic precursors, was conducted with high yield and improved performance showing promise for gas (CO 2) and water adsorption applications. Unlike conventional synthesis, which takes 72 h, this kinetic study showed that NiMOF-74 forms within 12 h under dry-gel conditions with similar performance characteristics and exhibits the best performance characteristics after 48 h of heating.

  20. CTAB-assisted synthesis of monoclinic BiVO4 photocatalyst and its highly efficient degradation of organic dye under visible-light irradiation.

    PubMed

    Yin, Wenzong; Wang, Wenzhong; Zhou, Lin; Sun, Songmei; Zhang, Ling

    2010-01-15

    A highly efficient monoclinic BiVO(4) photocatalyst (C-BVO) was synthesized by an aqueous method with the assistance of cetyltrimethylammonium bromide (CTAB). The structure, morphology and photophysical properties of the C-BVO were characterized by XRD, FE-SEM and diffuse reflectance spectroscopy, respectively. The photocatalytic efficiencies were evaluated by the degradation of rhodamine B (RhB) under visible-light irradiation, revealing that the degradation rate over the C-BVO was much higher than that over the reference BiVO(4) prepared by aqueous method and over the one prepared by solid-state reaction. The efficiency of de-ethylation and that of the cleavage of conjugated chromophore structure were investigated, respectively. The chemical oxygen demand (COD) values of the RhB were measured after the photocatalytic degradation over the C-BVO and demonstrated a 53% decrease in COD. The effects of CTAB on the synthesis of C-BVO were investigated, which revealed that CTAB not only changed the reaction process via the formation of BiOBr as an intermediate, but also facilitated the transition from BiOBr to BiVO(4). Comparison experiments were carried out and showed that the existence of impurity level makes significant contribution to the high photocatalytic efficiency of the C-BVO.

  1. An Efficient Synthesis of de novo Imidates via Aza-Claisen Rearrangements of N-Allyl Ynamides

    PubMed Central

    DeKorver, Kyle A.; North, Troy D.; Hsung, Richard P.

    2010-01-01

    A novel thermal 3-aza-Claisen rearrangement of N-allyl ynamides for the synthesis of α-allyl imidates is described. Also, a sequential aza-Claisen, Pd-catalyzed Overman rearrangement is described for the synthesis of azapine-2-ones. PMID:21278848

  2. Multigram Synthesis of a Chiral Substituted Indoline Via Copper-Catalyzed Alkene Aminooxygenation

    PubMed Central

    Sequeira, Fatima C.; Bovino, Michael T.; Chipre, Anthony J.

    2012-01-01

    (S)-5-Fluoro-2-(2,2,6,6-tetramethylpiperidin-1-yloxymethyl)-1-tosylindoline, a 2-methyleneoxy-substituted chiral indoline, was synthesized on multigram scale using an efficient copper-catalyzed enantioselective intramolecular alkene aminooxygenation. The synthesis is accomplished in four steps and the indoline is obtained in 89% ee (>98% after one recrystallization). Other highlights include efficient gram-scale synthesis of the (4R,5S)-di-Ph-box ligand and efficient separation of a monoallylaniline from its bis(allyl)aniline by-product by distillation under reduced pressure. PMID:22639473

  3. Preparation and characterization of a supported system of Ni2P/Ni12P5 nanoparticles and their use as the active phase in chemoselective hydrogenation of acetophenone

    NASA Astrophysics Data System (ADS)

    Costa, Dolly C.; Soldati, Analía L.; Pecchi, Gina; Bengoa, José Fernando; Marchetti, Sergio Gustavo; Vetere, Virginia

    2018-05-01

    Ni2P/Ni12P5 nanoparticles were obtained by thermal decomposition of nickel organometallic salt at low temperature. The use of different characterization techniques allowed us to determine that this process produced a mixture of two nickel phosphide phases: Ni2P and Ni12P5. These nickel phosphides nanoparticles, supported on mesoporous silica, showed activity and high selectivity for producing the hydrogenation of the acetophenone carbonyl group to obtain 1-phenylethanol. This is a first report that demonstrates the ability of supported Ni2P/Ni12P5 nanoparticles to produce the chemoselective hydrogenation of acetophenone. We attribute these special catalytic properties to the particular geometry of the Ni–P sites on the surface of the nanoparticles. This is an interesting result because the nickel phosphides have a wide composition range (from Ni3P to NiP3), with different crystallographic structures, therefore we think that different phases could be active and selective to hydrogenate many important molecules with more than one functional group.

  4. Rapid and accurate synthesis of TALE genes from synthetic oligonucleotides.

    PubMed

    Wang, Fenghua; Zhang, Hefei; Gao, Jingxia; Chen, Fengjiao; Chen, Sijie; Zhang, Cuizhen; Peng, Gang

    2016-01-01

    Custom synthesis of transcription activator-like effector (TALE) genes has relied upon plasmid libraries of pre-fabricated TALE-repeat monomers or oligomers. Here we describe a novel synthesis method that directly incorporates annealed synthetic oligonucleotides into the TALE-repeat units. Our approach utilizes iterative sets of oligonucleotides and a translational frame check strategy to ensure the high efficiency and accuracy of TALE-gene synthesis. TALE arrays of more than 20 repeats can be constructed, and the majority of the synthesized constructs have perfect sequences. In addition, this novel oligonucleotide-based method can readily accommodate design changes to the TALE repeats. We demonstrated an increased gene targeting efficiency against a genomic site containing a potentially methylated cytosine by incorporating non-conventional repeat variable di-residue (RVD) sequences.

  5. High efficient perovskite solar cell material CH3NH3PbI3: Synthesis of films and their characterization

    NASA Astrophysics Data System (ADS)

    Bera, Amrita Mandal; Wargulski, Dan Ralf; Unold, Thomas

    2018-04-01

    Hybrid organometal perovskites have been emerged as promising solar cell material and have exhibited solar cell efficiency more than 20%. Thin films of Methylammonium lead iodide CH3NH3PbI3 perovskite materials have been synthesized by two different (one step and two steps) methods and their morphological properties have been studied by scanning electron microscopy and optical microscope imaging. The morphology of the perovskite layer is one of the most important parameters which affect solar cell efficiency. The morphology of the films revealed that two steps method provides better surface coverage than the one step method. However, the grain sizes were smaller in case of two steps method. The films prepared by two steps methods on different substrates revealed that the grain size also depend on the substrate where an increase of the grain size was found from glass substrate to FTO with TiO2 blocking layer to FTO without any change in the surface coverage area. Present study reveals that an improved quality of films can be obtained by two steps method by an optimization of synthesis processes.

  6. Efficient Synthesis and Discovery of Schiff Bases as Potent Cholinesterase Inhibitors.

    PubMed

    Razik, Basma M Abd; Osman, Hasnah; Ezzat, Mohammed O; Basiri, Alireza; Salhin, Abdussalam; Kia, Yalda; Murugaiyah, Vikneswaran

    2016-01-01

    The search for new cholinesterase inhibitors is still a promising approach for management of Alzheimer`s disease. Schiff bases are considered as important class of organic compounds, which have wide range of applications including as enzyme inhibitors. In the present study, a new green ionic liquid mediated strategy was developed for convenient synthesis of two series of Schiff bases 3(a-j) and 5(a-j) as potential cholinesterase inhibitors using aromatic aldehydes and primary amines in [bmim]Br. The synthesized compounds were evaluated for their acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) inhibitory potential by modified Ellman's method. The molecular interactions between the most active compound and the enzyme were analyzed by molecular docking. Among them, 3j displayed higher inhibitory activities than reference drug, galanthamine, with IC50 values of 2.05 and 5.77 µM, for AChE and BChE, respectively. Interestingly, all the compounds except 3b displayed higher BChE inhibitions than galanthamine with IC50 values ranging from 5.77 to 18.52 µM. Molecular docking of compound 3j inside the TcAChE and hBChE completely coincided with the inhibitory activities observed. The compound forms strong hydrogen bonding at the peripheral anionic site of AChE whereas on BChE, it had hydrophobic and mild polar interactions. An efficient and eco-friendly synthetic methodology has been developed to synthesize Schiff bases in a very short reaction time and excellent yields in ionic solvent, whereby the compounds from series 3 showed promising cholinesterase inhibitory activity.

  7. Asymmetric Synthesis of Apratoxin E.

    PubMed

    Mao, Zhuo-Ya; Si, Chang-Mei; Liu, Yi-Wen; Dong, Han-Qing; Wei, Bang-Guo; Lin, Guo-Qiang

    2016-10-21

    An efficient method for asymmetric synthesis of apratoxin E 2 is described in this report. The chiral lactone 8, recycled from the degradation of saponin glycosides, was utilized to prepare the non-peptide fragment 6. In addition to this "from nature to nature" strategy, olefin cross-metathesis (CM) was applied as an alternative approach for the formation of the double bond. Moreover, pentafluorophenyl diphenylphosphinate was found to be an efficient condensation reagent for the macrocyclization.

  8. Catalyst-Free Difunctionalization of Activated Alkenes in Water: Efficient Synthesis of β-Keto Sulfides and Sulfones.

    PubMed

    Wang, Huamin; Wang, Guangyu; Lu, Qingquan; Chiang, Chien-Wei; Peng, Pan; Zhou, Jiufu; Lei, Aiwen

    2016-10-04

    Difunctionalization of activated alkenes, a powerful strategy in chemical synthesis, has been accomplished for direct synthesis of a series of β-keto sulfides and β-keto sulfones. The transformation, mediated by O2 , proceeds smoothly in water and without any catalyst. Prominent advantages of this method include mild reaction conditions, purification simplicity, and gram-scale synthesis, underlining the practical utility of this methodology. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Novel and Efficient Synthesis of the Promising Drug Candidate Discodermolide

    DTIC Science & Technology

    2010-02-01

    stereotriad building blocks for discodermolide and related polyketide antibiotics could be obtained from variations on a short, scalable scheme that did...chains required for the chemical synthesis of the nonaromatic polyketides is usually based on the iterative lengthening of an acyclic substituted chain...burden estimate or any other aspect of this collection of information, including suggestions for reducing this burden to Department of Defense

  10. An Eco-Friendly Improved Protocol for the Synthesis of Bis(3-indolyl)methanes Using Poly(4-vinylpyridinium)hydrogen Sulfate as Efficient, Heterogeneous, and Recyclable Solid Acid Catalyst

    PubMed Central

    Banothu, Janardhan; Gali, Rajitha; Velpula, Ravibabu; Bavantula, Rajitha; Crooks, Peter A.

    2013-01-01

    Highly efficient and eco-friendly protocol for the synthesis of bis(3-indolyl)methanes by the electrophilic substitution reaction of indole with aldehydes catalyzed by poly(4-vinylpyridinium)hydrogen sulfate was described. Excellent yields, shorter reaction times, simple work-up procedure, avoiding hazardous organic solvents, and reusability of the catalyst are the most obvious advantages of this method. PMID:24052864

  11. Spray-combustion synthesis: Efficient solution route to high-performance oxide transistors

    PubMed Central

    Yu, Xinge; Smith, Jeremy; Zhou, Nanjia; Zeng, Li; Guo, Peijun; Xia, Yu; Alvarez, Ana; Aghion, Stefano; Lin, Hui; Yu, Junsheng; Chang, Robert P. H.; Bedzyk, Michael J.; Ferragut, Rafael; Marks, Tobin J.; Facchetti, Antonio

    2015-01-01

    Metal-oxide (MO) semiconductors have emerged as enabling materials for next generation thin-film electronics owing to their high carrier mobilities, even in the amorphous state, large-area uniformity, low cost, and optical transparency, which are applicable to flat-panel displays, flexible circuitry, and photovoltaic cells. Impressive progress in solution-processed MO electronics has been achieved using methodologies such as sol gel, deep-UV irradiation, preformed nanostructures, and combustion synthesis. Nevertheless, because of incomplete lattice condensation and film densification, high-quality solution-processed MO films having technologically relevant thicknesses achievable in a single step have yet to be shown. Here, we report a low-temperature, thickness-controlled coating process to create high-performance, solution-processed MO electronics: spray-combustion synthesis (SCS). We also report for the first time, to our knowledge, indium-gallium-zinc-oxide (IGZO) transistors having densification, nanoporosity, electron mobility, trap densities, bias stability, and film transport approaching those of sputtered films and compatible with conventional fabrication (FAB) operations. PMID:25733848

  12. Spray-combustion synthesis: efficient solution route to high-performance oxide transistors.

    PubMed

    Yu, Xinge; Smith, Jeremy; Zhou, Nanjia; Zeng, Li; Guo, Peijun; Xia, Yu; Alvarez, Ana; Aghion, Stefano; Lin, Hui; Yu, Junsheng; Chang, Robert P H; Bedzyk, Michael J; Ferragut, Rafael; Marks, Tobin J; Facchetti, Antonio

    2015-03-17

    Metal-oxide (MO) semiconductors have emerged as enabling materials for next generation thin-film electronics owing to their high carrier mobilities, even in the amorphous state, large-area uniformity, low cost, and optical transparency, which are applicable to flat-panel displays, flexible circuitry, and photovoltaic cells. Impressive progress in solution-processed MO electronics has been achieved using methodologies such as sol gel, deep-UV irradiation, preformed nanostructures, and combustion synthesis. Nevertheless, because of incomplete lattice condensation and film densification, high-quality solution-processed MO films having technologically relevant thicknesses achievable in a single step have yet to be shown. Here, we report a low-temperature, thickness-controlled coating process to create high-performance, solution-processed MO electronics: spray-combustion synthesis (SCS). We also report for the first time, to our knowledge, indium-gallium-zinc-oxide (IGZO) transistors having densification, nanoporosity, electron mobility, trap densities, bias stability, and film transport approaching those of sputtered films and compatible with conventional fabrication (FAB) operations.

  13. Musical sound analysis/synthesis using vector-quantized time-varying spectra

    NASA Astrophysics Data System (ADS)

    Ehmann, Andreas F.; Beauchamp, James W.

    2002-11-01

    A fundamental goal of computer music sound synthesis is accurate, yet efficient resynthesis of musical sounds, with the possibility of extending the synthesis into new territories using control of perceptually intuitive parameters. A data clustering technique known as vector quantization (VQ) is used to extract a globally optimum set of representative spectra from phase vocoder analyses of instrument tones. This set of spectra, called a Codebook, is used for sinusoidal additive synthesis or, more efficiently, for wavetable synthesis. Instantaneous spectra are synthesized by first determining the Codebook indices corresponding to the best least-squares matches to the original time-varying spectrum. Spectral index versus time functions are then smoothed, and interpolation is employed to provide smooth transitions between Codebook spectra. Furthermore, spectral frames are pre-flattened and their slope, or tilt, extracted before clustering is applied. This allows spectral tilt, closely related to the perceptual parameter ''brightness,'' to be independently controlled during synthesis. The result is a highly compressed format consisting of the Codebook spectra and time-varying tilt, amplitude, and Codebook index parameters. This technique has been applied to a variety of harmonic musical instrument sounds with the resulting resynthesized tones providing good matches to the originals.

  14. Flow microreactor synthesis in organo-fluorine chemistry

    PubMed Central

    Nagaki, Aiichiro

    2013-01-01

    Summary Organo-fluorine compounds are the substances of considerable interest in various industrial fields due to their unique physical and chemical properties. Despite increased demand in wide fields of science, synthesis of fluoro-organic compounds is still often faced with problems such as the difficulties in handling of fluorinating reagents and in controlling of chemical reactions. Recently, flow microreactor synthesis has emerged as a new methodology for producing chemical substances with high efficiency. This review outlines the successful examples of synthesis and reactions of fluorine-containing molecules by the use of flow microreactor systems to overcome long-standing problems in fluorine chemistry. PMID:24367443

  15. The origin of polynucleotide-directed protein synthesis

    NASA Technical Reports Server (NTRS)

    Orgel, Leslie E.

    1989-01-01

    If protein synthesis evolved in an RNA world it was probably preceded by simpler processes by means of which interaction with amino acids conferred selective advantage on replicating RNA molecules. It is suggested that at first the simple attachment of amino acids to the 2'(3') termini of RNA templates favored initiation of replication at the end of the template rather than at internal positions. The second stage in the evolution of protein synthesis would probably have been the association of pairs of charged RNA adaptors in such a way as to favor noncoded formation of peptides. Only after this process had become efficient could coded synthesis have begun.

  16. Rumen microbial protein synthesis and nitrogen efficiency as affected by tanniferous and non-tanniferous forage legumes incubated individually or together in Rumen Simulation Technique.

    PubMed

    Grosse Brinkhaus, Anja; Bee, Giuseppe; Schwarm, Angela; Kreuzer, Michael; Dohme-Meier, Frigga; Zeitz, Johanna O

    2018-03-01

    A limited availability of microbial protein can impair productivity in ruminants. Ruminal nitrogen efficiency might be optimised by combining high-quality forage legumes such as red clover (RC), which has unfavourably high ruminal protein degradability, with tanniferous legumes like sainfoin (SF) and birdsfoot trefoil (BT). Silages from SF and from BT cultivars [Bull (BB) and Polom (BP)] were incubated singly or in combination with RC using the Rumen Simulation Technique (n = 6). The tanniferous legumes, when compared to RC, changed the total short-chain fatty acid profile by increasing propionate proportions at the expense of butyrate. Silage from SF contained the most condensed tannins (CTs) (136 g CT kg -1 dry matter) and clearly differed in various traits from the BT and RC silages. The apparent nutrient degradability (small with SF), microbial protein synthesis, and calculated content of potentially utilisable crude protein (large with SF) indicated that SF had the greatest efficiency in ruminal protein synthesis. The effects of combining SF with RC were mostly linear. The potential of sainfoin to improve protein supply, demonstrated either individually or in combination with a high-performance forage legume, indicates its potential usefulness in complementing protein-deficient ruminant diets and high-quality forages rich in rumen-degradable protein. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  17. Synthesis of Resveratrol Tetramers via a Stereoconvergent Radical Equilibrium

    PubMed Central

    Keylor, Mitchell H.; Matsuura, Bryan S.; Griesser, Markus; Chauvin, Jean-Philippe R.; Harding, Ryan A.; Kirillova, Mariia S.; Zhu, Xu; Fischer, Oliver J.; Pratt, Derek A.; Stephenson, Corey R. J.

    2017-01-01

    Persistent free radicals have become indispensable in the synthesis of organic materials by living radical polymerization. However, examples of their use in the synthesis of small molecules are rare. Herein, we report the application of persistent radical and quinone methide intermediates to the synthesis of the resveratrol tetramers nepalensinol B and vateriaphenol C. The spontaneous cleavage and reconstitution of exceptionally weak carbon-carbon bonds has enabled a stereoconvergent oxidative dimerization of racemic materials in a transformation that likely coincides with the biogenesis of these natural products. The efficient synthesis of higher-order oligomers of resveratrol will facilitate the biological studies necessary to elucidate their mechanism(s) of action. PMID:27940867

  18. Efficient synthesis of methylene exo-glycals: another use of glycosylthiomethyl chlorides.

    PubMed

    Zhu, Xiangming; Jin, Ying; Wickham, John

    2007-03-30

    A new approach to the synthesis of methylene exo-glycals is described. Oxidation of glycosylthiolmethyl chloride (GTM-Cl) with mCPBA afforded the corresponding glycosylchloromethyl sulfone in almost quantitative yield, which underwent KOtBu-induced Ramberg-Bäcklund rearrangement to furnish the desired methylene exo-glycal in excellent yield.

  19. Highly efficient molybdenum-based catalysts for enantioselective alkene metathesis

    PubMed Central

    Malcolmson, Steven J.; Meek, Simon J.; Sattely, Elizabeth S.; Schrock, Richard R.; Hoveyda, Amir H.

    2009-01-01

    Discovery of efficient catalysts is one of the most compelling objectives of modern chemistry. Chiral catalysts are in particularly high demand, as they facilitate synthesis of enantiomerically enriched small molecules that are critical to developments in medicine, biology and materials science1. Especially noteworthy are catalysts that promote—with otherwise inaccessible efficiency and selectivity levels—reactions demonstrated to be of great utility in chemical synthesis. Here we report a class of chiral catalysts that initiate alkene metathesis1 with very high efficiency and enantioselectivity. Such attributes arise from structural fluxionality of the chiral catalysts and the central role that enhanced electronic factors have in the catalytic cycle. The new catalysts have a stereogenic metal centre and carry only monodentate ligands; the molybdenum-based complexes are prepared stereoselectively by a ligand exchange process involving an enantiomerically pure aryloxide, a class of ligands scarcely used in enantioselective catalysis2,3. We demonstrate the application of the new catalysts in an enantioselective synthesis of the Aspidosperma alkaloid, quebrachamine, through an alkene metathesis reaction that cannot be promoted by any of the previously reported chiral catalysts. PMID:19011612

  20. DNA-Encoded Solid-Phase Synthesis: Encoding Language Design and Complex Oligomer Library Synthesis.

    PubMed

    MacConnell, Andrew B; McEnaney, Patrick J; Cavett, Valerie J; Paegel, Brian M

    2015-09-14

    The promise of exploiting combinatorial synthesis for small molecule discovery remains unfulfilled due primarily to the "structure elucidation problem": the back-end mass spectrometric analysis that significantly restricts one-bead-one-compound (OBOC) library complexity. The very molecular features that confer binding potency and specificity, such as stereochemistry, regiochemistry, and scaffold rigidity, are conspicuously absent from most libraries because isomerism introduces mass redundancy and diverse scaffolds yield uninterpretable MS fragmentation. Here we present DNA-encoded solid-phase synthesis (DESPS), comprising parallel compound synthesis in organic solvent and aqueous enzymatic ligation of unprotected encoding dsDNA oligonucleotides. Computational encoding language design yielded 148 thermodynamically optimized sequences with Hamming string distance ≥ 3 and total read length <100 bases for facile sequencing. Ligation is efficient (70% yield), specific, and directional over 6 encoding positions. A series of isomers served as a testbed for DESPS's utility in split-and-pool diversification. Single-bead quantitative PCR detected 9 × 10(4) molecules/bead and sequencing allowed for elucidation of each compound's synthetic history. We applied DESPS to the combinatorial synthesis of a 75,645-member OBOC library containing scaffold, stereochemical and regiochemical diversity using mixed-scale resin (160-μm quality control beads and 10-μm screening beads). Tandem DNA sequencing/MALDI-TOF MS analysis of 19 quality control beads showed excellent agreement (<1 ppt) between DNA sequence-predicted mass and the observed mass. DESPS synergistically unites the advantages of solid-phase synthesis and DNA encoding, enabling single-bead structural elucidation of complex compounds and synthesis using reactions normally considered incompatible with unprotected DNA. The widespread availability of inexpensive oligonucleotide synthesis, enzymes, DNA sequencing, and PCR

  1. Total Synthesis of Adunctin B.

    PubMed

    Dethe, Dattatraya H; Dherange, Balu D

    2018-03-16

    Total synthesis of (±)-adunctin B, a natural product isolated from Piper aduncum (Piperaceae), has been achieved using two different strategies, in seven and three steps. The efficient approach features highly atom economical and diastereoselective Friedel-Crafts acylation, alkylation reaction and palladium catalyzed Wacker type oxidative cyclization.

  2. Total synthesis of mycobacterial arabinogalactan containing 92 monosaccharide units

    NASA Astrophysics Data System (ADS)

    Wu, Yong; Xiong, De-Cai; Chen, Si-Cong; Wang, Yong-Shi; Ye, Xin-Shan

    2017-03-01

    Carbohydrates are diverse bio-macromolecules with highly complex structures that are involved in numerous biological processes. Well-defined carbohydrates obtained by chemical synthesis are essential to the understanding of their functions. However, synthesis of carbohydrates is greatly hampered by its insufficient efficiency. So far, assembly of long carbohydrate chains remains one of the most challenging tasks for synthetic chemists. Here we describe a highly efficient assembly of a 92-mer polysaccharide by the preactivation-based one-pot glycosylation protocol. Several linear and branched oligosaccharide/polysaccharide fragments ranging from 5-mer to 31-mer in length have been rapidly constructed in one-pot manner, which enables the first total synthesis of a biologically important mycobacterial arabinogalactan through a highly convergent [31+31+30] coupling reaction. Our results show that the preactivation-based one-pot glycosylation protocol may provide access to the construction of long and complicated carbohydrate chains.

  3. Templated synthesis of nickel nanoparticles: Toward heterostructured nanocomposites for efficient hydrogen storage

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Nelson, Nicholas Cole

    2013-01-01

    The world is currently facing an energy and environmental crisis for which new technologies are needed. Development of cost-competitive materials for catalysis and hydrogen storage on-board motor vehicles is crucial to lead subsequent generations into a more sustainable and energy independent future. This thesis presents work toward the scalable synthesis of bimetallic heterostructures that can enable hydrogen to compete with carbonaceous fuels by meeting the necessary gravimetric and volumetric energy densities and by enhancing hydrogen sorption/desorption kinetics near ambient temperatures and pressures. Utilizing the well-known phenomenon of hydrogen spillover, these bimetallic heterostructures could work by lowering the activation energy for hydrogenation and dehydrogenation of metals. Herein, we report a novel method for the scalable synthesis of silica templated zero-valent nickel particles (Nimore » $$\\subset$$ SiO 2) that hold promise for the synthesis of nickel nanorods for use in bimetallic heterostructures for hydrogen storage. Our synthesis proceeds by chemical reduction of a nickel-hydrazine complex with sodium borohydride followed by calcination under hydrogen gas to yield silica encapsulated nickel particles. Transmission electron microscopy and powder X-ray diffraction were used to characterize the general morphology of the resultant nanocapsules as well as the crystalline phases of the incorporated Ni 0 nanocrystals. The structures display strong magnetic behavior at room temperature and preliminary data suggests nickel particle size can be controlled by varying the amount of nickel precursor used in the synthesis. Calcination under different environments and TEM analysis provides evidence for an atomic migration mechanism of particle formation. Ni$$\\subset$$SiO 2 nanocapsules were used as seeds to induce heterogeneous nucleation and subsequent growth within the nanocapsule via electroless nickel plating. Nickel nanoparticle growth occurs under

  4. Facile Synthesis of Monodisperse Gold Nanocrystals Using Virola oleifera

    NASA Astrophysics Data System (ADS)

    Milaneze, Bárbara A.; Oliveira, Jairo P.; Augusto, Ingrid; Keijok, Wanderson J.; Côrrea, Andressa S.; Ferreira, Débora M.; Nunes, Otalíbio C.; Gonçalves, Rita de Cássia R.; Kitagawa, Rodrigo R.; Celante, Vinícius G.; da Silva, André Romero; Pereira, Ana Claudia H.; Endringer, Denise C.; Schuenck, Ricardo P.; Guimarães, Marco C. C.

    2016-10-01

    The development of new routes and strategies for nanotechnology applications that only employ green synthesis has inspired investigators to devise natural systems. Among these systems, the synthesis of gold nanoparticles using plant extracts has been actively developed as an alternative, efficient, cost-effective, and environmentally safe method for producing nanoparticles, and this approach is also suitable for large-scale synthesis. This study reports reproducible and completely natural gold nanocrystals that were synthesized using Virola oleifera extract. V. oleifera resin is rich in epicatechin, ferulic acid, gallic acid, and flavonoids (i.e., quercetin and eriodictyol). These gold nanoparticles play three roles. First, these nanoparticles exhibit remarkable stability based on their zeta potential. Second, these nanoparticles are functionalized with flavonoids, and third, an efficient, economical, and environmentally friendly mechanism can be employed to produce green nanoparticles with organic compounds on the surface. Our model is capable of reducing the resin of V. oleifera, which creates stability and opens a new avenue for biological applications. This method does not require painstaking conditions or hazardous agents and is a rapid, efficient, and green approach for the fabrication of monodisperse gold nanoparticles.

  5. Anchoring of Cu(II) onto surface of porous metal-organic framework through post-synthesis modification for the synthesis of benzimidazoles and benzothiazoles

    NASA Astrophysics Data System (ADS)

    Kardanpour, Reihaneh; Tangestaninejad, Shahram; Mirkhani, Valiollah; Moghadam, Majid; Mohammadpoor-Baltork, Iraj; Zadehahmadi, Farnaz

    2016-03-01

    Efficient synthesis of various benzimidazoles and benzothiazoles under mild conditions catalyzed by Cu(II) anchored onto UiO-66-NH2 metal organic framework is reported. In this manner, first, the aminated UiO-66 was modified with thiophene-2-carbaldehyde and then the prepared Schiff base was reacted with CuCl2. The prepared catalyst was characterized by FT-IR, UV-vis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). The UiO-66-NH2-TC-Cu was applied as a highly efficient catalyst for synthesis of benzimidazole and benzothiazole derivatives by the reaction of aldehydes with 1,2-diaminobenzene or 2-aminothiophenol. The Cu(II)-containing MOF was reused several times without any appreciable loss of its efficiency.

  6. Stereoselective heterocycle synthesis through oxidative carbon-hydrogen bond activation.

    PubMed

    Liu, Lei; Floreancig, Paul E

    2010-01-01

    Heterocycles are ubiquitous structures in both drugs and natural products, and efficient methods for their construction are being pursued constantly. Carbon-hydrogen bond activation offers numerous advantages for the synthesis of heterocycles with respect to minimizing the length of synthetic routes and reducing waste. As interest in chiral medicinal leads increases, stereoselective methods for heterocycle synthesis must be developed. The use of carbon-hydrogen bond activation reactions for stereoselective heterocycle synthesis has produced a range of creative transformations that provide a wide array of structural motifs, selected examples of which are described in this review.

  7. One-Step Nickel Foam Assisted Synthesis of Holey G-Carbon Nitride Nanosheets for Efficient Visible-light Photocatalytic H2 Evolution.

    PubMed

    Fang, Zhenyuan; Hong, Yuanzhi; Li, Di; Luo, Bifu; Mao, Baodong; Shi, Weidong

    2018-06-01

    Graphitic carbon nitride (g-C3N4) with layered structure represents one of the most promising metal-free photocatalysts. As yet, the direct one-step synthesis of ultrathin g-C3N4 nanosheets remains a challenge. Here, few-layered holey g-C3N4 nanosheets (CNS) were fabricated by simply introducing a piece of nickel foam over the precursors during the heating process. The as-prepared CNS with unique structural advantages exhibited superior photocatalytic water splitting activity (1871.09 µmol h-1 g-1) than bulk g-C3N4 (BCN) under visible light (λ>420 nm) (≈31 fold). Its outstanding photocatalytic performance originated from the high specific surface area (240.34 m2 g-1) and mesoporous structure, which endows CNS with more active sites, efficient exciton dissociation and prolonged charge carrier lifetime. Moreover, the obvious up-shift of the conduction band leads to a larger thermodynamic driving force for photocatalytic proton reduction. This methodology not only had the advantages for the direct and green synthesis of g-C3N4 nanosheets, but also paved a new avenue to modify molecular structure and textural of g-C3N4 for advanced applications.

  8. A review on green synthesis of silver nanoparticles and their applications.

    PubMed

    Rafique, Muhammad; Sadaf, Iqra; Rafique, M Shahid; Tahir, M Bilal

    2017-11-01

    Development of reliable and eco-accommodating methods for the synthesis of nanoparticles is a vital step in the field of nanotechnology. Silver nanoparticles are important because of their exceptional chemical, physical, and biological properties, and hence applications. In the last decade, numerous efforts were made to develop green methods of synthesis to avoid the hazardous byproducts. This review describes the methods of green synthesis for Ag-NPs and their numerous applications. It also describes the comparison of efficient synthesis methods via green routes over physical and chemical methods, which provide strong evidence for the selection of suitable method for the synthesis of Ag-NPs.

  9. Reduction of unsaturated compounds under interstellar conditions: chemoselective reduction of C≡C and C=C bonds over C=O functional group

    NASA Astrophysics Data System (ADS)

    Jonusas, Mindaugas; Guillemin, Jean-Claude; Krim, Lahouari

    2017-07-01

    The knowledge of the H-addition reactions on unsaturated organic molecules bearing a triple or a double carbon-carbon bond such as propargyl or allyl alcohols and a CO functional group such as propynal, propenal or propanal may play an important role in the understanding of the chemical complexity of the interstellar medium. Why different aldehydes like methanal, ethanal, propynal and propanal are present in dense molecular clouds while the only alcohol detected in those cold regions is methanol? In addition, ethanol has only been detected in hot molecular cores. Are those saturated and unsaturated aldehyde and alcohol species chemically linked in molecular clouds through solid phase H-addition surface reactions or are they formed through different chemical routes? To answer such questions, we have investigated a hydrogenation study of saturated and unsaturated aldehydes and alcohols at 10 K. We prove through this experimental study that while pure unsaturated alcohol ices bombarded by H atoms lead to the formation of the corresponding fully or partially saturated alcohols, surface H-addition reactions on unsaturated aldehyde ices exclusively lead to the formation of fully saturated aldehyde. Such results show that in addition to a chemoselective reduction of C≡C and C=C bonds over the C=O group, there is no link between aldehydes and their corresponding alcohols in reactions involving H atoms in dense molecular clouds. Consequently, this could be one of the reasons why some aldehydes such as propanal are abundant in dense molecular clouds in contrast to the non-detection of alcohol species larger than methanol.

  10. Eco-Efficient Synthesis of Highly Porous CoCO3 Anodes from Supercritical CO2 for Li+ and Na+ Storage.

    PubMed

    Li, Hui-Ying; Tseng, Chuan-Ming; Yang, Cheng-Hsien; Lee, Tai-Chou; Su, Ching-Yuan; Hsieh, Chien-Te; Chang, Jeng-Kuei

    2017-06-09

    An eco-efficient synthetic route for the preparation of high-performance carbonate anodes for Li + and Na + batteries is developed. With supercritical CO 2 (scCO 2 ) as the precursor, which has gas-like diffusivity, extremely low viscosity, and near-zero surface tension, CoCO 3 particles are uniformly formed and tightly connected on graphene nanosheets (GNSs). This synthesis can be conducted at 50 °C, which is considerably lower than the temperature required for conventional preparation methods, minimizing energy consumption. The obtained CoCO 3 particles (ca. 20 nm in diameter), which have a unique interpenetrating porous structure, can increase the number of electroactive sites, promote electrolyte accessibility, shorten ion diffusion length, and readily accommodate the strain generated upon charging/discharging. With a reversible capacity of 1105 mAh g -1 , the proposed CoCO 3 /GNS anode shows an excellent rate capability, as it can deliver 745 mAh g -1 in 7.5 min. More than 98 % of the initial capacity is retained after 200 cycles. These properties are clearly superior to those of previously reported CoCO 3 -based electrodes for Li + storage, indicating the merit of our scCO 2 -based synthesis, which is facile, green, and can be easily scaled up for mass production. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. α-Oxo-Ketenimines from Isocyanides and α-Haloketones: Synthesis and Divergent Reactivity.

    PubMed

    Mamboury, Mathias; Wang, Qian; Zhu, Jieping

    2017-09-18

    The palladium-catalyzed reaction of α-haloketones with isocyanides afforded α-oxo-ketenimines through β-hydride elimination of the β-oxo-imidoyl palladium intermediates. Reaction of these relatively stable α-oxo-ketenimines with nucleophiles such as hydrazines, hydrazoic acid, amines, and Grignard reagent afforded pyrazoles, tetrazole, β-keto amidines, and enaminone, respectively, with high chemoselectivity. Whereas amines attack exclusively on the ketenimine functions, the formal [3+2] cycloaddition between N-monosubstituted hydrazines and α-oxo-ketenimines was initiated by nucleophilic addition to the carbonyl group. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Stereoselectivity in N-Iminium Ion Cyclization: Development of an Efficient Synthesis of (±)-Cephalotaxine.

    PubMed

    Liu, Hao; Yu, Jing; Li, Xinyu; Yan, Rui; Xiao, Ji-Chang; Hong, Ran

    2015-09-18

    A stereoselective N-iminium ion cyclization with allylsilane to construct vicinal quaternary-tertiary carbon centers was developed for the concise synthesis of (±)-cephalotaxine. The current strategy features a TiCl4-promoted cyclization and ring-closure metathesis to furnish the spiro-ring system. The stereochemical outcome in the N-acyliminium ion cyclization was rationalized by the stereoelectronic effect of the Z- or E-allylsilane. Two diastereomers arising from the cyclization were merged into the formal synthesis of (±)-cephalotaxine.

  13. Indium-mediated asymmetric Barbier-type propargylations: additions to aldehydes and ketones and mechanistic investigation of the organoindium reagents.

    PubMed

    Haddad, Terra D; Hirayama, Lacie C; Buckley, Jannise J; Singaram, Bakthan

    2012-01-20

    We report a simple, efficient, and general method for the indium-mediated enantioselective propargylation of aromatic and aliphatic aldehydes under Barbier-type conditions in a one-pot synthesis affording the corresponding chiral alcohol products in very good yield (up to 90%) and enantiomeric excess (up to 95%). The extension of this methodology to ketones demonstrated the need for electrophilic ketones more reactive than acetophenone as the reaction would not proceed with just acetophenone. Using the Lewis acid indium triflate [In(OTf)(3)] induced regioselective formation of the corresponding homoallenic alcohol product from acetophenone. However, this methodology demonstrated excellent chemoselectivity in formation of only the corresponding secondary homopropargylic alcohol product in the presence of a ketone functionality. Investigation of the organoindium intermediates under our reaction conditions shows the formation of allenylindium species, and we suggest that these species contain an indium(III) center. In addition, we have observed the presence of a shiny, indium(0) nugget throughout the reaction, irrespective of the stoichiometry, indicating disproportionation of indium halide byproduct formed during the reaction.

  14. Design and Stereoselective Preparation of a New Class of Chiral Olefin Metathesis Catalysts and Application to Enantioselective Synthesis of Quebrachamine: Catalyst Development Inspired by Natural Product Synthesis

    PubMed Central

    Sattely, Elizabeth S.; Meek, Simon J.; Malcolmson, Steven J.; Schrock, Richard R.; Hoveyda, Amir H.

    2010-01-01

    A total synthesis of the Aspidosperma alkaloid quebrachamine in racemic form is first described. A key catalytic ring-closing metathesis of an achiral triene is used to establish the all-carbon quaternary stereogenic center and the tetracyclic structure of the natural product; the catalytic transformation proceeds with reasonable efficiency through the use of existing achiral Ru or Mo catalysts. Ru- or Mo-based chiral olefin metathesis catalysts have proven to be inefficient and entirely nonselective in cases where the desired product is observed. In the present study, the synthesis route thus serves as a platform for the discovery of new olefin metathesis catalysts that allow for efficient completion of an enantioselective synthesis of quebrachamine. Accordingly, on the basis of mechanistic principles, stereogenic-at-Mo complexes bearing only monodentate ligands have been designed. The new catalysts provide significantly higher levels of activity than observed with the previously reported Ru- or Mo-based complexes. Enantiomerically enriched chiral alkylidenes are generated through diastereoselective reactions involving achiral Mo-based bispyrrolides and enantiomerically pure silyl-protected binaphthols. Such chiral catalysts initiate the key enantioselective ring-closing metathesis step in the total synthesis of quebrachamine efficiently (1 mol % loading, 22 °C, 1 h, >98% conversion, 84% yield) and with high selectivity (98:2 er, 96% ee). PMID:19113867

  15. Integrating theory, synthesis, spectroscopy and device efficiency to design and characterize donor materials for organic photovoltaics: a case study including 12 donors

    DOE PAGES

    Oosterhout, S. D.; Kopidakis, N.; Owczarczyk, Z. R.; ...

    2015-04-07

    There have been remarkable improvements in the power conversion efficiency of solution-processable Organic Photovoltaics (OPV) have largely been driven by the development of novel narrow bandgap copolymer donors comprising an electron-donating (D) and an electron-withdrawing (A) group within the repeat unit. The large pool of potential D and A units and the laborious processes of chemical synthesis and device optimization, has made progress on new high efficiency materials slow with a few new efficient copolymers reported every year despite the large number of groups pursuing these materials. In our paper we present an integrated approach toward new narrow bandgap copolymersmore » that uses theory to guide the selection of materials to be synthesized based on their predicted energy levels, and time-resolved microwave conductivity (TRMC) to select the best-performing copolymer–fullerene bulk heterojunction to be incorporated into complete OPV devices. We validate our methodology by using a diverse group of 12 copolymers, including new and literature materials, to demonstrate good correlation between (a) theoretically determined energy levels of polymers and experimentally determined ionization energies and electron affinities and (b) photoconductance, measured by TRMC, and OPV device performance. The materials used here also allow us to explore whether further copolymer design rules need to be incorporated into our methodology for materials selection. For example, we explore the effect of the enthalpy change (ΔH) during exciton dissociation on the efficiency of free charge carrier generation and device efficiency and find that ΔH of -0.4 eV is sufficient for efficient charge generation.« less

  16. Combustion and Plasma Synthesis of High Temperature Materials

    DTIC Science & Technology

    1989-10-01

    photodetectors were constructed having tin oxide electrodes deposited under more and less severe condi- tions. The relative quantum efficiencies of these de ...PROPAGATING REACTION PROCESS 19 N. Sata, N. Sanada, T. Hirano, and M. Nilno COMBUSTION SYNTHESIS OF OXIDE -CARBIDE COMPOSITES L. L. Wang, Z. A. Munir, and J...SYNTHESIS OF CERAMIC POWDERS J. S. McFeaters and J. J. Moore 46 DEVELOPMENT OF TIN OXIDE COATINGS FOR USE AS ELECTRODES IN MERCURIC IODIDE

  17. NAP enzyme recruitment in simultaneous bioremediation and nanoparticles synthesis.

    PubMed

    Eltarahony, Marwa; Zaki, Sahar; Kheiralla, Zeinab; Abd-El-Haleem, Desouky

    2018-06-01

    The periplasmic nitrate reductase enzyme (NAP) has become attractive catalyst, whose exploitation has emerged as one of the indispensable strategies toward environmentally benign applications. To achieve them efficiently and overcome the sensitivity of NAP in harsh environmental circumstances, the immobilization for denitrifying bacteria and NAP enzyme for simultaneous bioremediation and bionanoparticles synthesis was studied. NAP catalyzed NO 3 - reduction at V max of 0.811 μM/min and K m of 14.02 mM. Concurrently, the immobilized MMT cells completely removed NO 3 - upon 192 h with AgNPs synthesis ranging from 23.26 to 58.14 nm as indicated by SEM. Wherase, immobilized NAP exhibited lower efficiency with 28.6% of NO 3 - elimination within 288 h and large aggregated AgNPs ranging from 94.44 nm to 172.22 nm. To the best of author knowledge, the immobilization for denitrifying bacteria and NAP enzyme for simultaneous bioremediation and bionanoparticles synthesis was not studied before.

  18. AutoBayes Program Synthesis System System Internals

    NASA Technical Reports Server (NTRS)

    Schumann, Johann Martin

    2011-01-01

    This lecture combines the theoretical background of schema based program synthesis with the hands-on study of a powerful, open-source program synthesis system (Auto-Bayes). Schema-based program synthesis is a popular approach toward program synthesis. The lecture will provide an introduction into this topic and discuss how this technology can be used to generate customized algorithms. The synthesis of advanced numerical algorithms requires the availability of a powerful symbolic (algebra) system. Its task is to symbolically solve equations, simplify expressions, or to symbolically calculate derivatives (among others) such that the synthesized algorithms become as efficient as possible. We will discuss the use and importance of the symbolic system for synthesis. Any synthesis system is a large and complex piece of code. In this lecture, we will study Autobayes in detail. AutoBayes has been developed at NASA Ames and has been made open source. It takes a compact statistical specification and generates a customized data analysis algorithm (in C/C++) from it. AutoBayes is written in SWI Prolog and many concepts from rewriting, logic, functional, and symbolic programming. We will discuss the system architecture, the schema libary and the extensive support infra-structure. Practical hands-on experiments and exercises will enable the student to get insight into a realistic program synthesis system and provides knowledge to use, modify, and extend Autobayes.

  19. A 15-Step Synthesis of (+)-Ryanodol

    PubMed Central

    Chuang, Kangway V.; Xu, Chen; Reisman, Sarah E.

    2017-01-01

    (+)-Ryanodine and (+)-ryanodol are complex diterpenoids that modulate intracellular Ca2+ release at ryanodine receptors, ion channels critical for skeletal and cardiac muscle excitation–contraction coupling and synaptic transmission. Chemical derivatization of these diterpenoids has demonstrated that certain peripheral structural modifications can alter binding affinity and selectivity among ryanodine receptor isoforms. Here we report a short chemical synthesis of (+)-ryanodol that proceeds in only 15 steps from the commercially available terpene (S)-pulegone. The efficiency of the synthesis derives from the use of a Pauson-Khand reaction to rapidly build the carbon framework, and a remarkable SeO2-mediated oxidation to install three oxygen atoms in single step. This work highlights how strategic C–O bond constructions can streamline the synthesis of poly-hydroxylated terpenes by minimizing protecting group and redox adjustments. PMID:27563092

  20. Seedless synthesis and efficient recyclable catalytic activity of Ag@Fe nanocomposites towards methyl orange

    NASA Astrophysics Data System (ADS)

    Alzahrani, Salma Ahmed; Malik, Maqsood Ahmad; Al-Thabaiti, Shaeel Ahmed; Khan, Zaheer

    2018-03-01

    This work demonstrates a competitive reduction method of synthesis of nanomaterials. In this method along cetyltrimethylammonium bromide (CTAB), the reduction of Ag+ and Fe3+ ions is achieved by ascorbic acid-to-bimetallic Ag@Fe yellow-colored nanomaterials. The shape of UV-visible spectra and wavelengths absorbed of Ag@Fe can be tuned from ca. 290-600 nm by controlling [CTAB] and [Ag+]. The apparent first-order rate constants were calculated within the approximation of 6.1 × 10-3 s-1. The as-prepared Ag@Fe NPs have been found to be very important catalyst in terms of depredate methyl orange in vicinity of sodium borohydride (NaBH4), which exhibits excellent efficiency and re-usability in the prototypical reaction. The cmc of cationic surfactant CTAB has been determined by conductivity method under different experimental conditions. In the presence of CTAB, Ag+ and Fe3+ ions reduce to Ag@Fe core/shell nanoparticles, comprehend a change in wavelength and intensity of SRP band. The apparent first-order rate constant, activation energy, and turnover frequency for the methyl orange reduction catalyzed by Ag@Fe NPs were found to be 1.6 × 10-3 s-1, 58.2 kJ mol-1, and 1.1 × 10-3 s-1, respectively.

  1. Enantioselective synthesis of pactamycin, a complex antitumor antibiotic.

    PubMed

    Malinowski, Justin T; Sharpe, Robert J; Johnson, Jeffrey S

    2013-04-12

    Medicinal application of many complex natural products is precluded by the impracticality of their chemical synthesis. Pactamycin, the most structurally intricate aminocyclopentitol antibiotic, displays potent antiproliferative properties across multiple phylogenetic domains, but it is highly cytotoxic. A limited number of analogs produced by genetic engineering technologies show reduced cytotoxicity against mammalian cells, renewing promise for therapeutic applications. For decades, an efficient synthesis of pactamycin amenable to analog derivatizations has eluded researchers. Here, we present a short asymmetric total synthesis of pactamycin. An enantioselective Mannich reaction and symmetry-breaking reduction sequence was designed to enable assembly of the entire carbon core skeleton in under five steps and control critical three-dimensional (stereochemical) functional group relationships. This modular route totals 15 steps and is immediately amenable for structural analog synthesis.

  2. Ultrasonic activated efficient synthesis of chromenes using amino-silane modified Fe3O4 nanoparticles: A versatile integration of high catalytic activity and facile recovery

    NASA Astrophysics Data System (ADS)

    Safari, Javad; Zarnegar, Zohre

    2014-08-01

    An efficient synthesis of 2-amino-4H-chromenes is achieved by one pot three component coupling reaction of aldehyde, malononitrile, and resorcinol using amino-silane modified Fe3O4 nanoparticles (MNPs-NH2) heterogeneous nanocatalyst under sonic condition. The attractive advantages of the present process are mild reaction conditions, short reaction times, easy isolation of products, good yields and simple operational procedures. Combination of the advantages of ultrasonic irradiation and magnetic nanoparticles provides important methodology to carry out catalytic transformations.

  3. The Use of Aryl Hydrazide Linkers for the Solid Phase Synthesis of Chemically Modified Peptides

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Woo, Y; Mitchell, A R; Camarero, J A

    2006-11-03

    Since Merrifield introduced the concept of solid phase synthesis in 1963 for the rapid preparation of peptides, a large variety of different supports and resin-linkers have been developed that improve the efficiency of peptide assembly and expand the myriad of synthetically feasible peptides. The aryl hydrazide is one of the most useful resin-linkers for the synthesis of chemically modified peptides. This linker is completely stable during Boc- and Fmoc-based solid phase synthesis and yet it can be cleaved under very mild oxidative conditions. The present article reviews the use of this valuable linker for the rapid and efficient synthesis ofmore » C-terminal modified peptides, head-to-tail cyclic peptides and lipidated peptides.« less

  4. Witting Reaction Using a Stabilized Phosphorus Ylid: An Efficient and Stereoselective Synthesis of Ethyl Trans-Cinnamate

    ERIC Educational Resources Information Center

    Speed, Traci J.; Mclntyre, Jean P.; Thamattoor, Dasan M.

    2004-01-01

    An instructive experiment for the synthesis of ethyl trans-cinnamate, a pleasant smelling ester used in perfumery and flavoring by the reaction of benzaldehyde with the stable ylid triphenylphosphorane is described. The synthesis, workup and characterization of trans-cinnamate may be accomplished in a single laboratory session with commonly…

  5. Design synthesis and optimization of permanent magnet synchronous machines based on computationally-efficient finite element analysis

    NASA Astrophysics Data System (ADS)

    Sizov, Gennadi Y.

    In this dissertation, a model-based multi-objective optimal design of permanent magnet ac machines, supplied by sine-wave current regulated drives, is developed and implemented. The design procedure uses an efficient electromagnetic finite element-based solver to accurately model nonlinear material properties and complex geometric shapes associated with magnetic circuit design. Application of an electromagnetic finite element-based solver allows for accurate computation of intricate performance parameters and characteristics. The first contribution of this dissertation is the development of a rapid computational method that allows accurate and efficient exploration of large multi-dimensional design spaces in search of optimum design(s). The computationally efficient finite element-based approach developed in this work provides a framework of tools that allow rapid analysis of synchronous electric machines operating under steady-state conditions. In the developed modeling approach, major steady-state performance parameters such as, winding flux linkages and voltages, average, cogging and ripple torques, stator core flux densities, core losses, efficiencies and saturated machine winding inductances, are calculated with minimum computational effort. In addition, the method includes means for rapid estimation of distributed stator forces and three-dimensional effects of stator and/or rotor skew on the performance of the machine. The second contribution of this dissertation is the development of the design synthesis and optimization method based on a differential evolution algorithm. The approach relies on the developed finite element-based modeling method for electromagnetic analysis and is able to tackle large-scale multi-objective design problems using modest computational resources. Overall, computational time savings of up to two orders of magnitude are achievable, when compared to current and prevalent state-of-the-art methods. These computational savings allow

  6. Diazo Compounds: Versatile Tools for Chemical Biology.

    PubMed

    Mix, Kalie A; Aronoff, Matthew R; Raines, Ronald T

    2016-12-16

    Diazo groups have broad and tunable reactivity. That and other attributes endow diazo compounds with the potential to be valuable reagents for chemical biologists. The presence of diazo groups in natural products underscores their metabolic stability and anticipates their utility in a biological context. The chemoselectivity of diazo groups, even in the presence of azido groups, presents many opportunities. Already, diazo compounds have served as chemical probes and elicited novel modifications of proteins and nucleic acids. Here, we review advances that have facilitated the chemical synthesis of diazo compounds, and we highlight applications of diazo compounds in the detection and modification of biomolecules.

  7. Emulating the logic of monoterpenoid alkaloid biogenesis to access a skeletally diverse chemical library.

    PubMed

    Liu, Song; Scotti, John S; Kozmin, Sergey A

    2013-09-06

    We have developed a synthetic strategy that mimics the diversity-generating power of monoterpenoid indole alkaloid biosynthesis. Our general approach goes beyond diversification of a single natural product-like substructure and enables production of a highly diverse collection of small molecules. The reaction sequence begins with rapid and highly modular assembly of the tetracyclic indoloquinolizidine core, which can be chemoselectively processed into several additional skeletally diverse structural frameworks. The general utility of this approach was demonstrated by parallel synthesis of two representative chemical libraries containing 847 compounds with favorable physicochemical properties to enable its subsequent broad pharmacological evaluation.

  8. High-yielding continuous-flow synthesis of antimalarial drug hydroxychloroquine

    PubMed Central

    Telang, Nakul S; Kong, Caleb J; Verghese, Jenson; Gilliland III, Stanley E; Ahmad, Saeed; Dominey, Raymond N

    2018-01-01

    Numerous synthetic methods for the continuous preparation of fine chemicals and active pharmaceutical ingredients (API’s) have been reported in recent years resulting in a dramatic improvement in process efficiencies. Herein we report a highly efficient continuous synthesis of the antimalarial drug hydroxychloroquine (HCQ). Key improvements in the new process include the elimination of protecting groups with an overall yield improvement of 52% over the current commercial process. The continuous process employs a combination of packed bed reactors with continuous stirred tank reactors for the direct conversion of the starting materials to the product. This high-yielding, multigram-scale continuous synthesis provides an opportunity to achieve increase global access to hydroxychloroquine for treatment of malaria. PMID:29623120

  9. Rapid Size- Controlled Synthesis of Dextran-Coated, Copper-Doped Iron Oxide Nanoparticles

    NASA Astrophysics Data System (ADS)

    Wong, Ray M.

    2011-12-01

    Development of dual modality probes enabled for magnetic resonance imaging (MRI) and positron emission tomography (PET) has been on the rise in recent years due to the potential for these probes to facilitate combining the complementary high resolution of MRI and the high sensitivity of PET. The efficient synthesis of multimodal probes that include the radiolabels for PET can be hindered due to prolonged reaction times during radioisotope incorporation, and the resulting decay of the radiolabel. Along with a time-efficient synthesis, one also needs an optimal synthesis that yields products in a desirable size range (between 20-100 nm) to increase blood retention time. In this work, we describe a novel, rapid, microwave-based synthesis of dextran-coated iron oxide nanoparticles doped with copper (DIO/Cu). Traditional methods for synthesizing dextran-coated iron oxide particles require refluxing for 2 hours and result in approximately 50 nm particles. We demonstrate that microwave synthesis can produce 50 nm nanoparticles in 5 minutes of heating. We discuss the various parameters used in the microwave synthesis protocol to vary the size distribution of DIO/Cu, and demonstrate the successful incorporation of copper into these particles with the aim of future use for rapid 64Cu incorporation.

  10. The rate of polymerase release upon filling the gap between Okazaki fragments is inadequate to support cycling during lagging strand synthesis.

    PubMed

    Dohrmann, Paul R; Manhart, Carol M; Downey, Christopher D; McHenry, Charles S

    2011-11-18

    Upon completion of synthesis of an Okazaki fragment, the lagging strand replicase must recycle to the next primer at the replication fork in under 0.1 s to sustain the physiological rate of DNA synthesis. We tested the collision model that posits that cycling is triggered by the polymerase encountering the 5'-end of the preceding Okazaki fragment. Probing with surface plasmon resonance, DNA polymerase III holoenzyme initiation complexes were formed on an immobilized gapped template. Initiation complexes exhibit a half-life of dissociation of approximately 15 min. Reduction in gap size to 1 nt increased the rate of dissociation 2.5-fold, and complete filling of the gap increased the off-rate an additional 3-fold (t(1/2)~2 min). An exogenous primed template and ATP accelerated dissociation an additional 4-fold in a reaction that required complete filling of the gap. Neither a 5'-triphosphate nor a 5'-RNA terminated oligonucleotide downstream of the polymerase accelerated dissociation further. Thus, the rate of polymerase release upon gap completion and collision with a downstream Okazaki fragment is 1000-fold too slow to support an adequate rate of cycling and likely provides a backup mechanism to enable polymerase release when the other cycling signals are absent. Kinetic measurements indicate that addition of the last nucleotide to fill the gap is not the rate-limiting step for polymerase release and cycling. Modest (approximately 7 nt) strand displacement is observed after the gap between model Okazaki fragments is filled. To determine the identity of the protein that senses gap filling to modulate affinity of the replicase for the template, we performed photo-cross-linking experiments with highly reactive and non-chemoselective diazirines. Only the α subunit cross-linked, indicating that it serves as the sensor. Copyright © 2011 Elsevier Ltd. All rights reserved.

  11. Synthesis of the human insulin gene. Part III. Chemical synthesis of 5'-phosphomonoester group containing deoxyribooligonucleotides by the modified phosphotriester method. Its application in the synthesis of seventeen fragments constituting human insulin C-chain DNA.

    PubMed Central

    Hsiung, H M; Sung, W L; Brousseau, R; Wu, R; Narang, S A

    1980-01-01

    A method for phosphorylating a protected deoxyribooligonucleotide containing phosphotriester linkages is described. The modified phosphotriester method of chemical synthesis is further refined in terms of (i) better final deblocking conditions and (ii) new chromatography solvent systems containing acetone-water-ethyl acetate to yield pure oligomers. The effectiveness of these improvements has been demonstrated in the rapid and efficient synthesis of seventeen fragments constituting the sequence of human insulin C-chain DNA. Images PMID:7008029

  12. Efficient Hydrogenation of Ketones and Aldehydes Catalyzed by Well-Defined Iron(II) PNP Pincer Complexes: Evidence for an Insertion Mechanism

    PubMed Central

    2014-01-01

    We have prepared and structurally characterized a new class of Fe(II) PNP pincer hydride complexes [Fe(PNP-iPr)(H)(CO)(L)]n (L = Br–, CH3CN, pyridine, PMe3, SCN–, CO, BH4–; n = 0, +1) based on the 2,6-diaminopyridine scaffold where the PiPr2 moieties of the PNP ligand are connected to the pyridine ring via NH and/or NMe spacers. Complexes [Fe(PNP-iPr)(H)(CO)(L)]n with labile ligands (L = Br–, CH3CN, BH4–) and NH spacers are efficient catalysts for the hydrogenation of both ketones and aldehydes to alcohols under mild conditions, while those containing inert ligands (L = pyridine, PMe3, SCN–, CO) are catalytically inactive. Interestingly, complex [Fe(PNPMe-iPr)(H)(CO)(Br)], featuring NMe spacers, is an efficient catalyst for the chemoselective hydrogenation of aldehydes. The first type of complexes involves deprotonation of the PNP ligand as well as heterolytic dihydrogen cleavage via metal-alkoxide cooperation, but no reversible aromatization/deprotonation of the PNP ligand. In the case of the N-methylated complex the mechanism remains unclear, but obviously does not allow bifunctional activation of dihydrogen. The experimental results complemented by DFT calculations strongly support an insertion of the C=O bond of the carbonyl compound into the Fe–H bond. PMID:27642211

  13. Synthesis and antiproliferative activity of two diastereomeric lignan amides serving as dimeric caffeic acid-l-DOPA hybrids.

    PubMed

    Magoulas, George E; Rigopoulos, Andreas; Piperigkou, Zoi; Gialeli, Chrysostomi; Karamanos, Nikos K; Takis, Panteleimon G; Troganis, Anastassios N; Chrissanthopoulos, Athanassios; Maroulis, George; Papaioannou, Dionissios

    2016-06-01

    Two new diastereomeric lignan amides (4 and 5) serving as dimeric caffeic acid-l-DOPA hybrids were synthesized. The synthesis involved the FeCl3-mediated phenol oxidative coupling of methyl caffeate to afford trans-diester 1a as a mixture of enantiomers, protection of the catechol units, regioselective saponification, coupling with a suitably protected l-DOPA derivative, separation of the two diastereomers thus obtained by flash column chromatography and finally global chemoselective deprotection of the catechol units. The effect of hybrids 4 and 5 and related compounds on the proliferation of two breast cancer cell lines with different metastatic potential and estrogen receptor status (MDA-MB-231 and MCF-7) and of one epithelial lung cancer cell line, namely A-549, was evaluated for concentrations ranging from 1 to 256μM and periods of treatment of 24, 48 and 72h. Both hybrids showed interesting and almost equipotent antiproliferative activities (IC50 64-70μM) for the MDA-MB-231 cell line after 24-48h of treatment, but they were more selective and much more potent (IC50 4-16μM) for the MCF-7 cells after 48h of treatment. The highest activity for both hybrids and both breast cancer lines was observed after 72h of treatment (IC50 1-2μM), probably as the result of slow hydrolysis of their methyl ester functions. Copyright © 2016 Elsevier Inc. All rights reserved.

  14. Studies toward brevisulcenal F via convergent strategies for marine ladder polyether synthesis.

    PubMed

    Katcher, Matthew; Jamison, Timothy F

    2018-03-15

    Shortly after the initial isolation of marine ladder polyether natural products, biomimetic epoxide-opening cascade reactions were proposed as an efficient strategy for the synthesis of these compounds. However, difficulties in assembling the cascade precursors have limited the realization of these cascades. In this report, we describe strategies that provide convergent access to cascade precursors via regioselective allylation and efficient fragment coupling. We then investigate epoxide-opening cascades promoted by strong bases for the formation of fused tetrahydropyrans. These strategies are evaluated in the context of the synthesis of rings CDEFG of brevisulcenal F.

  15. Glucose Synthesis in a Protein-Based Artificial Photosynthesis System.

    PubMed

    Lu, Hao; Yuan, Wenqiao; Zhou, Jack; Chong, Parkson Lee-Gau

    2015-09-01

    The objective of this study was to understand glucose synthesis of a protein-based artificial photosynthesis system affected by operating conditions, including the concentrations of reactants, reaction temperature, and illumination. Results from non-vesicle-based glyceraldehyde-3-phosphate (GAP) and glucose synthesis showed that the initial concentrations of ribulose-1,5-bisphosphate (RuBP) and adenosine triphosphate (ATP), lighting source, and temperature significantly affected glucose synthesis. Higher initial concentrations of RuBP and ATP significantly enhanced GAP synthesis, which was linearly correlated to glucose synthesis, confirming the proper functions of all catalyzing enzymes in the system. White fluorescent light inhibited artificial photosynthesis and reduced glucose synthesis by 79.2 % compared to in the dark. The reaction temperature of 40 °C was optimum, whereas lower or higher temperature reduced glucose synthesis. Glucose synthesis in the vesicle-based artificial photosynthesis system reconstituted with bacteriorhodopsin, F 0 F 1 ATP synthase, and polydimethylsiloxane-methyloxazoline-polydimethylsiloxane triblock copolymer was successfully demonstrated. This system efficiently utilized light-induced ATP to drive glucose synthesis, and 5.2 μg ml(-1) glucose was synthesized in 0.78-ml reaction buffer in 7 h. Light-dependent reactions were found to be the bottleneck of the studied artificial photosynthesis system.

  16. 9-Fluorenylmethyloxycarbonyl/ tbutyl-based convergent protein synthesis.

    PubMed

    Barlos, K; Gatos, D

    1999-01-01

    Besides linear solid phase peptide synthesis, segment condensation in solution and chemical ligation, convergent peptide synthesis (CPS) was developed in order to enable the efficient preparation of complex peptides and small proteins. According to this synthetic strategy, solid phase synthesized and suitably protected peptide fragments corresponding to the entire peptide/protein-sequence are condensed on a solid support or in solution, to the target protein. This review summarizes CPS performed utilizing the mild 9-fluorenylmethyloxycarbonyl/tbutyloxycarbonyl-based protecting scheme for the amino acids. Copyright 1999 John Wiley & Sons, Inc.

  17. Synthesis of POSS-based ionic conductors with low glass transition temperatures for efficient solid-state dye-sensitized solar cells.

    PubMed

    Zhang, Wei; Wang, Zhong-Sheng

    2014-07-09

    Replacing liquid-state electrolytes with solid-state electrolytes has been proven to be an effective way to improve the durability of dye-sensitized solar cells (DSSCs). We report herein the synthesis of amorphous ionic conductors based on polyhedral oligomeric silsesquioxane (POSS) with low glass transition temperatures for solid-state DSSCs. As the ionic conductor is amorphous and in the elastomeric state at the operating temperature of DSSCs, good pore filling in the TiO2 film and good interfacial contact between the solid-state electrolyte and the TiO2 film can be guaranteed. When the POSS-based ionic conductor containing an allyl group is doped with only iodine as the solid-state electrolyte without any other additives, power conversion efficiency of 6.29% has been achieved with good long-term stability under one-sun soaking for 1000 h.

  18. Controllable synthesis of mesoporous carbon nanospheres and Fe-N/carbon nanospheres as efficient oxygen reduction electrocatalysts

    NASA Astrophysics Data System (ADS)

    Wei, Jing; Liang, Yan; Zhang, Xinyi; Simon, George P.; Zhao, Dongyuan; Zhang, Jin; Jiang, Sanping; Wang, Huanting

    2015-03-01

    The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions and show additional Coulombic interactions with chloride ions (acts as mediators). This kind of enhanced interaction is similar to that of the ``I+X-S+'' mechanism in the synthesis of mesoporous metal oxide, which can effectively retard the cross-linking rate of resol molecules and avoid macroscopic phase separation during the hydrothermal synthesis. Due to their uniform spherical morphology, small diameter, and high surface areas, MCNs can be modified with Fe and N species via impregnation of cheap precursors (ferric nitrate and dicyandiamide), which are further converted into nonprecious electrocatalysts for oxygen reduction reactions. The resulting Fe-N/MCNs exhibit high catalytic activities, long-term stability and improved methanol tolerance under alkaline conditions, which can be potentially used in direct methanol fuel cells and metal-air batteries.The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions

  19. Synthesis of spiro-4H-pyrazole-oxindoles and fused 1H-pyrazoles via divergent, thermally induced tandem cyclization/migration of alkyne-tethered diazo compounds.

    PubMed

    Zhang, Cheng; Dong, Shanliang; Zheng, Yang; He, Ciwang; Chen, Jiaolong; Zhen, Jingsen; Qiu, Lihua; Xu, Xinfang

    2018-01-31

    A thermally induced, substrate-dependent reaction of alkynyl diazo compounds has been developed. This transformation produces spiro-4H-pyrazole-oxindoles and fused 1H-pyrazoles in good to high yields from the corresponding alpha-cyano and alpha-sulfonyl diazo compounds. The salient features of this reaction include excellent chemoselectivity and atom-economy, mild reaction conditions, simple purification and potential for large scale production.

  20. High-Efficiency Synthesis of Human α-Endorphin and Magainin in the Erythrocytes of Transgenic Mice: A Production System for Therapeutic Peptides

    NASA Astrophysics Data System (ADS)

    Sharma, Ajay; Khoury-Christianson, Anastasia M.; White, Steven P.; Dhanjal, Nirpal K.; Huang, Wen; Paulhiac, Clara; Friedman, Eric J.; Manjula, Belur N.; Kumar, Ramesh

    1994-09-01

    Chemical synthesis of peptides, though feasible, is hindered by considerations of cost, purity, and efficiency of synthesizing longer chains. Here we describe a transgenic system for producing peptides of therapeutic interest as fusion proteins at low cost and high purity. Transgenic hemoglobin expression technology using the locus control region was employed to produce fusion hemoglobins in the erythrocytes of mice. The fusion hemoglobin contains the desired peptide as an extension at the C end of human α-globin. A protein cleavage site is inserted between the C end of the α-globin chain and the N-terminal residue of the desired peptide. The peptide is recovered after cleavage of the fusion protein with enzymes that recognize this cleavage signal as their substrate. Due to the selective compartmentalization of hemoglobin in the erythrocytes, purification of the fusion hemoglobin is easy and efficient. Because of its compact and highly ordered structure, the internal sites of hemoglobin are resistant to protease digestion and the desired peptide is efficiently released and recovered. The applicability of this approach was established by producing a 16-mer α-endorphin peptide and a 26-mer magainin peptide in transgenic mice. Transgenic animals and their progeny expressing these fusion proteins remain healthy, even when the fusion protein is expressed at >25% of the total hemoglobin in the erythrocytes. Additional applications and potential improvements of this methodology are discussed.

  1. Prebiotic Amino Acid Thioester Synthesis: Thiol-Dependent Amino Acid Synthesis from Formose substrates (Formaldehyde and Glycolaldehyde) and Ammonia

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    1998-01-01

    Formaldehyde and glycolaldehyde (substrates of the formose autocatalytic cycle) were shown to react with ammonia yielding alanine and homoserine under mild aqueous conditions in the presence of thiol catalysts. Since similar reactions carried out without ammonia yielded alpha-hydroxy acid thioesters, the thiol-dependent synthesis of alanine and homoserine is presumed to occur via amino acid thioesters-intermediates capable of forming peptides. A pH 5.2 solution of 20 mM formaldehyde, 20 mM glycolaldehyde, 20 mM ammonium chloride, 23 mM 3-mercaptopropionic acid, and 23 mM acetic acid that reacted for 35 days at 40 C yielded (based on initial formaldehyde) 1.8% alanine and 0.08% homoserine. In the absence of thiol catalyst, the synthesis of alanine and homoserine was negligible. Alanine synthesis required both formaldehyde and glycolaldehyde, but homoserine synthesis required only glycolaldehyde. At 25 days the efficiency of alanine synthesis calculated from the ratio of alanine synthesized to formaldehyde reacted was 2.1%, and the yield (based on initial formaldehyde) of triose and tetrose intermediates involved in alanine and homoserine synthesis was 0.3 and 2.1%, respectively. Alanine synthesis was also seen in similar reactions containing only 10 mM each of aldehyde substrates, ammonia, and thiol. The prebiotic significance of these reactions that use the formose reaction to generate sugar intermediates that are converted to reactive amino acid thioesters is discussed.

  2. An efficient one-pot synthesis of 1,4-disubstituted 1,2,3-triazoles at room temperature by green synthesized Cu NPs using Otostegia persica leaf extract.

    PubMed

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Mirzaei, Yousef

    2016-04-15

    In this study, copper nanoparticles (Cu NPs) were synthesized using a rapid, single step and completely green biosynthetic method by reduction of CuCl2 · 2H2O solution with aqueous extract of leaves of Otostegia persica containing flavonoid and other phenolics as a main factor which acts as reducing agent and efficient stabilizer. UV-vis spectra gave surface plasmon resonance (SPR) at 560 nm. The Cu NPs were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). A possible synthesis mechanism of Cu NPs was presented. In addition, we investigated the catalytic activity of Cu NPs for the one-pot synthesis of 1,4-disubstituted 1,2,3-triazoles under mild reaction conditions with good to excellent yields. The catalyst could be easily recovered by centrifugation and reused at least five recycles with no significant decreases in the yields. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. Synthesis of 1-O-methylchlorogenic acid: reassignment of structure for MCGA3 isolated from bamboo (Phyllostachys edulis) leaves

    USDA-ARS?s Scientific Manuscript database

    The first synthesis of 1-O-methylchlorogenic acid is described. The short and efficient synthesis of this compound provides laboratory-scale quantities of the material to investigate its biological properties. The synthesis involved C-1 alkylation of the known (-)-4,5-cyclohexylidenequinic acid lact...

  4. Efficient and scalable synthesis of bardoxolone methyl (cddo-methyl ester).

    PubMed

    Fu, Liangfeng; Gribble, Gordon W

    2013-04-05

    Bardoxolone methyl (2-cyano-3,12-dioxooleane-1,9(11)-dien-28-oic acid methyl ester; CDDO-Me) (1), a synthetic oleanane triterpenoid with highly potent anti-inflammatory activity (levels below 1 nM), has completed a successful phase I clinical trial for the treatment of cancer and a successful phase II trial for the treatment of chronic kidney disease in type 2 diabetes patients. Our synthesis of bardoxolone methyl (1) proceeds in ∼50% overall yield in five steps from oleanolic acid (2), requires only one to two chromatographic purifications, and can provide gram quantities of 1.

  5. Fabrication of highly efficient ZnO nanoscintillators

    NASA Astrophysics Data System (ADS)

    Procházková, Lenka; Gbur, Tomáš; Čuba, Václav; Jarý, Vítězslav; Nikl, Martin

    2015-09-01

    Photo-induced synthesis of high-efficiency ultrafast nanoparticle scintillators of ZnO was demonstrated. Controlled doping with Ga(III) and La(III) ions together with the optimized method of ZnO synthesis and subsequent two-step annealing in air and under reducing atmosphere allow to achieve very high intensity of UV exciton luminescence, up to 750% of BGO intensity magnitude. Fabricated nanoparticles feature extremely short sub-nanosecond photoluminescence decay times. Temperature dependence of the photoluminescence spectrum within 8-340 K range was investigated and shows the absence of visible defect-related emission within all temperature intervals.

  6. The effect of adding CTAB template in ZSM-5 synthesis

    NASA Astrophysics Data System (ADS)

    Widayat, Widayat; Annisa, Arianti Nuur

    2017-11-01

    In general, ZSM-5 synthesis is performed using a hydrothermal process that takes place at high temperature and high pressure (> 373 K,> 1 bar). The synthesis of ZSM-5 is influenced by the organic template used. The organic template serves as a determinant of the zeolite crystal structure formation. CTAB is an easily found organic template and the price is cheap so the production cost of ZSM-5 synthesis would be more efficient. In this research, ZSM-5 is synthesized by varying temperature and crystallization time. The result showed the optimal condition of ZSM-5 synthesis was at 363 K for the crystallization temperature with 8 hours of crystallization time. The crystalline product had 60.07% of crystallinity with an aluminosilicate composition of 72% w/w.

  7. Natural product synthesis at the interface of chemistry and biology

    PubMed Central

    2014-01-01

    Nature has evolved to produce unique and diverse natural products that possess high target affinity and specificity. Natural products have been the richest sources for novel modulators of biomolecular function. Since the chemical synthesis of urea by Wöhler, organic chemists have been intrigued by natural products, leading to the evolution of the field of natural product synthesis over the past two centuries. Natural product synthesis has enabled natural products to play an essential role in drug discovery and chemical biology. With the introduction of novel, innovative concepts and strategies for synthetic efficiency, natural product synthesis in the 21st century is well poised to address the challenges and complexities faced by natural product chemistry and will remain essential to progress in biomedical sciences. PMID:25043880

  8. Computerized Design Synthesis (CDS), A database-driven multidisciplinary design tool

    NASA Technical Reports Server (NTRS)

    Anderson, D. M.; Bolukbasi, A. O.

    1989-01-01

    The Computerized Design Synthesis (CDS) system under development at McDonnell Douglas Helicopter Company (MDHC) is targeted to make revolutionary improvements in both response time and resource efficiency in the conceptual and preliminary design of rotorcraft systems. It makes the accumulated design database and supporting technology analysis results readily available to designers and analysts of technology, systems, and production, and makes powerful design synthesis software available in a user friendly format.

  9. Total synthesis of the cyclopeptide alkaloid abyssenine A. Application of inter- and intramolecular copper-mediated coupling reactions in organic synthesis.

    PubMed

    Toumi, Mathieu; Couty, François; Evano, Gwilherm

    2007-11-23

    The first total synthesis of the 15-membered ring cyclopeptide alkaloid abyssenine A 1 has been achieved with a longest linear sequence of 15 steps. Central to the synthetic approach was an efficient copper-mediated Ullmann coupling/Claisen rearrangement sequence allowing for both ipso and ortho functionalization of aromatic iodide 4. This sequence was used for the synthesis of the aromatic core. The synthetic utility of copper-catalyzed coupling reactions was further demonstrated to install the enamide with a concomitant straightforward macrocyclization starting from acyclic alpha-amido-omega-vinyl iodide 13.

  10. Synthesis efficiency of heavy carbon clusters from ETFE ablated by different numbers of laser pulse in vacuum

    NASA Astrophysics Data System (ADS)

    Shibagaki, K.; Takada, N.; Sasaki, K.; Kadota, K.

    2002-09-01

    We have carried out mass spectral analysis of positive ions produced by laser ablation of a copolymer of ethylene and tetrafluoroethylene (ETFE: [CH 2CH 2CF 2CF 2] n) in vacuum using time-of-flight mass spectrometry (TOF-MS). The surfaces of the ETFE targets irradiated by different numbers of laser pulse were analyzed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Heavy carbon cluster ions C n+ with n≥30 were observed in the mass spectra. The fractional abundance of heavy clusters in the mass spectrum decreased with the number of laser pulse. On the other hand, carbon became rich in the atomic composition of the laser-irradiated surface, and the eroded area on the surface increased with the number of laser pulse. From these results, it is suggested that the carbon-rich material surface results in the less efficient production of heavy carbon clusters. In addition, it is also suggested that clustering reactions in eroded craters do not contribute to the synthesis of heavy clusters.

  11. Improvement of the BiOI photocatalytic activity optimizing the solvothermal synthesis

    NASA Astrophysics Data System (ADS)

    Mera, Adriana C.; Moreno, Yanko; Contreras, David; Escalona, Nestor; Meléndrez, Manuel F.; Mangalaraja, Ramalinga Viswanathan; Mansilla, Héctor D.

    2017-01-01

    BiOI nanostructured microspheres were obtained from the solvothermal synthesis route in the presence of ethylene glycol and KI as solvent and source of iodide, respectively. Optimal conditions for the synthesis were obtained by using multivariate analysis and choosing the photocatalytic oxidation rate constant of 3,4,5-trihydroxybenzoic acid (gallic acid) as response factor under simulated solar radiation. Response surface methodology (RSM) was used to determine the optimum values of the reaction time and temperature which were 18 h and 126 °C, respectively, to obtain the most active catalyst. In addition, BiOI synthesis using ionic liquid 1-butyl-3-methylimidazolium iodide ([bmim]I) as iodide source was also carried out for the comparison of microstructure and its photocatalytic efficiency. The obtained BiOI nanostructures were characterized by scanning electron microscopy (SEM) attached with energy dispersive spectrometer (EDS), nitrogen adsorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetry (TG), Fourier transform infrared (FTIR) spectrometry, diffuse reflectance spectroscopy (DRS) and cyclic voltammetry (CV) analyses for their changes in morphological and structural behaviors. It was observed that the synthesis temperature of BiOI nanostructures strongly influenced the morphology, crystalline phase, surface area and electrochemical behavior, and thus affecting the photocatalytic efficiency. The higher photocatalytic removal of gallic acid (60%) was reached within 30 min of irradiation with UV-A on microspheres obtained with ionic liquid. The (1 1 0) crystal phase of BiOI influenced the photocatalytic efficiency.

  12. Efficient Synthesis of γ-Lactams by a Tandem Reductive Amination/Lactamization Sequence

    PubMed Central

    Nöth, Julica; Frankowski, Kevin J.; Neuenswander, Benjamin; Aubé, Jeffrey; Reiser, Oliver

    2009-01-01

    A three-component method for synthesizing highly-substituted γ-lactams from readily available maleimides, aldehydes and amines is described. A new reductive amination/intramolecular lactamization sequence provides a straightforward route to the lactam products in a single manipulation. The general utility of this method is demonstrated by the parallel synthesis of a γ-lactam library. PMID:18338857

  13. Highly efficient one-step synthesis of carbon encapsulated nanocrystals by the oxidation of metal π-complexes

    NASA Astrophysics Data System (ADS)

    Liu, Boyang; Shao, Yingfeng; Xiang, Xin; Zhang, Fuhua; Yan, Shengchang; Li, Wenge

    2017-08-01

    Various carbon encapsulated nanocrystals, including MnS and MnO, Cr2O3, MoO2, Fe7S8 and Fe3O4, and ZrO2, are prepared in one step and in situ by a simple and highly efficient synthesis approach. The nanocrystals have an equiaxed morphology and a median size smaller than 30 nm. Tens and hundreds of these nanocrystals are entirely encapsulated by a wormlike amorphous carbon shell. The formation of a core-shell structure depends on the strongly exothermic reaction of metal π-complexes with ammonium persulfate in an autoclave at below 200 °C. During the oxidation process, the generated significant amounts of heat will destroy the molecular structure of the metal π-complex and cleave the ligands into small carbon fragments, which further transform into an amorphous carbon shell. The central metal atoms are oxidized to metal oxide/sulfide nanocrystals. The formation of a core-shell structure is independent of the numbers of ligands and carbon atoms as well as the metal types, implying that any metal π-complex can serve as a precursor and that various carbon encapsulated nanocrystals can be synthesized by this method.

  14. CdO nanorods and Cd(OH)2/Ag core/satellite nanorods: Rapid and efficient sonochemical synthesis, characterization and their magnetic properties.

    PubMed

    Abbas, Mohamed; Tawfik, Wael; Chen, Jiangang

    2018-01-01

    We have designed an efficient and direct sonochemical method for the facile synthesis of Cd(OH) 2 , CdO, and Cd(OH) 2 /Ag core/satellite nanorods. A Cd(OH) 2 nanorod was synthesized with a one-pot, environmentally-friendly aqueous sonochemical reaction, followed by calcination at 500°C to produce CdO nanorods. Thirty minutes of re-ultrasonicated CdO nanorods in the presence of the Ag precursor was sufficient for phase transformation from the cubic structure of CdO to the monoclinic crystalline structure of Cd(OH) 2 , accompanied by deposition of Ag nanodots on the surface to form Cd(OH) 2 /Ag core/satellite nanorods. X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, energy-dispersive spectroscopy, N 2 Brunauer-Emmett-Teller adsorption-desorption, and Fourier-transform infrared spectroscopy measurements confirmed the successful formation of the various phases and the unique morphology of the nanorods/satellites. We also measured the magnetic properties using a vibrating sample magnetometer at room temperature, and the produced nanorods showed weak unsaturated ferromagnetic properties with a magnetic moment values of 0.105 and 0.076emu/g for CdO and Cd(OH) 2 /Ag NRs, respectively. In conclusion, our one-pot, cost-effective, sonochemical approach holds promise for the synthesis of various oxides and core/satellite nanoparticles. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Diboron compound-based organic light-emitting diodes with high efficiency and reduced efficiency roll-off

    NASA Astrophysics Data System (ADS)

    Wu, Tien-Lin; Huang, Min-Jie; Lin, Chih-Chun; Huang, Pei-Yun; Chou, Tsu-Yu; Chen-Cheng, Ren-Wu; Lin, Hao-Wu; Liu, Rai-Shung; Cheng, Chien-Hong

    2018-04-01

    Organic light-emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) materials are promising for the realization of highly efficient light emitters. However, such devices have so far suffered from efficiency roll-off at high luminance. Here, we report the design and synthesis of two diboron-based molecules, CzDBA and tBuCzDBA, which show excellent TADF properties and yield efficient OLEDs with very low efficiency roll-off. These donor-acceptor-donor (D-A-D) type and rod-like compounds concurrently generate TADF with a photoluminescence quantum yield of 100% and an 84% horizontal dipole ratio in the thin film. A green OLED based on CzDBA exhibits a high external quantum efficiency of 37.8 ± 0.6%, a current efficiency of 139.6 ± 2.8 cd A-1 and a power efficiency of 121.6 ± 3.1 lm W-1 with an efficiency roll-off of only 0.3% at 1,000 cd m-2. The device has a peak emission wavelength of 528 nm and colour coordinates of the Commission International de ĺEclairage (CIE) of (0.31, 0.61), making it attractive for colour-display applications.

  16. Synthesis of Polycyclic Natural Products

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Nguyen, Tuan Hoang

    With the continuous advancements in molecular biology and modern medicine, organic synthesis has become vital to the support and extension of those discoveries. The isolations of new natural products allow for the understanding of their biological activities and therapeutic value. Organic synthesis is employed to aid in the determination of the relationship between structure and function of these natural products. The development of synthetic methodologies in the course of total syntheses is imperative for the expansion of this highly interdisciplinary field of science. In addition to the practical applications of total syntheses, the structural complexity of natural products represents amore » worthwhile challenge in itself. The pursuit of concise and efficient syntheses of complex molecules is both gratifying and enjoyable.« less

  17. Controllable synthesis of mesoporous carbon nanospheres and Fe-N/carbon nanospheres as efficient oxygen reduction electrocatalysts.

    PubMed

    Wei, Jing; Liang, Yan; Zhang, Xinyi; Simon, George P; Zhao, Dongyuan; Zhang, Jin; Jiang, Sanping; Wang, Huanting

    2015-04-14

    The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions and show additional Coulombic interactions with chloride ions (acts as mediators). This kind of enhanced interaction is similar to that of the "I(+)X(-)S(+)" mechanism in the synthesis of mesoporous metal oxide, which can effectively retard the cross-linking rate of resol molecules and avoid macroscopic phase separation during the hydrothermal synthesis. Due to their uniform spherical morphology, small diameter, and high surface areas, MCNs can be modified with Fe and N species via impregnation of cheap precursors (ferric nitrate and dicyandiamide), which are further converted into nonprecious electrocatalysts for oxygen reduction reactions. The resulting Fe-N/MCNs exhibit high catalytic activities, long-term stability and improved methanol tolerance under alkaline conditions, which can be potentially used in direct methanol fuel cells and metal-air batteries.

  18. (E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation.

    PubMed

    Shi, Renyi; Zhang, Hua; Lu, Lijun; Gan, Pei; Sha, Yuchen; Zhang, Heng; Liu, Qiang; Beller, Matthias; Lei, Aiwen

    2015-02-21

    A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-α,β-unsaturated amide derivatives from easily available tertiary amines, olefins and CO.

  19. AutoBayes Program Synthesis System Users Manual

    NASA Technical Reports Server (NTRS)

    Schumann, Johann; Jafari, Hamed; Pressburger, Tom; Denney, Ewen; Buntine, Wray; Fischer, Bernd

    2008-01-01

    Program synthesis is the systematic, automatic construction of efficient executable code from high-level declarative specifications. AutoBayes is a fully automatic program synthesis system for the statistical data analysis domain; in particular, it solves parameter estimation problems. It has seen many successful applications at NASA and is currently being used, for example, to analyze simulation results for Orion. The input to AutoBayes is a concise description of a data analysis problem composed of a parameterized statistical model and a goal that is a probability term involving parameters and input data. The output is optimized and fully documented C/C++ code computing the values for those parameters that maximize the probability term. AutoBayes can solve many subproblems symbolically rather than having to rely on numeric approximation algorithms, thus yielding effective, efficient, and compact code. Statistical analysis is faster and more reliable, because effort can be focused on model development and validation rather than manual development of solution algorithms and code.

  20. Microwave assisted synthesis of bridgehead alkenes.

    PubMed

    Cleary, Leah; Yoo, Hoseong; Shea, Kenneth J

    2011-04-01

    A new, concise method to synthesize triene precursors for the type 2 intramolecular Diels-Alder reaction has been developed. Microwave irradiation of the trienes provides a convenient method for the synthesis of bridgehead alkenes. Higher yields, shorter reaction times, and lower reaction temperatures provide a general and efficient route to this interesting class of molecules.

  1. Combustion synthesis of ceramic-metal composite materials in microgravity

    NASA Technical Reports Server (NTRS)

    Moore, John

    1995-01-01

    Combustion synthesis, self-propagating high temperature synthesis (SHS) or reactive synthesis provides an attractive alternative to conventional methods of producing advanced materials since this technology is based on the ability of highly exothermic reactions to be self sustaining and, therefore, energetically efficient. The exothermic SHS reaction is initiated at the ignition temperature, T(sub ig), and generates heat which is manifested in a maximum or combustion temperature, T(sub c), which can exceed 3000 K . Such high combustion temperatures are capable of melting and/or volatilizing reactant and product species and, therefore, present an opportunity for producing structure and property modification and control through liquid-solid, vapor-liquid-solid, and vapor-solid transformations.

  2. Green Chemistry Techniques for Gold Nanoparticles Synthesis

    NASA Astrophysics Data System (ADS)

    Cannavino, Sarah A.; King, Christy A.; Ferrara, Davon W.

    Gold nanoparticles (AuNPs) are often utilized in many technological and research applications ranging from the detection of tumors, molecular and biological sensors, and as nanoantennas to probe physical processes. As these applications move from the research laboratory to industrial settings, there is a need to develop efficient and sustainable synthesis techniques. Recent research has shown that several food products and beverages containing polyphenols, a common antioxidant, can be used as reducing agents in the synthesis of AuNPs in solution. In this study, we explore a variety of products to determine which allow for the most reproducible solution of nanoparticles based on the size and shapes of particles present. We analyzed the AuNPs solutions using extinction spectroscopy and atomic force microscopy. We also develop a laboratory activity to introduce introductory chemistry and physics students to AuNP synthesis techniques and analysis.

  3. The art and science of knowledge synthesis.

    PubMed

    Tricco, Andrea C; Tetzlaff, Jennifer; Moher, David

    2011-01-01

    To review methods for completing knowledge synthesis. We discuss how to complete a broad range of knowledge syntheses. Our article is intended as an introductory guide. Many groups worldwide conduct knowledge syntheses, and some methods are applicable to most reviews. However, variations of these methods are apparent for different types of reviews, such as realist reviews and mixed-model reviews. Review validity is dependent on the validity of the included primary studies and the review process itself. Steps should be taken to avoid bias in the conduct of knowledge synthesis. Transparency in reporting will help readers assess review validity and applicability, increasing its utility. Given the magnitude of the literature, the increasing demands on knowledge syntheses teams, and the diversity of approaches, continuing efforts will be important to increase the efficiency, validity, and applicability of systematic reviews. Future research should focus on increasing the uptake of knowledge synthesis, how best to update reviews, the comparability between different types of reviews (eg, rapid vs. comprehensive reviews), and how to prioritize knowledge synthesis topics. Copyright © 2011 Elsevier Inc. All rights reserved.

  4. Protein Engineering and Homologous Expression of Serratia marcescens Lipase for Efficient Synthesis of a Pharmaceutically Relevant Chiral Epoxyester.

    PubMed

    Chen, Ke-Cai; Zheng, Ming-Min; Pan, Jiang; Li, Chun-Xiu; Xu, Jian-He

    2017-10-01

    The lipase isolated from Serratia marcescens (LipA) is a useful biocatalyst for kinetic resolution of a pharmaceutically relevant epoxyester, (±)-3-(4'-methoxyphenyl) glycidic acid methyl ester [(±)-MPGM], to afford optically pure (-)-MPGM, a key intermediate for the synthesis of diltiazem hydrochloride. Two mutants, LipA L315S and LipA S271F , were identified from the combinatorial saturation mutation library of 14 amino acid residues lining the substrate-binding pocket. LipA L315S , LipA S271F , and their combination LipA L315S/S271F showed 2.6-, 2.2-, and 4.6-fold improvements in their specific activities towards para-nitrophenyl butyrate (pNPB), respectively. Among these positive mutants, LipA S271F displayed a 3.5-fold higher specific activity towards the pharmaco substrate (±)-MPGM. Kinetic study showed that the improvement in catalytic efficiency of LipA S271F against (±)-MPGM was mainly resulted from the enhanced affinity between substrate and enzyme, as indicated by the decrease of K m . Furthermore, to address the insoluble expression issue in Escherichia coli, the homologous expression of LipA gene in S. marcescens was achieved by introducing it into an expression vector pUC18, resulting in ca. 20-fold higher lipase production. The significantly improved volumeric production and specific activity of S. marcescens lipase make it very attractive as a new-generation biocatalyst for more efficient and economical manufacturing of (-)-MPGM.

  5. An efficient protocol for the synthesis of highly sensitive indole imines utilizing green chemistry: optimization of reaction conditions.

    PubMed

    Nisar, Bushra; Rubab, Syeda Laila; Raza, Abdul Rauf; Tariq, Sobia; Sultan, Ayesha; Tahir, Muhammad Nawaz

    2018-04-11

    Novel and highly sensitive indole-based imines have been synthesized. Their synthesis has been compared employing a variety of protocols. Ultimately, a convenient, economical and high yielding set of conditions employing green chemistry have been designed for their synthesis.

  6. The Pauson-Khand Reaction as a New Entry to the Synthesis of Bridged Bicyclic Heterocycles: Application to the Enantioselective Total Synthesis of (-)-Alstonerine.

    PubMed

    Miller, Kenneth A; Shanahan, Charles S; Martin, Stephen F

    2008-01-01

    The first application of the Pauson-Khand reaction (PKR) to the synthesis of azabridged bicyclic structures is described. Compounds containing azabicyclo[3.3.1]nonane and azabicyclo[3.2.1]octane rings fused to cyclopentenones were efficiently constructed via the PKR of cis-2,6-disubstituted N-acyl piperidine enyne substrates, many of which can be readily prepared from 4-methoxypyridine in a few steps. Moreover, the PKR of cis-2,6-disubstituted piperazine enynes allowed the preparation of diazabicyclo[3.3.1]nonanes fused to cyclopentenones. This new strategy for the synthesis of azabridged bicyclic frameworks was exploited as a key step in a concise, enantioselective total synthesis of the macroline alklaoid (-)-alstonerine.

  7. Natural product synthesis at the interface of chemistry and biology.

    PubMed

    Hong, Jiyong

    2014-08-11

    Nature has evolved to produce unique and diverse natural products that possess high target affinity and specificity. Natural products have been the richest sources for novel modulators of biomolecular function. Since the chemical synthesis of urea by Wöhler, organic chemists have been intrigued by natural products, leading to the evolution of the field of natural product synthesis over the past two centuries. Natural product synthesis has enabled natural products to play an essential role in drug discovery and chemical biology. With the introduction of novel, innovative concepts and strategies for synthetic efficiency, natural product synthesis in the 21st century is well poised to address the challenges and complexities faced by natural product chemistry and will remain essential to progress in biomedical sciences. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Protein chemical synthesis by α-ketoacid-hydroxylamine ligation.

    PubMed

    Harmand, Thibault J; Murar, Claudia E; Bode, Jeffrey W

    2016-06-01

    Total chemical synthesis of proteins allows researchers to custom design proteins without the complex molecular biology that is required to insert non-natural amino acids or the biocontamination that arises from methods relying on overexpression in cells. We describe a detailed procedure for the chemical synthesis of proteins with the α-ketoacid-hydroxylamine (KAHA ligation), using (S)-5-oxaproline (Opr) as a key building block. This protocol comprises two main parts: (i) the synthesis of peptide fragments by standard fluorenylmethoxycarbonyl (Fmoc) chemistry and (ii) the KAHA ligation between fragments containing Opr and a C-terminal peptide α-ketoacid. This procedure provides an alternative to native chemical ligation (NCL) that could be valuable for the synthesis of proteins, particularly targets that do not contain cysteine residues. The ligation conditions-acidic DMSO/H2O or N-methyl-2-pyrrolidinone (NMP)/H2O-are ideally suited for solubilizing peptide segments, including many hydrophobic examples. The utility and efficiency of the protocol is demonstrated by the total chemical synthesis of the mature betatrophin (also called ANGPTL8), a 177-residue protein that contains no cysteine residues. With this protocol, the total synthesis of the betatrophin protein has been achieved in around 35 working days on a multimilligram scale.

  9. Chemical Synthesis of Complex Molecules Using Nanoparticle Catalysis

    PubMed Central

    Cong, Huan; Porco, John A.

    2011-01-01

    Nanoparticle catalysis has emerged as an active topic in organic synthesis. Of particular interest is the development of enabling methodologies to efficiently assemble complex molecules using nanoparticle catalysis. This Viewpoint highlights recent developments and discusses future perspectives in this emerging field. PMID:22347681

  10. Palladium-Catalyzed [3 + 2]-C-C/N-C Bond-Forming Annulation.

    PubMed

    Liu, Yang; Mao, Zhongyi; Pradal, Alexandre; Huang, Pei-Qiang; Oble, Julie; Poli, Giovanni

    2018-06-13

    The synthesis of bi- and tricyclic structures incorporating pyrrolidone rings is disclosed, starting from resonance-stabilized acetamides and cyclic α,β-unsaturated-γ-oxycarbonyl derivatives. This process involves an intermolecular Tsuji-Trost allylation/intramolecular nitrogen 1,4-addition sequence. Crucial for the success of this bis-nucleophile/bis-electrophile [3 + 2] annulation is its well-defined step chronology in combination with the total chemoselectivity of the former step. When the newly formed annulation product carries a properly located o-haloaryl moiety at the nitrogen substituent, a further intramolecular keto α-arylation can join the cascade, thereby forming two new cycles and three new bonds in the same synthetic operation.

  11. N-O linkage in carbohydrates and glycoconjugates.

    PubMed

    Chen, N; Xie, J

    2016-11-29

    The importance of oligosaccharides and their conjugates in various biological and pathological processes has stimulated growing interest in the development of (neo)glycoconjugates. Thanks to its high nucleophilicity, hydroxylamine has been employed as a powerful chemoselective ligation tool. Great effort has been focused on carbohydrates bearing aminooxy or N-hydroxy amino groups for organic synthesis, glycobiology and drug discovery. This review provides an overview of N-O linked carbohydrates and glycoconjugates, focusing particularly on the synthetic methodologies and chemical and physicochemical properties as well as biological and medical applications of N-glycosyl and O-glycosyl hydroxylamines, N-hydroxy amino and O-amino sugar as well as sugar aminooxy acid derivatives.

  12. Amino Acid Bound Surfactants: A New Synthetic Family of Polymeric Monoliths Open Up Possibilities for Chiral Separations in Capillary Electrochromatography

    PubMed Central

    He, Jun; Wang, Xiaochun; Morrill, Mike; Shamsi, Shahab A.

    2012-01-01

    By combining a novel chiral amino-acid surfactant containing acryloyl amide tail, carbamate linker and leucine head group of different chain lengths with a conventional cross linker and a polymerization technique, a new “one-pot”, synthesis for the generation of amino-acid based polymeric monolith is realized. The method promises to open up the discovery of amino-acid based polymeric monolith for chiral separations in capillary electrochromatography (CEC). Possibility of enhanced chemoselectivity for simultaneous separation of ephedrine and pseudoephedrine containing multiple chiral centers, and the potential use of this amino-acid surfactant bound column for CEC and CEC coupled to mass spectrometric detection is demonstrated. PMID:22607448

  13. Tuning Thermoresponsive Properties of Cationic Elastin-like Polypeptides by Varying Counterions and Side-Chains.

    PubMed

    Petitdemange, Rosine; Garanger, Elisabeth; Bataille, Laure; Bathany, Katell; Garbay, Bertrand; Deming, Timothy J; Lecommandoux, Sébastien

    2017-05-17

    We report the synthesis of methionine-containing recombinant elastin-like polypeptides (ELPs) of different lengths that contain periodically spaced methionine residues. These ELPs were chemoselectively alkylated at all methionine residues to give polycationic derivatives. Some of these samples were found to possess solubility transitions in water, where the temperature of these transitions varied with ELP concentration, nature of the methionine alkylating group, and nature of the sulfonium counterions. These studies show that introduction and controlled spacing of methionine sulfonium residues into ELPs can be used as a means both to tune their solubility transition temperatures in water using a variety of different parameters and to introduce new side-chain functionality.

  14. Microwave Assisted Synthesis of Bridgehead Alkenes

    PubMed Central

    Cleary, Leah; Yoo, Hoseong; Shea, Kenneth J.

    2011-01-01

    A new, concise method to synthesize triene precursors for the type 2 intramolecular Diels–Alder reaction has been developed. Microwave irradiation of the trienes provides a convenient method for the synthesis of bridgehead alkenes. Higher yields, shorter reaction times and lower reaction temperatures provide a general and efficient route to this interesting class of molecules. PMID:21384818

  15. Transaminases for the synthesis of enantiopure beta-amino acids

    PubMed Central

    2012-01-01

    Optically pure β-amino acids constitute interesting building blocks for peptidomimetics and a great variety of pharmaceutically important compounds. Their efficient synthesis still poses a major challenge. Transaminases (also known as aminotransferases) possess a great potential for the synthesis of optically pure β-amino acids. These pyridoxal 5'-dependent enzymes catalyze the transfer of an amino group from a donor substrate to an acceptor, thus enabling the synthesis of a wide variety of chiral amines and amino acids. Transaminases can be applied either for the kinetic resolution of racemic compounds or the asymmetric synthesis starting from a prochiral substrate. This review gives an overview over microbial transaminases with activity towards β-amino acids and their substrate spectra. It also outlines current strategies for the screening of new biocatalysts. Particular emphasis is placed on activity assays which are applicable to high-throughput screening. PMID:22293122

  16. Thermolysis of Geminal Diazides: Reagent-Free Synthesis of 3-Hydroxypyridines.

    PubMed

    Erhardt, Hellmuth; Kunz, Kevin A; Kirsch, Stefan F

    2017-01-06

    An operationally simple protocol for the rapid and efficient construction of highly substituted 3-hydroxypyridines is presented. The thermally induced cyclization of easily constructed geminal diazides derived from β-ketoesters having an additional olefin moiety affords the title compounds in yields up to 97% under reagent-free conditions. The new method allows for the synthesis of preparative quantities of material. Additionally, the synthetic utility of the pyridine products for the synthesis of valuable heterocycles is described.

  17. The Pauson-Khand Reaction as a New Entry to the Synthesis of Bridged Bicyclic Heterocycles: Application to the Enantioselective Total Synthesis of (−)-Alstonerine

    PubMed Central

    Miller, Kenneth A.; Shanahan, Charles S.; Martin, Stephen F.

    2008-01-01

    The first application of the Pauson-Khand reaction (PKR) to the synthesis of azabridged bicyclic structures is described. Compounds containing azabicyclo[3.3.1]nonane and azabicyclo[3.2.1]octane rings fused to cyclopentenones were efficiently constructed via the PKR of cis-2,6-disubstituted N-acyl piperidine enyne substrates, many of which can be readily prepared from 4-methoxypyridine in a few steps. Moreover, the PKR of cis-2,6-disubstituted piperazine enynes allowed the preparation of diazabicyclo[3.3.1]nonanes fused to cyclopentenones. This new strategy for the synthesis of azabridged bicyclic frameworks was exploited as a key step in a concise, enantioselective total synthesis of the macroline alklaoid (−)-alstonerine. PMID:19122869

  18. A Student Synthesis of the Housefly Sex Attractant.

    ERIC Educational Resources Information Center

    Cormier, Russell; And Others

    1979-01-01

    A novel and efficient (34 percent overall) multi-step synthesis of the housefly sex attractant, muscalure, is described. Each of the steps involves types of reactions with which the undergraduate student would be familiar after one-and-one-half semesters of organic chemistry. (BB)

  19. Synthesis and toughness properties of resins and composites

    NASA Technical Reports Server (NTRS)

    Johnston, N. J.

    1984-01-01

    Tensile and shear moduli of four ACEE (Aircraft Energy Efficiency Program) resins are presented along with ACEE composite material modulus predictions based on micromechanics. Compressive strength and fracture toughness of the resins and composites were discussed. In addition, several resin synthesis techniques are reviewed.

  20. Synthesis of modified proanthocyanidins: easy and general introduction of a hydroxy group at C-6 of catechin; efficient synthesis of elephantorrhizol.

    PubMed

    Boyer, François-Didier; Es-Safi, Nour-Eddine; Beauhaire, Josiane; Guernevé, Christine Le; Ducrot, Paul-Henri

    2005-02-01

    A general procedure for the oxidation of catechin derivatives is described, leading to the introduction of a new hydroxy group at C-6. This procedure has been applied for the synthesis of elephantorrhizol, a natural flavan-3-ol exhibiting a fully substituted cycle A.

  1. Identification of cis-acting elements on positive-strand subgenomic mRNA required for the synthesis of negative-strand counterpart in bovine coronavirus.

    PubMed

    Yeh, Po-Yuan; Wu, Hung-Yi

    2014-07-30

    It has been demonstrated that, in addition to genomic RNA, sgmRNA is able to serve as a template for the synthesis of the negative-strand [(-)-strand] complement. However, the cis-acting elements on the positive-strand [(+)-strand] sgmRNA required for (-)-strand sgmRNA synthesis have not yet been systematically identified. In this study, we employed real-time quantitative reverse transcription polymerase chain reaction to analyze the cis-acting elements on bovine coronavirus (BCoV) sgmRNA 7 required for the synthesis of its (-)-strand counterpart by deletion mutagenesis. The major findings are as follows. (1) Deletion of the 5'-terminal leader sequence on sgmRNA 7 decreased the synthesis of the (-)-strand sgmRNA complement. (2) Deletions of the 3' untranslated region (UTR) bulged stem-loop showed no effect on (-)-strand sgmRNA synthesis; however, deletion of the 3' UTR pseudoknot decreased the yield of (-)-strand sgmRNA. (3) Nucleotides positioned from -15 to -34 of the sgmRNA 7 3'-terminal region are required for efficient (-)-strand sgmRNA synthesis. (4) Nucleotide species at the 3'-most position (-1) of sgmRNA 7 is correlated to the efficiency of (-)-strand sgmRNA synthesis. These results together suggest, in principle, that the 5'- and 3'-terminal sequences on sgmRNA 7 harbor cis-acting elements are critical for efficient (-)-strand sgmRNA synthesis in BCoV.

  2. Synthesis of quantum dots

    DOEpatents

    McDaniel, Hunter

    2017-10-17

    Common approaches to synthesizing alloyed quantum dots employ high-cost, air-sensitive phosphine complexes as the selenium precursor. Disclosed quantum dot synthesis embodiments avoid these hazardous and air-sensitive selenium precursors. Certain embodiments utilize a combination comprising a thiol and an amine that together reduce and complex the elemental selenium to form a highly reactive selenium precursor at room temperature. The same combination of thiol and amine acts as the reaction solvent, stabilizing ligand, and sulfur source in the synthesis of quantum dot cores. A non-injection approach may also be used. The optical properties of the quantum dots synthesized by this new approach can be finely tuned for a variety of applications by controlling size and/or composition of size and composition. Further, using the same approach, a shell can be grown around a quantum dot core that improves stability, luminescence efficiency, and may reduce toxicity.

  3. Developing Inhibitors of Translesion DNA Synthesis as Therapeutic Agents against Lung Cancer

    DTIC Science & Technology

    2015-12-01

    normal DNA synthesis. In contrast, pol eta shows a combination of high efficiency and low fidelity when replicating 8-oxo-G. These combined properties...are consistent with a pro- mutagenic role for pol eta when replicating this DNA lesion under cellular conditions. Studies with modified nucleotide...analogs indicate that pol eta relies heavily on hydrogen-bonding interactions during normal and translesion synthesis. However, some nucleobase

  4. Click mechanochemistry: quantitative synthesis of "ready to use" chiral organocatalysts by efficient two-fold thiourea coupling to vicinal diamines.

    PubMed

    Štrukil, Vjekoslav; Igrc, Marina D; Eckert-Maksić, Mirjana; Friščić, Tomislav

    2012-07-02

    Mechanochemical methods of neat grinding and liquid-assisted grinding have been applied to the synthesis of mono- and bis(thiourea)s by using the click coupling of aromatic and aliphatic diamines with aromatic isothiocyanates. The ability to modify the reaction conditions allowed the optimization of each reaction, leading to the quantitative formation of chiral bis(thiourea)s with known uses as organocatalysts or anion sensors. Quantitative reaction yields, combined with the fact that mechanochemical reaction conditions avoid the use of bulk solvents, enabled solution-based purification methods (such as chromatography or recrystallization) to be completely avoided. Importantly, by using selected model reactions, we also show that the described mechanochemical reaction procedures can be readily scaled up to at least the one-gram scale. In that way, mechanochemical synthesis provides a facile method to fully transform valuable enantiomerically pure reagents into useful products that can immediately be applied in their designed purpose. This was demonstrated by using some of the mechanochemically prepared reagents as organocatalysts in a model Morita-Baylis-Hillman reaction and as cyanide ion sensors in organic solvents. The use of electronically and sterically hindered ortho-phenylenediamine revealed that mechanochemical reaction conditions can be readily optimized to form either the 1:1 or the 1:2 click-coupling product, demonstrating that reaction stoichiometry can be more efficiently controlled under these conditions than in solution-based syntheses. In this way, it was shown that excellent stoichiometric control by mechanochemistry, previously established for mechanochemical syntheses of cocrystals and coordination polymers, can also be achieved in the context of covalent-bond formation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Efficient Synthesis of Molecular Precursors for Para-Hydrogen-Induced Polarization of Ethyl Acetate-1-(13) C and Beyond.

    PubMed

    Shchepin, Roman V; Barskiy, Danila A; Coffey, Aaron M; Manzanera Esteve, Isaac V; Chekmenev, Eduard Y

    2016-05-10

    A scalable and versatile methodology for production of vinylated carboxylic compounds with (13) C isotopic label in C1 position is described. It allowed synthesis of vinyl acetate-1-(13) C, which is a precursor for preparation of (13) C hyperpolarized ethyl acetate-1-(13) C, which provides a convenient vehicle for potential in vivo delivery of hyperpolarized acetate to probe metabolism in living organisms. Kinetics of vinyl acetate molecular hydrogenation and polarization transfer from para-hydrogen to (13) C via magnetic field cycling were investigated. Nascent proton nuclear spin polarization (%PH ) of ca. 3.3 % and carbon-13 polarization (%P13C ) of ca. 1.8 % were achieved in ethyl acetate utilizing 50 % para-hydrogen corresponding to ca. 50 % polarization transfer efficiency. The use of nearly 100% para-hydrogen and the improvements of %PH of para-hydrogen-nascent protons may enable production of (13) C hyperpolarized contrast agents with %P13C of 20-50 % in seconds using this chemistry. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. A comparative study of three different synthesis routes for hydrophilic fluorophore-doped silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Shahabi, Shakiba; Treccani, Laura; Rezwan, Kurosch

    2016-01-01

    The synthesis of fluorophore-doped silica nanoparticles (FDS NPs) with two conventional approaches, Stöber and microemulsion, as well as a novel amino acid-catalyzed seeds regrowth technique (ACSRT) is presented. The efficiency of each applied synthesis route toward incorporation of selected hydrophilic fluorophores, including rhodamine B isothiocyanate and fluorescein isothiocyanate, without and with an amine-containing crosslinker, into silica matrix was systematically studied. Our results clearly highlight the advantages of ACSRT to obtain FDS NPs with a remarkable encapsulation efficiency, high quantum yield, and enhanced stability against bleaching and dye leaking due to efficient embedding of the dyes inside silica network even without the amine-containing silane reagent. Moreover, evaluation of photostability of FDNPs internalized in human bone cells demonstrates the merits of ACSRT.

  7. Efficient One-Pot Synthesis of Colloidal Zirconium Oxide Nanoparticles for High-Refractive-Index Nanocomposites.

    PubMed

    Liu, Chao; Hajagos, Tibor Jacob; Chen, Dustin; Chen, Yi; Kishpaugh, David; Pei, Qibing

    2016-02-01

    Zirconium oxide nanoparticles are promising candidates for optical engineering, photocatalysis, and high-κ dielectrics. However, reported synthetic methods for the colloidal zirconium oxide nanoparticles use unstable alkoxide precursors and have various other drawbacks, limiting their wide application. Here, we report a facile one-pot method for the synthesis of colloidally stable zirconium oxide nanoparticles. Using a simple solution of zirconium trifluoroacetate in oleylamine, highly stable zirconium oxide nanoparticles have been synthesized with high yield, following a proposed amidization-assisted sol-gel mechanism. The nanoparticles can be readily dispersed in nonpolar solvents, forming a long-term stable transparent solution, which can be further used to fabricate high-refractive-index nanocomposites in both monolith and thin-film forms. In addition, the same method has also been extended to the synthesis of titanium oxide nanoparticles, demonstrating its general applicability to all group IVB metal oxide nanoparticles.

  8. Biological synthesis of nanoparticles in biofilms.

    PubMed

    Tanzil, Abid H; Sultana, Sujala T; Saunders, Steven R; Shi, Liang; Marsili, Enrico; Beyenal, Haluk

    2016-12-01

    The biological synthesis of nanoparticles (NPs) by bacteria and biofilms via extracellular redox reactions has received attention because of the minimization of harmful chemicals, low cost, and ease of culturing and downstream processing. Bioreduction mechanisms vary across bacteria and growth conditions, which leads to various sizes and shapes of biosynthesized NPs. NP synthesis in biofilms offers additional advantages, such as higher biomass concentrations and larger surface areas, which can lead to more efficient and scalable biosynthesis. Although biofilms have been used to produce NPs, the mechanistic details of NP formation are not well understood. In this review, we identify three critical areas of research and development needed to advance our understanding of NP production by biofilms: 1) synthesis, 2) mechanism and 3) stabilization. Advancement in these areas could result in the biosynthesis of NPs that are suitable for practical applications, especially in drug delivery and biocatalysis. Specifically, the current status of methods and mechanisms of nanoparticle synthesis and surface stabilization using planktonic bacteria and biofilms is discussed. We conclude that the use of biofilms to synthesize and stabilize NPs is underappreciated and could provide a new direction in biofilm-based NP production. Copyright © 2016 Elsevier Inc. All rights reserved.

  9. Efficient Synthesis and Antimicrobial Evaluation of Pyrazolopyranopyrimidines in the Presence of SBA-Pr-SO3H as a Nanoporous Acid Catalyst

    PubMed Central

    Mohammadi Ziarani, Ghodsi; Aleali, Faezeh; Lashgari, Negar; Badiei, Alireza; Abolhasani Soorki, Ali

    2018-01-01

    A simple, efficient, and environmentally friendly method has been developed for the synthesis of a series of tricyclic fused pyrazolopyranopyrimidines via a one-pot three-component reaction of barbituric acids, aromatic aldehydes, and 3-methyl-5-pyrazolone in the presence of SBA-Pr-SO3H. SBA-15 mesoporous silica material functionalized with propyl sulfonic acid groups was used as a heterogeneous Brønsted acid catalyst with hexagonal structure, high surface area, thick walls, and large uniform pores. All reactions were performed under reflux conditions in water in the presence of a catalytic amount of SBA-Pr-SO3H. High yields, mild reaction conditions, short reaction times, and simple work-up procedures are some advantages of this method. The antimicrobial activities of the synthesized compounds were also evaluated and some products exhibited significant antibacterial activities at low concentrations. PMID:29881410

  10. Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels.

    PubMed

    Singh, Meenesh R; Clark, Ezra L; Bell, Alexis T

    2015-11-10

    Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32-42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0-0.9 V, 0.9-1.95 V, and 1.95-3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices.

  11. Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

    NASA Astrophysics Data System (ADS)

    Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

    2015-11-01

    Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32-42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0-0.9 V, 0.9-1.95 V, and 1.95-3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices.

  12. Synthesis and characterization of natural and modified antifreeze glycopeptides: glycosylated foldamers.

    PubMed

    Nagel, Lilly; Plattner, Carolin; Budke, Carsten; Majer, Zsuzsanna; DeVries, Arthur L; Berkemeier, Thomas; Koop, Thomas; Sewald, Norbert

    2011-08-01

    In Arctic and Antarctic marine regions, where the temperature declines below the colligative freezing point of physiological fluids, efficient biological antifreeze agents are crucial for the survival of polar fish. One group of such agents is classified as antifreeze glycoproteins (AFGP) that usually consist of a varying number (n = 4-55) of [AAT]( n )-repeating units. The threonine side chain of each unit is glycosidically linked to β-D: -galactosyl-(1 → 3)-α-N-acetyl-D: -galactosamine. These biopolymers can be considered as biological antifreeze foldamers. A preparative route for stepwise synthesis of AFGP allows for efficient synthesis. The diglycosylated threonine building block was introduced into the peptide using microwave-enhanced solid phase synthesis. By this versatile solid phase approach, glycosylated peptides of varying sequences and lengths could be obtained. Conformational studies of the synthetic AFGP analogs were performed by circular dichroism experiments (CD). Furthermore, the foldamers were analysed microphysically according to their inhibiting effect on ice recrystallization and influence on the crystal habit.

  13. Chemoenzymatic convergent synthesis of 2'-O,4'-C-methyleneribonucleosides.

    PubMed

    Sharma, Vivek K; Kumar, Manish; Olsen, Carl E; Prasad, Ashok K

    2014-07-03

    Novozyme-435-catalyzed efficient regioselective acetylation of one of the two diastereotopic hydroxymethyl functions in 3-O-benzyl-4-C-hydroxymethyl-1,2-O-isopropylidene-α-d-ribofuranose has been achieved. The enzymatic methodology has been successfully utilized for convergent synthesis of bicyclic nucleosides (LNA monomers) T, U, A, and C. Further, it has been demonstrated that Novozyme-435 can be used for 10 cycles of the acylation reaction without losing selectivity and efficiency.

  14. Efficient enzymatic synthesis and dual-colour fluorescent labelling of DNA probes using long chain azido-dUTP and BCN dyes

    PubMed Central

    Ren, Xiaomei; El-Sagheer, Afaf H.; Brown, Tom

    2016-01-01

    A sterically undemanding azide analogue of dTTP (AHP dUTP) with an alkyl chain and ethynyl attachment to the nucleobase was designed and incorporated into DNA by primer extension, reverse transcription and polymerase chain reaction (PCR). An azide-modified 523 bp PCR amplicon with all 335 thymidines replaced by AHP dU was shown to be a perfect copy of the template from which it was amplified. Replacement of thymidine with AHP dU increases duplex stability, accounting in part for the high incorporation efficiency of the azide-modified triphosphate. Single-stranded azide-labelled DNA was conveniently prepared from PCR products by λ-exonuclease digestion and streptavidin magnetic bead isolation. Efficient fluorescent labelling of single and double-stranded DNA was carried out using dyes functionalized with bicyclo[6.1.0]non-4-yne (BCN) via the strain-promoted alkyne-azide cycloaddition (SPAAC) reaction. This revealed that the degree of labelling must be carefully controlled to achieve optimum fluorescence and avoid fluorescence quenching. Dual-coloured probes were obtained in a single tube fluorescent labelling reaction; and varying the ratios of the two dyes provides a simple method to prepare DNA probes with unique fluorescent signatures. AHP dUTP is a versatile clickable nucleotide with potentially wide applications in biology and nanotechnology including single molecule studies and synthesis of modified aptamer libraries via SELEX. PMID:26819406

  15. An efficient microwave-assisted synthesis method for the production of water soluble amine-terminated Si nanoparticles.

    PubMed

    Atkins, Tonya M; Louie, Angelique Y; Kauzlarich, Susan M

    2012-07-27

    Silicon nanoparticles can be considered a green material, especially when prepared via a microwave-assisted method without the use of highly reactive reducing agents or hydrofluoric acid. A simple solution synthesis of hydrogen-terminated Si- and Mn-doped Si nanoparticles via microwave-assisted synthesis is demonstrated. The reaction of the Zintl salt, Na(4)Si(4), or Mn-doped Na(4)Si(4), Na(4)Si(4(Mn)), with ammonium bromide, NH(4)Br, produces small dispersible nanoparticles along with larger particles that precipitate. Allylamine and 1-amino-10-undecene were reacted with the hydrogen-terminated Si nanoparticles to provide water solubility and stability. A one-pot, single-reaction process and a one-pot, two-step reaction process were investigated. Details of the microwave-assisted process are provided, with the optimal synthesis being the one-pot, two-step reaction procedure and a total time of about 15 min. The nanoparticles were characterized by transmission electron microscopy (TEM), x-ray diffraction, and fluorescence spectroscopies. The microwave-assisted method reliably produces a narrow size distribution of Si nanoparticles in solution.

  16. Flow Chemistry for Designing Sustainable Chemical Synthesis (journal article)

    EPA Science Inventory

    An efficiently designed continuous flow chemical process can lead to significant advantages in developing a sustainable chemical synthesis or process. These advantages are the direct result of being able to impart a higher degree of control on several key reactor and reaction par...

  17. One-Pot Parallel Synthesis of Lipid Library via Thiolactone Ring Opening and Screening for Gene Delivery.

    PubMed

    Molla, Mijanur R; Böser, Alexander; Rana, Akshita; Schwarz, Karina; Levkin, Pavel A

    2018-04-18

    Efficient delivery of nucleic acids into cells is of great interest in the field of cell biology and gene therapy. Despite a lot of research, transfection efficiency and structural diversity of gene-delivery vectors are still limited. A better understanding of the structure-function relationship of gene delivery vectors is also essential for the design of novel and intelligent delivery vectors, efficient in "difficult-to-transfect" cells and in vivo clinical applications. Most of the existing strategies for the synthesis of gene-delivery vectors require multiple steps and lengthy procedures. Here, we demonstrate a facile, three-component one-pot synthesis of a combinatorial library of 288 structurally diverse lipid-like molecules termed "lipidoids" via a thiolactone ring opening reaction. This strategy introduces the possibility to synthesize lipidoids with hydrophobic tails containing both unsaturated bonds and reducible disulfide groups. The whole synthesis and purification are convenient, extremely fast, and can be accomplished within a few hours. Screening of the produced lipidoids using HEK293T cells without addition of helper lipids resulted in identification of highly stable liposomes demonstrating ∼95% transfection efficiency with low toxicity.

  18. Formal Synthesis of (±)-Aplykurodinone-1 through a Hetero-Pauson-Khand Cycloaddition Approach.

    PubMed

    Tao, Cheng; Zhang, Jing; Chen, Xiaoming; Wang, Huifei; Li, Yun; Cheng, Bin; Zhai, Hongbin

    2017-03-03

    The tricyclic intermediate 2 has been synthesized in eight steps from known compound 6 in 20% overall yield. As such, this constitutes a highly efficient formal synthesis of (±)-aplykurodinone-1. This synthesis features a unique, one-pot, intramolecular hetero-Pauson-Khand reaction (h-PKR)/desilylation sequence to expeditiously construct the tricyclic framework, providing valuable insights for expanding the scope and boundaries of h-PKR.

  19. Pharmacophore mapping in the laulimalide series: total synthesis of a vinylogue for a late-stage metathesis diversification strategy.

    PubMed

    Wender, Paul A; Hilinski, Michael K; Skaanderup, Philip R; Soldermann, Nicolas G; Mooberry, Susan L

    2006-08-31

    An efficient synthesis of the macrocyclic core of laulimalide with a pendant vinyl group at C20 is described, allowing for late-stage introduction of various side chains through a selective and efficient cross metathesis diversification step. Representative analogues reported herein are the first to contain modifications to only the side chain dihydropyran of laulimalide and des-epoxy laulimalide. This step-economical strategy enables the rapid synthesis of new analogues using alkenes as an inexpensive, abundantly available diversification feedstock.

  20. Growth, oxygen consumption, and protein and RNA synthesis rates in the yolk sac larvae of the African catfish (Clarias gariepinus).

    PubMed

    Smith, Richard W; Ottema, Colin

    2006-03-01

    Rapidly growing African catfish yolk sac larvae were investigated during the first 22 h after hatching. Body compartment protein concentration increased fourfold yet oxygen consumption remained constant (mean=21.3 +/- 3.2 nmol O2 mg(-1) protein h(-1)), suggesting fast growth results mainly from yolk sac protein absorption. The protein synthesis rates at 1-2 and 5-6 h also equaled the highest conceivable rates of muscle protein synthesis; 11.6-11.9% and 7.4-7.9% day(-1), respectively. Therefore the corresponding energetic costs of protein synthesis were almost the theoretical minimum; 13.0 +/- 1.7-16.3 +/- 2.8 micromol O2 mg(-1) protein synthesised. Total protein synthesis expenditure (74.5-77.7 micromol O2 g(-1) protein h(-1)) was also less than other yolk sac larvae. These protein synthesis rates resulted from high RNA concentrations (113.2 +/- 3.4 microg RNA mg(-1) protein) and were also correlated with RNA translational efficiency. High translational efficiency (1 h; 1.2+/-0.1 mg protein synthesised microg(-1) RNA day(-1)) equaled high synthesis rate (36.8 +/- 5.4 microg RNA microg(-1) DNA day(-1)) and both declined over 22 h. This investigation suggests rapid growth combines growth efficiency and compensatory energy partitioning. This accommodates the ontogenetic and phylogenetic standpoints imposed by energy budget limitations.

  1. Synthesis of (+)-dumetorine and congeners by using flow chemistry technologies.

    PubMed

    Riva, Elena; Rencurosi, Anna; Gagliardi, Stefania; Passarella, Daniele; Martinelli, Marisa

    2011-05-23

    An efficient total synthesis of the natural alkaloid (+)-dumetorine by using flow technology is described. The process entailed five separate steps starting from the enantiopure (S)-2-(piperidin-2-yl)ethanol 4 with 29% overall yield. Most of the reactions were carried out by exploiting solvent superheating and by using packed columns of immobilized reagents or scavengers to minimize handling. New protocols for performing classical reactions under continuous flow are disclosed: the ring-closing metathesis reaction with a novel polyethylene glycol-supported Hoveyda catalyst and the unprecedented flow deprotection/Eschweiler-Clarke methylation sequence. The new protocols developed for the synthesis of (+)-dumetorine were applied to the synthesis of its simplified natural congeners (-)-sedamine and (+)-sedridine. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Identifying and managing inappropriate hospital utilization: a policy synthesis.

    PubMed Central

    Payne, S M

    1987-01-01

    Utilization review, the assessment of the appropriateness and efficiency of hospital care through review of the medical record, and utilization management, deliberate action by payers or hospital administrators to influence providers of hospital services to increase the efficiency and effectiveness with which services are provided, are valuable but relatively unfamiliar strategies for containing hospital costs. The purpose of this synthesis is to increase awareness of the scope of and potential for these approaches among health services managers and administrators, third-party payers, policy analysts, and health services researchers. The synthesis will assist the reader to trace the conceptual context and the historical development of utilization review from unstructured methods using individual physicians' professional judgment to structured methods using explicit criteria; to establish the context of utilization review and clarify its uses; to understand the concepts and tools used in assessing the efficiency of hospital use; and to select, design, and evaluate utilization review and utilization management programs. The extent of inappropriate (medical unnecessary) hospital utilization and the factors associated with it are described. Implications for managers, providers, and third-party payers in targeting utilization review and in designing and evaluating utilization management programs are discussed. PMID:3121538

  3. Status and prospects in higher alcohols synthesis from syngas.

    PubMed

    Luk, Ho Ting; Mondelli, Cecilia; Ferré, Daniel Curulla; Stewart, Joseph A; Pérez-Ramírez, Javier

    2017-03-06

    Higher alcohols are important compounds with widespread applications in the chemical, pharmaceutical and energy sectors. Currently, they are mainly produced by sugar fermentation (ethanol and isobutanol) or hydration of petroleum-derived alkenes (heavier alcohols), but their direct synthesis from syngas (CO + H 2 ) would comprise a more environmentally-friendly, versatile and economical alternative. Research efforts in this reaction, initiated in the 1930s, have fluctuated along with the oil price and have considerably increased in the last decade due to the interest to exploit shale gas and renewable resources to obtain the gaseous feedstock. Nevertheless, no catalytic system reported to date has performed sufficiently well to justify an industrial implementation. Since the design of an efficient catalyst would strongly benefit from the establishment of synthesis-structure-function relationships and a deeper understanding of the reaction mechanism, this review comprehensively overviews syngas-based higher alcohols synthesis in three main sections, highlighting the advances recently made and the challenges that remain open and stimulate upcoming research activities. The first part critically summarises the formulations and methods applied in the preparation of the four main classes of materials, i.e., Rh-based, Mo-based, modified Fischer-Tropsch and modified methanol synthesis catalysts. The second overviews the molecular-level insights derived from microkinetic and theoretical studies, drawing links to the mechanisms of Fischer-Tropsch and methanol syntheses. Finally, concepts proposed to improve the efficiency of reactors and separation units as well as to utilise CO 2 and recycle side-products in the process are described in the third section.

  4. Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis

    DOE PAGES

    Kitano, Masaaki; Kanbara, Shinji; Inoue, Yasunori; ...

    2015-03-30

    We actively sough novel approaches to efficient ammonia synthesis at an ambient pressure so as to reduce the cost of ammonia production and to allow for compact production facilities. It is accepted that the key is the development of a high-performance catalyst that significantly enhances dissociation of the nitrogen-nitrogen triple bond, which is generally considered a rate-determining step. Here we examine the kinetics of nitrogen and hydrogen isotope exchange and hydrogen adsorption/desorption reactions for a recently discovered efficient catalyst for ammonia synthesis --ruthenium-loaded 12CaO∙7AI 2O 3 electride (Ru/C12A7:more » $$\\bar{e}$$ )--and find that the rate controlling step of ammonia synthesis over Ru/C12A7:$$\\bar{e}$$ is not dissociation of the nitrogen-nitrogen triple bond but the subsequent formation of N-H n species. A mechanism of ammonia synthesis involving reversible storage and release of hydrogen atoms on the Ru/C12A7:$$\\bar{e}$$ surface is proposed on the basis of observed hydrogen adsorption/desorption kinetics.« less

  5. Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kitano, Masaaki; Kanbara, Shinji; Inoue, Yasunori

    We actively sough novel approaches to efficient ammonia synthesis at an ambient pressure so as to reduce the cost of ammonia production and to allow for compact production facilities. It is accepted that the key is the development of a high-performance catalyst that significantly enhances dissociation of the nitrogen-nitrogen triple bond, which is generally considered a rate-determining step. Here we examine the kinetics of nitrogen and hydrogen isotope exchange and hydrogen adsorption/desorption reactions for a recently discovered efficient catalyst for ammonia synthesis --ruthenium-loaded 12CaO∙7AI 2O 3 electride (Ru/C12A7:more » $$\\bar{e}$$ )--and find that the rate controlling step of ammonia synthesis over Ru/C12A7:$$\\bar{e}$$ is not dissociation of the nitrogen-nitrogen triple bond but the subsequent formation of N-H n species. A mechanism of ammonia synthesis involving reversible storage and release of hydrogen atoms on the Ru/C12A7:$$\\bar{e}$$ surface is proposed on the basis of observed hydrogen adsorption/desorption kinetics.« less

  6. Chemoenzymatic synthesis and cytotoxicity of oenanthotoxin and analogues.

    PubMed

    Sommerwerk, Sven; Heller, Lucie; Siewert, Bianka; Csuk, René

    2015-09-01

    We developed a synthetic scheme for the synthesis of naturally occurring (14R)-oenanthotoxin and several analogs. Key-steps of this synthesis were an efficient homo-coupling of alkynes and a chemoenzymatic resolution of racemic oenanthotoxin using novozyme 435 and vinyl acetate. The compounds were screened for their cytotoxic activity using a photometric sulforhodamine B assays and several human tumor cell lines. Oenanthotoxin and many derivatives thereof were cytotoxic to tumor cell lines as well as to non-malignant mouse fibroblasts. The highest activity was determined for human ovarian cancer cells A2780 with EC50 = 3.8 μM. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Optimization of the Technological Synthesis of Refractory Compounds

    NASA Astrophysics Data System (ADS)

    Gaidar, S. M.; Karelina, M. Yu.; Prikhod'ko, V. M.; Volkov, A. A.

    2017-12-01

    The results of experimental studies, which are related to the regulation of the fractional composition of refractory compounds by roll milling in using controlled roll opening and unbalanced peripheral speeds of rollers, are reported. The content of prepared fine, middle, and coarse fractions is within 50-80%; in this case, the milling time of synthesis products is less than the time of ball milling by an order of magnitude. The application of roll milling for refining the products of self-propagating high-temperature synthesis can be most efficient in using together with heat-generating reactor to solve the main problem of self-propagating synthesis (SHS), which is a problem for recent several decades (the problem is the creation of intense automated production of refractory compounds in using continuous manufacturing cycle within a energotechnological system with the recovery of a great quantity of heat released during SHS).

  8. Aminofluorene-Mediated Biomimetic Domino Amination-Oxygenation of Aldehydes to Amides.

    PubMed

    Ghosh, Santanu; Jana, Chandan K

    2016-11-18

    A conceptually novel biomimetic strategy based on a domino amination-oxygenation reaction was developed for direct amidation of aldehydes under metal-free conditions employing molecular oxygen as the oxidant. 9-Aminofluorene derivatives acted as pyridoxamine-5'-phosphate equivalents for efficient, chemoselective, and operationally simple amine-transfer oxygenation reaction. Unprecedented RNH transfer involving secondary amine to produce secondary amides was achieved. In the presence of 18 O 2 , 18 O-amide was formed with excellent (95%) isotopic purity.

  9. Photochemistry of tricyclo[5.2.2.0(2,6)]undeca-4,10-dien-8-ones: an efficient general route to substituted linear triquinanes from 2-methoxyphenols. Total synthesis of (+/-)-Delta(9(12))-capnellene.

    PubMed

    Hsu, Day-Shin; Chou, Yu-Yu; Tung, Yen-Shih; Liao, Chun-Chen

    2010-03-08

    An efficient and short entry to polyfunctionalized linear triquinanes from 2-methoxyphenols is described by utilizing the following chemistry. The Diels-Alder reactions of masked o-benzoquinones, derived from 2-methoxyphenols, with cyclopentadiene afford tricyclo[5.2.2.0(2,6)]undeca-4,10-dien-8-ones. Photochemical oxa-di-pi-methane (ODPM) rearrangements and 1,3-acyl shifts of the Diels-Alder adducts are investigated. The ODPM-rearranged products are further converted to linear triquinanes by using an O-stannyl ketyl fragmentation. Application of this efficient strategy to the total synthesis of (+/-)-Delta(9(12))-capnellene was accomplished from 2-methoxy-4-methylphenol in nine steps with 20 % overall yield.

  10. Total Synthesis of the Post-translationally Modified Polyazole Peptide Antibiotic Goadsporin.

    PubMed

    Dexter, Hannah L; Williams, Huw E L; Lewis, William; Moody, Christopher J

    2017-03-06

    The structurally unique polyazole antibiotic goadsporin contains six heteroaromatic oxazole and thiazole rings integrated into a linear array of amino acids that also contains two dehydroalanine residues. An efficient total synthesis of goadsporin is reported in which the key steps are the use of rhodium(II)-catalyzed reactions of diazocarbonyl compounds to generate the four oxazole rings, which demonstrates the power of rhodium carbene chemistry in organic chemical synthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. High performance of a cobalt–nitrogen complex for the reduction and reductive coupling of nitro compounds into amines and their derivatives

    PubMed Central

    Zhou, Peng; Jiang, Liang; Wang, Fan; Deng, Kejian; Lv, Kangle; Zhang, Zehui

    2017-01-01

    Replacement of precious noble metal catalysts with low-cost, non-noble heterogeneous catalysts for chemoselective reduction and reductive coupling of nitro compounds holds tremendous promise for the clean synthesis of nitrogen-containing chemicals. We report a robust cobalt–nitrogen/carbon (Co–Nx/C-800-AT) catalyst for the reduction and reductive coupling of nitro compounds into amines and their derivates. The Co–Nx/C-800-AT catalyst was prepared by the pyrolysis of cobalt phthalocyanine–silica colloid composites and the subsequent removal of silica template and cobalt nanoparticles. The Co–Nx/C-800-AT catalyst showed extremely high activity, chemoselectivity, and stability toward the reduction of nitro compounds with H2, affording full conversion and >97% selectivity in water after 1.5 hours at 110°C and under a H2 pressure of 3.5 bar for all cases. The hydrogenation of nitrobenzene over the Co–Nx/C-800-AT catalyst can even be smoothly performed under very mild conditions (40°C and a H2 pressure of 1 bar) with an aniline yield of 98.7%. Moreover, the Co–Nx/C-800-AT catalyst has high activity toward the transfer hydrogenation of nitrobenzene into aniline and the reductive coupling of nitrobenzene into other derivates with high yields. These processes were carried out in an environmentally friendly manner without base and ligands. PMID:28232954

  12. Plasma-Assisted Synthesis and Surface Modification of Electrode Materials for Renewable Energy.

    PubMed

    Dou, Shuo; Tao, Li; Wang, Ruilun; El Hankari, Samir; Chen, Ru; Wang, Shuangyin

    2018-05-01

    Renewable energy technology has been considered as a "MUST" option to lower the use of fossil fuels for industry and daily life. Designing critical and sophisticated materials is of great importance in order to realize high-performance energy technology. Typically, efficient synthesis and soft surface modification of nanomaterials are important for energy technology. Therefore, there are increasing demands on the rational design of efficient electrocatalysts or electrode materials, which are the key for scalable and practical electrochemical energy devices. Nevertheless, the development of versatile and cheap strategies is one of the main challenges to achieve the aforementioned goals. Accordingly, plasma technology has recently appeared as an extremely promising alternative for the synthesis and surface modification of nanomaterials for electrochemical devices. Here, the recent progress on the development of nonthermal plasma technology is highlighted for the synthesis and surface modification of advanced electrode materials for renewable energy technology including electrocatalysts for fuel cells, water splitting, metal-air batteries, and electrode materials for batteries and supercapacitors, etc. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

    PubMed Central

    Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

    2015-01-01

    Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32–42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0–0.9 V, 0.9–1.95 V, and 1.95–3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices. PMID:26504215

  14. Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

    DOE PAGES

    Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

    2015-10-26

    Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32–42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0–0.9 V, 0.9–1.95 V, and 1.95–3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO 2 reduction on silver and coppermore » cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H 2 and CO) and Hythane (H 2 and CH 4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. Finally, we show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C 2H 4 have high profitability indices.« less

  15. High-Yield Synthesis and Optical Properties of Carbon Nanotube Porins

    DOE PAGES

    Tunuguntla, Ramya H.; Chen, Xi; Belliveau, Allison; ...

    2017-01-18

    Carbon nanotube porins (CNTPs) are a convenient membrane-based model system for studying nanofluidic transport that replicates a number of key structural features of biological membrane channels. We present a generalized approach for CNTP synthesis using sonochemistry-assisted segmenting of carbon nanotubes. Prolonged tip sonication in the presence of lipid molecules debundles and fragments long carbon nanotube aggregates into stable and water-soluble individual CNTPs with lengths in the range 5–20 nm. We discuss the main parameters that determine the efficiency and the yield of this process, describe the optimized conditions for high-yield CNTP synthesis, and demonstrate that this methodology can be adaptedmore » for synthesis of CNTPs of different diameters. We also present the optical properties of CNTPs and show that a combination of Raman and UV–vis–NIR spectroscopy can be used to monitor the quality of the CNTP synthesis. Altogether, CNTPs represent a versatile nanopore building block for creating higher-order functional biomimetic materials.« less

  16. Increased yield of PCR products by addition of T4 gene 32 protein to the SMART PCR cDNA synthesis system.

    PubMed

    Villalva, C; Touriol, C; Seurat, P; Trempat, P; Delsol, G; Brousset, P

    2001-07-01

    Under certain conditions, T4 gene 32 protein is known to increase the efficiency of different enzymes, such as Taq DNA polymerase, reverse transcriptase, and telomerase. In this study, we compared the efficiency of the SMART PCR cDNA synthesis kit with and without the T4 gene 32 protein. The use of this cDNA synthesis procedure, in combination with T4 gene 32 protein, increases the yield of RT-PCR products from approximately 90% to 150%. This effect is even observed for long mRNA templates and low concentrations of total RNA (25 ng). Therefore, we suggest the addition of T4 gene 32 protein in the RT-PCR mixture to increase the efficiency of cDNA synthesis, particularly in cases when low amounts of tissue are used.

  17. Rational engineering of p-hydroxybenzoate hydroxylase to enable efficient gallic acid synthesis via a novel artificial biosynthetic pathway.

    PubMed

    Chen, Zhenya; Shen, Xiaolin; Wang, Jian; Wang, Jia; Yuan, Qipeng; Yan, Yajun

    2017-11-01

    Gallic acid (GA) is a naturally occurring phytochemical that has strong antioxidant and antibacterial activities. It is also used as a potential platform chemical for the synthesis of diverse high-value compounds. Hydrolytic degradation of tannins by acids, bases or microorganisms serves as a major way for GA production, which however, might cause environmental pollution and low yield and efficiency. Here, we report a novel approach for efficient microbial production of GA. First, structure-based rational engineering of PobA, a p-hydroxybenzoate hydroxylase from Pseudomonas aeruginosa, generated a new mutant, Y385F/T294A PobA, which displayed much higher activity toward 3,4-dihydroxybenzoic acid (3,4-DHBA) than the wild-type and any other reported mutants. Remarkably, expression of this mutant in Escherichia coli enabled generation of 1149.59 mg/L GA from 1000 mg/L 4-hydroxybenzoic acid (4-HBA), representing a 93% molar conversion ratio. Based on that, we designed and reconstituted a novel artificial biosynthetic pathway of GA and achieved 440.53 mg/L GA production from simple carbon sources in E. coli. Further enhancement of precursor supply through reinforcing shikimate pathway was able to improve GA de novo production to 1266.39 mg/L in shake flasks. Overall, this study not only led to the development of a highly active PobA variant for hydroxylating 3,4-DHBA into GA via structure-based protein engineering approach, but also demonstrated a promising pathway for bio-based manufacturing of GA and its derived compounds. Biotechnol. Bioeng. 2017;114: 2571-2580. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  18. Gold Nanoparticle Microwave Synthesis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Krantz, Kelsie E.; Christian, Jonathan H.; Coopersmith, Kaitlin

    At the nanometer scale, numerous compounds display different properties than those found in bulk material that can prove useful in areas such as medicinal chemistry. Gold nanoparticles, for example, display promise in newly developed hyperthermia therapies for cancer treatment. Currently, gold nanoparticle synthesis is performed via the hot injection technique which has large variability in final particle size and a longer reaction time. One underdeveloped area by which these particles could be produced is through microwave synthesis. To initiate heating, microwaves agitate polar molecules creating a vibration that gives off the heat energy needed. Previous studies have used microwaves formore » gold nanoparticle synthesis; however, polar solvents were used that partially absorbed incident microwaves, leading to partial thermal heating of the sample rather than taking full advantage of the microwave to solely heat the gold nanoparticle precursors in a non-polar solution. Through this project, microwaves were utilized as the sole heat source, and non-polar solvents were used to explore the effects of microwave heating only as pertains to the precursor material. Our findings show that the use of non-polar solvents allows for more rapid heating as compared to polar solvents, and a reduction in reaction time from 10 minutes to 1 minute; this maximizes the efficiency of the reaction, and allows for reproducibility in the size/shape of the fabricated nanoparticles.« less

  19. Fully Synthetic Granulocyte Colony-Stimulating Factor Enabled by Isonitrile-Mediated Coupling of Large, Side-Chain-Unprotected Peptides

    PubMed Central

    Roberts, Andrew G.; Johnston, Eric V.; Shieh, Jae-Hung; Sondey, Joseph P.; Hendrickson, Ronald C.; Moore, Malcolm A. S.; Danishefsky, Samuel J.

    2015-01-01

    Human granulocyte colony-stimulating factor (G-CSF) is an endogenous glycoprotein involved in hematopoiesis. Natively glycosylated and nonglycosylated recombinant forms, lenograstim and filgrastim, respectively, are used clinically to manage neutropenia in patients undergoing chemotherapeutic treatment. Despite their comparable therapeutic potential, the purpose of O-linked glycosylation at Thr133 remains a subject of controversy. In light of this, we have developed a synthetic platform to prepare G-CSF aglycone with the goal of enabling access to native and designed glycoforms with site-selectivity and glycan homogeneity. To address the synthesis of a relatively large, aggregation-prone sequence, we advanced an isonitrile-mediated ligation method. The chemoselective activation and coupling of C-terminal peptidyl Gly thioacids with the N-terminus of an unprotected peptide provide ligated peptides directly in a manner complementary to that with conventional native chemical ligation–desulfurization strategies. Herein, we describe the details and application of this method as it enabled the convergent total synthesis of G-CSF aglycone. PMID:26401918

  20. Pot economy and one-pot synthesis.

    PubMed

    Hayashi, Yujiro

    2016-02-01

    The one-pot synthesis of a target molecule in the same reaction vessel is widely considered to be an efficient approach in synthetic organic chemistry. In this review, the characteristics and limitations of various one-pot syntheses of biologically active molecules are explained, primarily involving organocatalytic methods as key tactics. Besides catalysis, the pot-economy concepts presented herein are also applicable to organometallic and organic reaction methods in general.

  1. Cobalt ion-coordinated self-assembly synthesis of nitrogen-doped ordered mesoporous carbon nanosheets for efficiently catalyzing oxygen reduction.

    PubMed

    Wang, Haitao; Wang, Wei; Asif, Muhammad; Yu, Yang; Wang, Zhengyun; Wang, Junlei; Liu, Hongfang; Xiao, Junwu

    2017-10-19

    The design and synthesis of a promising porous carbon-based electrocatalyst with an ordered and uninterrupted porous structure for oxygen reduction reaction (ORR) is still a significant challenge. Herein, an efficient catalyst based on cobalt-embedded nitrogen-doped ordered mesoporous carbon nanosheets (Co/N-OMCNS) is successfully prepared through a two-step procedure (cobalt ion-coordinated self-assembly and carbonization process) using 3-aminophenol as a nitrogen source, cobalt acetate as a cobalt source and Pluronic F127 as a mesoporous template. This work indicates that the formation of a two dimensional nanosheet structure is directly related to the extent of the cobalt ion coordination interaction. Moreover, the critical roles of pyrolysis temperature in nitrogen doping and ORR catalytic activity are also investigated. Benefiting from the high surface area and graphitic degree, high contents of graphitic N and pyridinic N, ordered interconnected mesoporous carbon framework, as well as synergetic interaction between the cobalt nanoparticles and protective nitrogen doped graphitic carbon layer, the resultant optimal catalyst Co/N-OMCNS-800 (pyrolyzed at 800 °C) exhibits comparable ORR catalytic activity to Pt/C, superior tolerance to methanol crossover and stability.

  2. Synthesis and antibacterial activity of novel enolphosphate derivatives.

    PubMed

    Grison, Claude; Barthes, Nicolas; Finance, Chantal; Duval, Raphael E

    2010-10-01

    A new class of enolphosphates derivatives, the 1-alkenyldiphosphates, was designed and a rapid and efficient synthesis for these compounds was developed. These new molecules showed interesting in vitro antibacterial activities (MIC) against Gram-positive bacteria (Staphylococcus aureus) and Gram-negative pathogens including Pseudomonas aeruginosa and Escherichia coli. 2010 Elsevier Inc. All rights reserved.

  3. Controlled synthesis of phosphorylcholine derivatives of poly(serine) and poly(homoserine).

    PubMed

    Yakovlev, Ilya; Deming, Timothy J

    2015-04-01

    We report methods for the synthesis of polypeptides that are fully functionalized with desirable phosphorylcholine, PC, groups. Because of the inherent challenges in the direct incorporation of the PC group into α-amino acid N-carboxyanhydride (NCA) monomers, we developed a synthetic approach that combined functional NCA polymerization with efficient postpolymerization modification. While poly(L-phosphorylcholine serine) was found to be unstable upon synthesis, we successfully prepared poly(L-phosphorylcholine homoserine) with controlled chain lengths and found these to be water-soluble with disordered chain conformations.

  4. Investigation of innovative synthesis of biologically active compounds on the basis of newly developed reactions.

    PubMed

    Honda, Toshio

    2012-01-01

    Synthesis of biologically active compounds, including natural products and pharmaceutical agents, is an important and interesting research area since the large structural diversity and complexity of bioactive compounds make them an important source of leads and scaffolds in drug discovery and development. Many structurally and also biologically interesting compounds, including marine natural products, have been isolated from nature and have also been prepared on the basis of a computational design for the purpose of developing medicinal chemistry. In order to obtain a wide variety of derivatives of biologically active compounds from the viewpoint of medicinal chemistry, it is essential to establish efficient synthetic procedures for desired targets. Newly developed reactions should also be used for efficient synthesis of desired compounds. Thus, recent progress in the synthesis of biologically active compounds by focusing on the development of new reactions is summarized in this review article.

  5. Fungal Anticancer Metabolites: Synthesis Towards Drug Discovery.

    PubMed

    Barbero, Margherita; Artuso, Emma; Prandi, Cristina

    2018-01-01

    Fungi are a well-known and valuable source of compounds of therapeutic relevance, in particular of novel anticancer compounds. Although seldom obtainable through isolation from the natural source, the total organic synthesis still remains one of the most efficient alternatives to resupply them. Furthermore, natural product total synthesis is a valuable tool not only for discovery of new complex biologically active compounds but also for the development of innovative methodologies in enantioselective organic synthesis. We undertook an in-depth literature searching by using chemical bibliographic databases (SciFinder, Reaxys) in order to have a comprehensive insight into the wide research field. The literature has been then screened, refining the obtained results by subject terms focused on both biological activity and innovative synthetic procedures. The literature on fungal metabolites has been recently reviewed and these publications have been used as a base from which we consider the synthetic feasibility of the most promising compounds, in terms of anticancer properties and drug development. In this paper, compounds are classified according to their chemical structure. This review summarizes the anticancer potential of fungal metabolites, highlighting the role of total synthesis outlining the feasibility of innovative synthetic procedures that facilitate the development of fungal metabolites into drugs that may become a real future perspective. To our knowledge, this review is the first effort to deal with the total synthesis of these active fungi metabolites and demonstrates that total chemical synthesis is a fruitful means of yielding fungal derivatives as aided by recent technological and innovative advancements. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  6. Amino acid substrates impose polyamine, eIF5A, or hypusine requirement for peptide synthesis

    PubMed Central

    Shin, Byung-Sik; Katoh, Takayuki; Gutierrez, Erik; Kim, Joo-Ran; Suga, Hiroaki

    2017-01-01

    Abstract Whereas ribosomes efficiently catalyze peptide bond synthesis by most amino acids, the imino acid proline is a poor substrate for protein synthesis. Previous studies have shown that the translation factor eIF5A and its bacterial ortholog EF-P bind in the E site of the ribosome where they contact the peptidyl-tRNA in the P site and play a critical role in promoting the synthesis of polyproline peptides. Using misacylated Pro-tRNAPhe and Phe-tRNAPro, we show that the imino acid proline and not tRNAPro imposes the primary eIF5A requirement for polyproline synthesis. Though most proline analogs require eIF5A for efficient peptide synthesis, azetidine-2-caboxylic acid, a more flexible four-membered ring derivative of proline, shows relaxed eIF5A dependency, indicating that the structural rigidity of proline might contribute to the requirement for eIF5A. Finally, we examine the interplay between eIF5A and polyamines in promoting translation elongation. We show that eIF5A can obviate the polyamine requirement for general translation elongation, and that this activity is independent of the conserved hypusine modification on eIF5A. Thus, we propose that the body of eIF5A functionally substitutes for polyamines to promote general protein synthesis and that the hypusine modification on eIF5A is critically important for poor substrates like proline. PMID:28637321

  7. Elucidating the reaction pathways in the synthesis of organolead trihalide perovskite for high-performance solar cells.

    PubMed

    Wang, Baohua; Young Wong, King; Xiao, Xudong; Chen, Tao

    2015-05-28

    The past two years have witnessed unprecedentedly rapid development of organic-inorganic halide perovskite-based solar cells. The solution-processability and high efficiency make this technology extraordinarily attractive. The intensive investigations have accumulated rich experiences in the perovskite fabrication; while the mechanism of the chemical synthesis still remains unresolved. Here, we set up the chemical equation of the synthesis and elucidate the reactions from both thermodynamic and kinetic perspectives. Our study shows that gaseous products thermodynamically favour the reaction, while the activation energy and "collision" probability synergistically determine the reaction rate. These understandings enable us to finely tune the crystal size for high-quality perovskite film, leading to a record fill factor among similar device structures in the literature. This investigation provides a general strategy to explore the mechanism of perovskite synthesis and benefits the fabrication of high-efficiency perovskite photoactive layer.

  8. A Multidimensional Diversity‐Oriented Synthesis Strategy for Structurally Diverse and Complex Macrocycles

    PubMed Central

    Nie, Feilin; Kunciw, Dominique L.; Wilcke, David; Stokes, Jamie E.; Galloway, Warren R. J. D.; Bartlett, Sean; Sore, Hannah F.

    2016-01-01

    Abstract Synthetic macrocycles are an attractive area in drug discovery. However, their use has been hindered by a lack of versatile platforms for the generation of structurally (and thus shape) diverse macrocycle libraries. Herein, we describe a new concept in library synthesis, termed multidimensional diversity‐oriented synthesis, and its application towards macrocycles. This enabled the step‐efficient generation of a library of 45 novel, structurally diverse, and highly‐functionalized macrocycles based around a broad range of scaffolds and incorporating a wide variety of biologically relevant structural motifs. The synthesis strategy exploited the diverse reactivity of aza‐ylides and imines, and featured eight different macrocyclization methods, two of which were novel. Computational analyses reveal a broad coverage of molecular shape space by the library and provides insight into how the various diversity‐generating steps of the synthesis strategy impact on molecular shape. PMID:27484830

  9. Synthesis of Water-Soluble Palladium Nanoparticles Stabilized by Sulfonated N-Heterocyclic Carbenes.

    PubMed

    Asensio, Juan M; Tricard, Simon; Coppel, Yannick; Andrés, Román; Chaudret, Bruno; de Jesús, Ernesto

    2017-09-27

    A strategy involving the decomposition of palladium(II) organometallic complexes with sulfonated N-heterocyclic carbene ligands leads to the formation of stable and water-soluble Pd nanoparticles. Three different methodologies (thermal decomposition, reduction under 13 CO atmosphere, and reduction with H 2 ) gave particles with different shapes and sizes, ranging from 1.5 to 7 nm. The structures of the organometallic intermediates and organic decomposition products were elucidated by NMR spectroscopy. To check the accessibility of the surface, the nanoparticles were tested as catalysts for the chemoselective hydrogenation of styrene in water. An effect of the particle size on the catalyst activity was observed. The aqueous phase was recycled up to ten times without any precipitation of metallic palladium. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Oligoglyceric acid synthesis by autocondensation of glyceroyl thioester

    NASA Technical Reports Server (NTRS)

    Weber, A. L.

    1986-01-01

    The autocondensation of the glyceroyl thioester, S-glyceroyl-ethane-thiol, yielded olioglyceric acid. The rates of autocondensation and hydrolysis of the thioester increased from pH 6.5 to pH 7.5 in 2,6-lutidine and imidazole buffers. Autocondensation and hydrolysis were much more rapid in imidazole buffers as compared to 2,6-lutidine and phosphate buffers. The efficiency of ester bond synthesis was about 20% for 40 mM S-glyceroyl-ethane-thiol in 2,6-lutidine and imidazole buffers near neutral pH. The size and yield of the olioglyceric acid products increased when the concentration of the thioester was increased. The relationship of these results to prebiotic polymer synthesis is discussed.

  11. Automated optimization techniques for aircraft synthesis

    NASA Technical Reports Server (NTRS)

    Vanderplaats, G. N.

    1976-01-01

    Application of numerical optimization techniques to automated conceptual aircraft design is examined. These methods are shown to be a general and efficient way to obtain quantitative information for evaluating alternative new vehicle projects. Fully automated design is compared with traditional point design methods and time and resource requirements for automated design are given. The NASA Ames Research Center aircraft synthesis program (ACSYNT) is described with special attention to calculation of the weight of a vehicle to fly a specified mission. The ACSYNT procedures for automatically obtaining sensitivity of the design (aircraft weight, performance and cost) to various vehicle, mission, and material technology parameters are presented. Examples are used to demonstrate the efficient application of these techniques.

  12. The effect of reactor geometry on the synthesis of graphene materials in plasma jets

    NASA Astrophysics Data System (ADS)

    Shavelkina, M. B.; Amirov, R. H.; Shatalova, T. B.

    2017-05-01

    The possibility of synthesis of graphene and graphane (hydrogenated graphene) using the decomposition of hydrocarbons by thermal plasma has been investigated. Investigations of the influence of the plasma-forming gas on the efficiency of synthesis and the morphology of graphene materials were carried out. The synthesis products have been characterized by the methods of scanning microscopy, Raman spectroscopy and thermal analysis. It is found that the morphology of graphene materials is affected by the geometry of the reactor. It was demonstrated that the obtained graphene materials are uniformly distributed in the volume of plastic based on cyanate ester resins under mixing.

  13. Use of the 2-chlorotrityl chloride resin for microwave-assisted solid phase peptide synthesis.

    PubMed

    Ieronymaki, Matthaia; Androutsou, Maria Eleni; Pantelia, Anna; Friligou, Irene; Crisp, Molly; High, Kirsty; Penkman, Kirsty; Gatos, Dimitrios; Tselios, Theodore

    2015-09-01

    A fast and efficient microwave (MW)-assisted solid-phase peptide synthesis protocol using the 2-chlorotrityl chloride resin and the Fmoc/tBu methodology, has been developed. The established protocol combines the advantages of MW irradiation and the acid labile 2-chlorotrityl chloride resin. The effect of temperature during the MW irradiation, the degree of resin substitution during the coupling of the first amino acids and the rate of racemization for each amino acid were evaluated. The suggested solid phase methodology is applicable for orthogonal peptide synthesis and for the synthesis of cyclic peptides. © 2015 Wiley Periodicals, Inc.

  14. A facile and eco-friendly synthesis of diarylthiazoles and diarylimidazoles in water

    EPA Science Inventory

    A simple, efficient and high yielding greener protocol for the synthesis of substituted thiazoles and imidazoles is described that utilizes the reaction of readily available α-tosyloxy ketones with variety of thioamides/amidines in water

  15. Novel High Efficient Organic Photovoltaic Materials

    NASA Technical Reports Server (NTRS)

    Sun, Sam; Haliburton, James; Wang, Yi-Qing; Fan, Zhen; Taft, Charles; Maaref, Shahin; Bailey, Sheila (Technical Monitor)

    2003-01-01

    Solar energy is a renewable, nonpolluting, and most abundant energy source for human exploration of a remote site or outer space. In order to generate appreciable electrical power in space or on the earth, it is necessary to collect sunlight from large areas and with high efficiency due to the low density of sunlight. Future organic or polymer (plastic) solar cells appear very attractive due to their unique features such as light weight, flexible shape, tunability of energy band-gaps via versatile molecular or supramolecular design, synthesis, processing and device fabrication schemes, and much lower cost on large scale industrial production. It has been predicted that supramolecular and nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration due to improved electronic ultrastructure and morphology in comparison to polymer composite system. This presentation will describe our recent progress in the design, synthesis and characterization of a novel block copolymer system containing donor and acceptor blocks covalently attached. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (RO-PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (SF-PPV). The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block has a strong PL emission at around 560 nm, and acceptor block has a strong PL emission at around 520 nm, the PL emissions of final block copolymers are severely quenched. This verifies the expected electron transfer and charge separation due to interfaces of donor and acceptor nano phase separated blocks. The system therefore has potential for variety light harvesting applications, including high efficient photovoltaic applications.

  16. An efficient and more sustainable one-step continuous-flow multicomponent synthesis approach to chromene derivatives

    EPA Science Inventory

    A simple and rapid one-step continuous-flow synthesis route has been developed for the preparation of chromene derivatives from the reaction of aromatic aldehydes, α-cyanomethylene compounds and naphthols. In this contribution, a one-step continuous-flow protocol in a continuous ...

  17. 2,2,2-Trifluoroacetophenone as an organocatalyst for the oxidation of tertiary amines and azines to N-oxides.

    PubMed

    Limnios, Dimitris; Kokotos, Christoforos G

    2014-01-07

    A cheap, mild and environmentally friendly oxidation of tertiary amines and azines to the corresponding N-oxides is reported by using polyfluoroalkyl ketones as efficient organocatalysts. 2,2,2-Trifluoroacetophenone was identified as the optimum catalyst for the oxidation of aliphatic tertiary amines and azines. This oxidation is chemoselective and proceeds in high-to-quantitative yields utilizing 10 mol % of the catalyst and H2 O2 as the oxidant. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Synthesis-on” and “synthesis-off” modes of carbon arc operation during synthesis of carbon nanotubes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yatom, Shurik; Selinsky, Rachel S.; Koel, Bruce E.

    Arc discharge synthesis of single-walled carbon nanotubes (SWCNTs) remains largely uncontrollable, due to incomplete understanding of the synthetic process itself. Here, we show that synthesis of SWCNTs by a carbon arc may not constitute a single continuous process, but may instead consist of two distinct modes. One of these, a “synthesis-on” mode, produces the majority of the nanomaterials. During the synthesis-on mode, proportionally more carbon nanotubes are collected than in another mode, a “synthesis-off” mode. Both synthesis-on and synthesis-off modes for a typical arc configuration, employing a hollow anode filled with a mixture of powdered metal catalyst and graphite, weremore » characterized by using in situ electrical, imaging, and spectroscopic diagnostics, along with ex situ imaging and spectroscopy. The synthesis-on mode duration is rare compared to the total arc run-time, helping to explain the poor selectivity found in the final collected products, a known inadequacy of arc synthesis. Finally, the rarity of the synthesis on mode occurence may be due to the synthesis off mode being more favorable energetically.« less

  19. Synthesis-on” and “synthesis-off” modes of carbon arc operation during synthesis of carbon nanotubes

    DOE PAGES

    Yatom, Shurik; Selinsky, Rachel S.; Koel, Bruce E.; ...

    2017-09-09

    Arc discharge synthesis of single-walled carbon nanotubes (SWCNTs) remains largely uncontrollable, due to incomplete understanding of the synthetic process itself. Here, we show that synthesis of SWCNTs by a carbon arc may not constitute a single continuous process, but may instead consist of two distinct modes. One of these, a “synthesis-on” mode, produces the majority of the nanomaterials. During the synthesis-on mode, proportionally more carbon nanotubes are collected than in another mode, a “synthesis-off” mode. Both synthesis-on and synthesis-off modes for a typical arc configuration, employing a hollow anode filled with a mixture of powdered metal catalyst and graphite, weremore » characterized by using in situ electrical, imaging, and spectroscopic diagnostics, along with ex situ imaging and spectroscopy. The synthesis-on mode duration is rare compared to the total arc run-time, helping to explain the poor selectivity found in the final collected products, a known inadequacy of arc synthesis. Finally, the rarity of the synthesis on mode occurence may be due to the synthesis off mode being more favorable energetically.« less

  20. An efficient and practical synthesis of [2- 11C]indole via superfast nucleophilic [ 11C]cyanation and RANEY® Nickel catalyzed reductive cyclization

    DOE PAGES

    So Jeong Lee; Fowler, Joanna S.; Alexoff, David; ...

    2015-09-21

    We developed a rapid method for the synthesis of carbon-11 radiolabeled indole using a sub-nanomolar quantity of no-carrier-added [ 11C]cyanide as radio-precursor. Based upon a reported synthesis of 2-(2-nitrophenyl)acetonitrile (2), a highly reactive substrate 2-nitrobenzyl bromide (1) was evaluated for nucleophilic [ 11C]cyanation. Additionally, related reaction conditions were explored with the goal of obtaining of highly reactive 2-(2-nitrophenyl)-[1- 11C]acetonitrile ([ 11C]-2) while inhibiting its rapid conversion to 2,3-bis(2-nitrophenyl)-[1- 11C]propanenitrile ([ 11C]-3). Next, a Raney Nickel catalyzed reductive cyclization method was utilized for synthesizing the desired [2- 11C]indole with hydrazinium monoformate as the active reducing agent. Extensive and iterative screening ofmore » basicity, temperature and stoichiometry was required to overcome the large stoichiometry bias that favored 2-nitrobenzylbromide (1) over [ 11C]cyanide, which both caused further alkylation of the desired nitrile and poisoned the Raney Nickel catalyst. The result is an efficient two-step, streamlined method to reliably synthesize [2- 11C]indole with an entire radiochemical yield of 21 ± 2.2% (n = 5, ranging from 18 – 24%). The radiochemical purity of the final product was > 98% and specific activity was 176 ± 24.8 GBq/μmol (n = 5, ranging from 141 – 204 GBq/μmol). The total radiosynthesis time including product purification by semi-preparative HPLC was 50 – 55 min from end of cyclotron bombardment.« less

  1. An efficient and practical synthesis of [2- 11C]indole via superfast nucleophilic [ 11C]cyanation and RANEY® Nickel catalyzed reductive cyclization

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    So Jeong Lee; Fowler, Joanna S.; Alexoff, David

    We developed a rapid method for the synthesis of carbon-11 radiolabeled indole using a sub-nanomolar quantity of no-carrier-added [ 11C]cyanide as radio-precursor. Based upon a reported synthesis of 2-(2-nitrophenyl)acetonitrile (2), a highly reactive substrate 2-nitrobenzyl bromide (1) was evaluated for nucleophilic [ 11C]cyanation. Additionally, related reaction conditions were explored with the goal of obtaining of highly reactive 2-(2-nitrophenyl)-[1- 11C]acetonitrile ([ 11C]-2) while inhibiting its rapid conversion to 2,3-bis(2-nitrophenyl)-[1- 11C]propanenitrile ([ 11C]-3). Next, a Raney Nickel catalyzed reductive cyclization method was utilized for synthesizing the desired [2- 11C]indole with hydrazinium monoformate as the active reducing agent. Extensive and iterative screening ofmore » basicity, temperature and stoichiometry was required to overcome the large stoichiometry bias that favored 2-nitrobenzylbromide (1) over [ 11C]cyanide, which both caused further alkylation of the desired nitrile and poisoned the Raney Nickel catalyst. The result is an efficient two-step, streamlined method to reliably synthesize [2- 11C]indole with an entire radiochemical yield of 21 ± 2.2% (n = 5, ranging from 18 – 24%). The radiochemical purity of the final product was > 98% and specific activity was 176 ± 24.8 GBq/μmol (n = 5, ranging from 141 – 204 GBq/μmol). The total radiosynthesis time including product purification by semi-preparative HPLC was 50 – 55 min from end of cyclotron bombardment.« less

  2. Synthesis of potassium ferrate using residual ferrous sulfate as iron bearing material

    NASA Astrophysics Data System (ADS)

    Kanari, N.; Filippov, L.; Diot, F.; Mochón, J.; Ruiz-Bustinza, I.; Allain, E.; Yvon, J.

    2013-03-01

    This paper summarizes the results obtained during potassium ferrate (K2FeVIO4) synthesis which is a high added value material. This compound that contains iron in the rare hexavalent state is becoming a substance of growing importance for the water and effluent treatment industries. This is due to its multi-functional nature (oxidation, flocculation, elimination of heavy metals, decomposition of organic matter, etc.). The most well known synthesis methods for potassium ferrate synthesis are those involving the chemical and/or electrochemical oxidation of iron (II) and (III) from aqueous solutions having a high alkali concentration. These methods are generally characterized by a low FeVI efficiency due to the reaction of the potassium ferrate with water, leading to the reduction of FeVI into FeIII. Concerning the work pertinent to this paper, the synthesis of K2FeVIO4 was achieved by a simultaneous reaction of two solids (iron sulfate and KOH) and one gaseous oxidant (chlorine). The synthesis process is performed in a rotary reactor at room temperature and the global synthesis reaction is exothermic. The effects of different experimental parameters on the potassium ferrate synthesis are investigated to determine the optimal conditions for the process.

  3. Enantioselective synthesis of spirooxoindoles via chiral auxiliary (bicyclic lactam) controlled SNAr reactions.

    PubMed

    Sen, Subhabrata; Potti, Venkata R; Surakanti, Ramu; Murthy, Y L N; Pallepogu, Raghavaiah

    2011-01-21

    A highly efficient enantioselective S(N)Ar reaction of chiral acyl bicyclic lactam with substituted-2,4-dinitrobenzenes was developed, affording products containing quarternary stereogenic centers. They are further utilized towards an enantioselective synthesis of spirooxoindoles.

  4. Chemoenzymatic synthesis of Amaryllidaceae constituents and biological evaluation of their C-1 analogs. The next generation synthesis of 7-deoxypancratistatin and dihydrolycoricidine.1

    PubMed Central

    Collins, Jonathan; Rinner, Uwe; Moser, Michael; Hudlicky, Tomas; Ghiviriga, Ion; Romero, Anntherese E.; Kornienko, Alexander; Ma, Dennis; Griffin, Carly; Pandey, Siyaram

    2010-01-01

    An efficient synthesis of C-1 derivatives of 7-deoxypancratistatin is reported. The key steps include the following: selective opening of an epoxide with aluminum acetylide in the presence of an aziridine; solid-state silica-gel-catalyzed opening of an aziridine; oxidative cleavage of a phenanthrene core and its recyclization to phenanthridone to provide the key C-1 aldehyde 22. The conversion of this aldehyde to C-1 acetoxymethyl and C-1 hydroxymethyl derivatives is described along with the evaluation of their biological activity against several cancer cell lines and in an apoptosis study. The C-1 acetoxymethyl derivative has shown promising activity comparable to that of the natural product. In addition, a total synthesis of trans-dihydrolycoricidine and a formal total synthesis of 7-deoxypancratistatin are reported from aldehyde 22. Detailed experimental and spectral data are provided for all new compounds. PMID:20373760

  5. Fluorous tagging strategy for solution-phase synthesis of small molecules, peptides and oligosaccharides

    PubMed Central

    Zhang, Wei

    2005-01-01

    The purification of reaction mixtures is a slow process in organic synthesis, especially during the production of large numbers of analogs and compound libraries. Phase-tag methods such as solid-phase synthesis and fluorous synthesis, provide efficient ways of addressing the separation issue. Fluorous synthesis employs functionalized perfluoroalkyl groups attached to substrates or reagents. The separation of the resulting fluorous molecules can be achieved using strong and selective fluorous liquid-liquid extraction, fluorous silica gel-based solid-phase extraction or high-performance liquid chromatography. Fluorous technology is a novel solution-phase method, which has the advantages of fast reaction times in homogeneous environments, being readily adaptable to literature conditions, having easy intermediate analysis, and having flexibility in reaction scale and scope. In principle, any synthetic methods that use a solid-support could be conducted in solution-phase by replacing the polymer linker with a corresponding fluorous tag. This review summarizes the progress of fluorous tags in solution-phase synthesis of small molecules, peptides and oligosaccharides. PMID:15595439

  6. Reaction of Donor-Acceptor Cyclobutanes with Indoles: A General Protocol for the Formal Total Synthesis of (±)-Strychnine and the Total Synthesis of (±)-Akuammicine.

    PubMed

    Feng, Liang-Wen; Ren, Hai; Xiong, Hu; Wang, Pan; Wang, Lijia; Tang, Yong

    2017-03-06

    A ligand-promoted catalytic [4+2] annulation reaction using indole derivatives and donor-acceptor (D-A) cyclobutanes is reported, thus providing an efficient and atom-economical access to versatile cyclohexa-fused indolines with excellent levels of diastereoselectivity and a broad substrate scope. In the presence of a chiral SaBOX ligand, excellent enantioselectivity was realized with up to 94 % ee. This novel synthetic method is applied as a general protocol for the total synthesis of (±)-akuammicine and the formal total synthesis of (±)-strychnine from the same common-core scaffold. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Synthesis of the Pitstop family of clathrin inhibitors.

    PubMed

    Robertson, Mark J; Deane, Fiona M; Stahlschmidt, Wiebke; von Kleist, Lisa; Haucke, Volker; Robinson, Phillip J; McCluskey, Adam

    2014-07-01

    This protocol describes the synthesis of two classes of clathrin inhibitors, Pitstop 1 and Pitstop 2, along with two inactive analogs that can be used as negative controls (Pitstop inactive controls, Pitnot-2 and Pitnot-2-100). Pitstop-induced inhibition of clathrin TD function acutely interferes with clathrin-mediated endocytosis (CME), synaptic vesicle recycling and cellular entry of HIV, whereas clathrin-independent internalization pathways and secretory traffic proceed unperturbed; these reagents can, therefore, be used to investigate clathrin function, and they have potential pharmacological applications. Pitstop 1 is synthesized in two steps: sulfonation of 1,8-naphthalic anhydride and subsequent reaction with 4-amino(methyl)aniline. Pitnot-1 results from the reaction of 4-amino(methyl)aniline with commercially available 4-sulfo-1,8-naphthalic anhydride potassium salt. Reaction of 1-naphthalene sulfonyl chloride with pseudothiohydantoin followed by condensation with 4-bromobenzaldehyde yields Pitstop 2. The synthesis of the inactive control commences with the condensation of 4-bromobenzaldehyde with the rhodanine core. Thioketone methylation and displacement with 1-napthylamine affords the target compound. Although Pitstop 1-series compounds are not cell permeable, they can be used in biochemical assays or be introduced into cells via microinjection. The Pitstop 2-series compounds are cell permeable. The synthesis of these compounds does not require specialist equipment and can be completed in 3-4 d. Microwave irradiation can be used to reduce the synthesis time. The synthesis of the Pitstop 2 family is easily adaptable to enable the synthesis of related compounds such as Pitstop 2-100 and Pitnot-2-100. The procedures are also simple, efficient and amenable to scale-up, enabling cost-effective in-house synthesis for users of these inhibitor classes.

  8. Mechanistic Investigations into the Application of Sulfoxides in Carbohydrate Synthesis

    PubMed Central

    Brabham, Robin

    2016-01-01

    Abstract The utility of sulfoxides in a diverse range of transformations in the field of carbohydrate chemistry has seen rapid growth since the first introduction of a sulfoxide as a glycosyl donor in 1989. Sulfoxides have since developed into more than just anomeric leaving groups, and today have multiple roles in glycosylation reactions. These include as activators for thioglycosides, hemiacetals, and glycals, and as precursors to glycosyl triflates, which are essential for stereoselective β‐mannoside synthesis, and bicyclic sulfonium ions that facilitate the stereoselective synthesis of α‐glycosides. In this review we highlight the mechanistic investigations undertaken in this area, often outlining strategies employed to differentiate between multiple proposed reaction pathways, and how the conclusions of these investigations have and continue to inform upon the development of more efficient transformations in sulfoxide‐based carbohydrate synthesis. PMID:26744250

  9. Diastereoselective Pyrrolidine Synthesis via Copper Promoted Intramolecular Aminooxygenation of Alkenes; Formal Synthesis of (+)-Monomorine

    PubMed Central

    Paderes, Monissa C; Chemler, Sherry R

    2009-01-01

    The diastereoselectivity of the copper-promoted intramolecular aminooxygenation of various alkene substrates was investigated. α-Substituted 4-pentenyl sulfonamides favor the formation of 2,5-cis-pyrrolidines (dr >20:1) giving excellent yields which range from 76–97% while γ-substituted substrates favor the 2,3-trans pyrrolidine adducts with moderate selectivity (ca. 3:1). A substrate whose N-substituent was directly tethered to the α-carbon exclusively yielded the 2,5-trans pyrrolidine. The synthetic utility of the method was demonstrated by a short and efficient formal synthesis of (+)-monomorine. PMID:19331361

  10. Investigation of Polyurethane Electrospinning Process Efficiency

    NASA Astrophysics Data System (ADS)

    Kimmer, Dusan; Zatloukal, Martin; Petras, David; Vincent, Ivo; Slobodian, Petr

    2009-07-01

    The electrospinning process efficiency of different PUs has been investigated. Specific attention has been paid to understand the role of PU soft segments and synthesis type on the stability of the PU solution and electrospinning process as well as on the quality/property changes of the produced nanofibres. PU samples before and after the process were analyzed rheologicaly and relaxation spectra were determined for all of them from frequency dependent loss and storage moduli measurements. It has been found that rheological analysis of PU, which is used for electrospinning process, can be useful tool from electrospinning process efficiency and optimization point of view. Nanolayers homogeneity during several hours of manufacture in optimized electrospinning process is proved by selected properties from aerosol filtration.

  11. Stereoselective synthesis of novel highly substituted isochromanone and isoquinolinone-containing exocyclic tetrasubstituted alkenes.

    PubMed

    Arthuis, Martin; Pontikis, Renée; Florent, Jean-Claude

    2009-03-06

    An efficient synthetic route toward the synthesis of highly substituted arylethylidene-isoquinolinones/isochromanones is reported. The tandem carbopalladation/Suzuki-Miyaura coupling sequence stereoselectively provided various functionalized polycyclic compounds in moderate to excellent yields.

  12. Highly efficient enzymatic synthesis of 2-monoacylglycerides and structured lipids and their production on a technical scale.

    PubMed

    Pfeffer, Jan; Freund, Andreas; Bel-Rhlid, Rachid; Hansen, Carl-Erik; Reuss, Matthias; Schmid, Rolf D; Maurer, Steffen C

    2007-10-01

    We report here a two-step process for the high-yield enzymatic synthesis of 2-monoacylglycerides (2-MAG) of saturated as well as unsaturated fatty acids with different chain lengths. The process consists of two steps: first the unselective esterification of fatty acids and glycerol leading to a triacylglyceride followed by an sn1,3-selective alcoholysis reaction yielding 2-monoacylglycerides. Remarkably, both steps can be catalyzed by lipase B from Candida antarctica (CalB). The whole process including esterification and alcoholysis was scaled up in a miniplant to a total volume of 10 l. With this volume, a two-step process catalyzed by CalB for the synthesis of 1,3-oleoyl-2-palmitoylglycerol (OPO) using tripalmitate as starting material was established. On a laboratory scale, we obtained gram quantities of the synthesized 2-monoacylglycerides of polyunsaturated fatty acids such as arachidonic-, docosahexaenoic- and eicosapentaenoic acids and up to 96.4% of the theoretically possible yield with 95% purity. On a technical scale (>100 g of product, >5 l of reaction volume), 97% yield was reached in the esterification and 73% in the alcoholysis and a new promising process for the enzymatic synthesis of OPO was established.

  13. Amino acid substrates impose polyamine, eIF5A, or hypusine requirement for peptide synthesis.

    PubMed

    Shin, Byung-Sik; Katoh, Takayuki; Gutierrez, Erik; Kim, Joo-Ran; Suga, Hiroaki; Dever, Thomas E

    2017-08-21

    Whereas ribosomes efficiently catalyze peptide bond synthesis by most amino acids, the imino acid proline is a poor substrate for protein synthesis. Previous studies have shown that the translation factor eIF5A and its bacterial ortholog EF-P bind in the E site of the ribosome where they contact the peptidyl-tRNA in the P site and play a critical role in promoting the synthesis of polyproline peptides. Using misacylated Pro-tRNAPhe and Phe-tRNAPro, we show that the imino acid proline and not tRNAPro imposes the primary eIF5A requirement for polyproline synthesis. Though most proline analogs require eIF5A for efficient peptide synthesis, azetidine-2-caboxylic acid, a more flexible four-membered ring derivative of proline, shows relaxed eIF5A dependency, indicating that the structural rigidity of proline might contribute to the requirement for eIF5A. Finally, we examine the interplay between eIF5A and polyamines in promoting translation elongation. We show that eIF5A can obviate the polyamine requirement for general translation elongation, and that this activity is independent of the conserved hypusine modification on eIF5A. Thus, we propose that the body of eIF5A functionally substitutes for polyamines to promote general protein synthesis and that the hypusine modification on eIF5A is critically important for poor substrates like proline. Published by Oxford University Press on behalf of Nucleic Acids Research 2017.

  14. Highly efficient and stable blue-emitting CsPbBr3@SiO2 nanospheres through low temperature synthesis for nanoprinting and WLED.

    PubMed

    Shao, He; Bai, Xue; Pan, Gencai; Cui, Haining; Zhu, Jinyang; Zhai, Yue; Liu, Jingshi; Dong, Biao; Xu, Lin; Song, Hongwei

    2018-07-13

    Inorganic perovskite quantum dots (QDs) have attracted wide attention in display and solid-state lighting because of their easily tunable band-gaps and high photoluminescence quantum yields (PLQY) of green light emission. However, some drawbacks limit their practical applications, including the low PLQY of blue light emission and the instability in the moisture environment. In this work, efficient blue-light emitting CsPbBr 3 perovskite QDs with PLQY of 72% were developed through a bandgap engineering approach. The achieved blue-light emitting PLQY is much higher than the values acquired in the inorganic perovskite QDs in the literature. And the emission color of the as-prepared QDs can be facially tuned by only adjusting the reaction temperature. Further, the mono-dispersed perovskite QDs@SiO 2 composites were constructed benefiting from the low temperature synthesis. The optical performance of the QDs could be well persisted even in the moisture environment. Finally, the as-prepared QDs@SiO 2 composite was fabricated as the QD ink on the anti-counterfeit printing technology, from which the obtained pattern would emit varied color under UV lamp. And the as-prepared composites was also applied for fabricating WLED, with Commission Internationale de l'Eclairage (CIE) color coordinates of (0.33, 0.38) and power efficiency of 32.5 lm W -1 , demonstrating their promising potentials in solid-state lighting.

  15. Highly efficient and stable blue-emitting CsPbBr3@SiO2 nanospheres through low temperature synthesis for nanoprinting and WLED

    NASA Astrophysics Data System (ADS)

    Shao, He; Bai, Xue; Pan, Gencai; Cui, Haining; Zhu, Jinyang; Zhai, Yue; Liu, Jingshi; Dong, Biao; Xu, Lin; Song, Hongwei

    2018-07-01

    Inorganic perovskite quantum dots (QDs) have attracted wide attention in display and solid-state lighting because of their easily tunable band-gaps and high photoluminescence quantum yields (PLQY) of green light emission. However, some drawbacks limit their practical applications, including the low PLQY of blue light emission and the instability in the moisture environment. In this work, efficient blue-light emitting CsPbBr3 perovskite QDs with PLQY of 72% were developed through a bandgap engineering approach. The achieved blue-light emitting PLQY is much higher than the values acquired in the inorganic perovskite QDs in the literature. And the emission color of the as-prepared QDs can be facially tuned by only adjusting the reaction temperature. Further, the mono-dispersed perovskite QDs@SiO2 composites were constructed benefiting from the low temperature synthesis. The optical performance of the QDs could be well persisted even in the moisture environment. Finally, the as-prepared QDs@SiO2 composite was fabricated as the QD ink on the anti-counterfeit printing technology, from which the obtained pattern would emit varied color under UV lamp. And the as-prepared composites was also applied for fabricating WLED, with Commission Internationale de l’Eclairage (CIE) color coordinates of (0.33, 0.38) and power efficiency of 32.5 lm W‑1, demonstrating their promising potentials in solid-state lighting.

  16. Overall energy conversion efficiency of a photosynthetic vesicle

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sener, Melih; Strumpfer, Johan; Singharoy, Abhishek

    The chromatophore of purple bacteria is an intracellular spherical vesicle that exists in numerous copies in the cell and that efficiently converts sunlight into ATP synthesis, operating typically under low light conditions. Building on an atomic-level structural model of a low-light-adapted chromatophore vesicle from Rhodobacter sphaeroides, we investigate the cooperation between more than a hundred protein complexes in the vesicle. The steady-state ATP production rate as a function of incident light intensity is determined after identifying quinol turnover at the cytochrome bc1 complex (cytbc1) as rate limiting and assuming that the quinone/quinol pool of about 900 molecules acts in amore » quasi-stationary state. For an illumination condition equivalent to 1% of full sunlight, the vesicle exhibits an ATP production rate of 82 ATP molecules/s. The energy conversion efficiency of ATP synthesis at illuminations corresponding to 1%–5% of full sunlight is calculated to be 0.12-0.04, respectively. The vesicle stoichiometry, evolutionarily adapted to the low light intensities in the habitat of purple bacteria, is suboptimal for steady-state ATP turnover for the benefit of protection against over-illumination.« less

  17. Overall energy conversion efficiency of a photosynthetic vesicle

    DOE PAGES

    Sener, Melih; Strumpfer, Johan; Singharoy, Abhishek; ...

    2016-08-26

    The chromatophore of purple bacteria is an intracellular spherical vesicle that exists in numerous copies in the cell and that efficiently converts sunlight into ATP synthesis, operating typically under low light conditions. Building on an atomic-level structural model of a low-light-adapted chromatophore vesicle from Rhodobacter sphaeroides, we investigate the cooperation between more than a hundred protein complexes in the vesicle. The steady-state ATP production rate as a function of incident light intensity is determined after identifying quinol turnover at the cytochrome bc1 complex (cytbc1) as rate limiting and assuming that the quinone/quinol pool of about 900 molecules acts in amore » quasi-stationary state. For an illumination condition equivalent to 1% of full sunlight, the vesicle exhibits an ATP production rate of 82 ATP molecules/s. The energy conversion efficiency of ATP synthesis at illuminations corresponding to 1%–5% of full sunlight is calculated to be 0.12-0.04, respectively. The vesicle stoichiometry, evolutionarily adapted to the low light intensities in the habitat of purple bacteria, is suboptimal for steady-state ATP turnover for the benefit of protection against over-illumination.« less

  18. Total Synthesis of (±)-Cis-Trikentrin B via Intermolecular 6,7-Indole Aryne Cycloaddition and Stille Cross-Coupling.

    PubMed

    Chandrasoma, Nalin; Brown, Neil; Brassfield, Allen; Nerurkar, Alok; Suarez, Susana; Buszek, Keith R

    2013-02-20

    An efficient total synthesis of the annulated indole natural product (±)- cis -trikentrin B was accomplished by means of a regioselectively generated 6,7-indole aryne cycloaddition via selective metal-halogen exchange from a 5,6,7-tribromoindole. The unaffected C-5 bromine was subsequently used for a Stille cross-coupling to install the butenyl side chain and complete the synthesis. This strategy provides rapid access into the trikentrins and the related herbindoles, and represents another application of this methodology to natural products total synthesis. The required 5,6,7-indole aryne precursor was prepared using the Leimgruber-Batcho indole synthesis.

  19. Apparatus for the laser ablative synthesis of carbon nanotubes

    DOEpatents

    Smith, Michael W.; Jordan, Kevin

    2010-02-16

    An RF-induction heated side-pumped synthesis chamber for the production of carbon nanotubes. Such an apparatus, while capable of producing large volumes of carbon nanotubes, concurrently provides a simplified apparatus that allows for greatly reduced heat up and cool down times and flexible flowpaths that can be readily modified for production efficiency optimization.

  20. Measurement of host-to-activator transfer efficiency in nano-crystalline Y{sub 2}O{sub 3}:Eu{sup 3+} under VUV excitation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Waite, Christopher; Mann, Rusty; Diaz, Anthony L., E-mail: DiazA@cwu.edu

    2013-02-15

    We have conducted a systematic study of the excitation and reflectance spectra of nano-crystalline Y{sub 2}O{sub 3}:Eu prepared by combustion synthesis. Excitation through the host lattice becomes relatively more efficient as the firing temperature of the precursor is increased, while reflectance properties remain essentially unchanged. Using these data, host-to-activator transfer efficiencies were calculated for excitation at the band edge of Y{sub 2}O{sub 3}, and evaluated using a competition kinetics model. From this analysis we conclude that the relatively low luminous efficiency of these materials is due more to poor bulk crystallinity than to surface loss effects. - Graphical abstract: Themore » low luminous efficiency of nano-crystalline Y{sub 2}O{sub 3}:Eu{sup 3+} prepared by combustion synthesis is due to poor bulk crystallinity rather than surface loss effects. Highlights: Black-Right-Pointing-Pointer We report on the optical properties of Y{sub 2}O{sub 3}:Eu{sup 3+} prepared by combustion synthesis. Black-Right-Pointing-Pointer Host-to-activator transfer efficiencies under VUV excitation were calculated. Black-Right-Pointing-Pointer The low luminous efficiency of these materials is due to poor bulk crystallinity.« less

  1. Biological Synthesis of Nanoparticles from Plants and Microorganisms.

    PubMed

    Singh, Priyanka; Kim, Yu-Jin; Zhang, Dabing; Yang, Deok-Chun

    2016-07-01

    Nanotechnology has become one of the most promising technologies applied in all areas of science. Metal nanoparticles produced by nanotechnology have received global attention due to their extensive applications in the biomedical and physiochemical fields. Recently, synthesizing metal nanoparticles using microorganisms and plants has been extensively studied and has been recognized as a green and efficient way for further exploiting microorganisms as convenient nanofactories. Here, we explore and detail the potential uses of various biological sources for nanoparticle synthesis and the application of those nanoparticles. Furthermore, we highlight recent milestones achieved for the biogenic synthesis of nanoparticles by controlling critical parameters, including the choice of biological source, incubation period, pH, and temperature. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Green Synthesis of Metal Nanoparticles Using Sprout Plants: Pros and Cons.

    PubMed

    Park, Sungmook; Sung, Hwa Kyung; Kim, Younghun

    2016-05-01

    A critical need in the field of nanotechnology is the development of a sustainable and eco-friendly process for the synthesis of metallic nanoparticles (NPs). To accomplish this, the use of live plants becomes essential for the production of low-cost, energy-efficient, and nontoxic metallic NPs. In this study, we tried in-vivo synthesis (green synthesis) of silver and gold NPs using seeds of bean, radish, and alfalfa, which were grown hydroponically in aqueous solutions containing metal salts, 20-25 nm sized NPs were found on the inner surfaces of the plants' vascular cylinders and cortex. The amounts of NPs taken up by the intracellular systems were clearly dependent on the exposure time and concentration of the metal salts. Although these results regarding the green synthesis of NPs on the growth of plant species are somewhat interesting and effective, metal salts adversely affected the root growth of the plants. Silver ions in the growth media showed a more negative impact on root growth compared to gold ions. Therefore, even though biosynthesis of metal NPs using live plants is considered as green synthesis, we have to consider their phytotoxicity on plant growth.

  3. Synthesis of Arbitrary Quantum Circuits to Topological Assembly: Systematic, Online and Compact.

    PubMed

    Paler, Alexandru; Fowler, Austin G; Wille, Robert

    2017-09-05

    It is challenging to transform an arbitrary quantum circuit into a form protected by surface code quantum error correcting codes (a variant of topological quantum error correction), especially if the goal is to minimise overhead. One of the issues is the efficient placement of magic state distillation sub circuits, so-called distillation boxes, in the space-time volume that abstracts the computation's required resources. This work presents a general, systematic, online method for the synthesis of such circuits. Distillation box placement is controlled by so-called schedulers. The work introduces a greedy scheduler generating compact box placements. The implemented software, whose source code is available at www.github.com/alexandrupaler/tqec, is used to illustrate and discuss synthesis examples. Synthesis and optimisation improvements are proposed.

  4. Synthesis of the Tellurium-Derivatized Phosphoramidites and their Incorporation into DNA Oligonucleotides

    PubMed Central

    Jiang, Sibo; Sheng, Jia

    2015-01-01

    Introduction In this unit, an efficient method for the synthesis of 2’-tellerium modified phosphoramidite and its incorporation into oligonucleotide are presented. We choose 5’-O-DMTr-2,2’-anhydro-uridine and -thymidine nucleosides (S.1, S.2) as starting materials due to their easy preparation. The 5’-O-DMTr-2,2’-anhydro-uridine and -thymidine can be converted to corresponding the 2’-tellerium-derivatized nucleosides by treating with the telluride nucleophiles. Subsequently, the 2’-Te-nucleosides can be transformed into 3’-phosphoramidites, which are the building blocks for DNA/RNA synthesis. The DNA synthesis, purification and applications of oligonucleotides containing 2’-Te-U or 2’-Te-T are described in this protocol. PMID:22147418

  5. Copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines: synthesis of imidazopyridine derivatives.

    PubMed

    Yu, Jipan; Jin, Yunhe; Zhang, Hao; Yang, Xiaobo; Fu, Hua

    2013-12-02

    A novel, efficient, and practical method for the synthesis of imidazopyridine derivatives has been developed through the copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines with N-(alkylidene)-4H-1,2,4-triazol-4-amines. The procedure occurs by cleavage of the N-N bond in the N-(alkylidene)-4H-1,2,4-triazol-4-amines and activation of an aryl C-H bond in the substituted pyridines. This is the first example of the preparation of imidazopyridine derivatives by using pyridines as the substrates by transition-metal-catalyzed C-H functionalization. This method should provide a novel and efficient strategy for the synthesis of other nitrogen heterocycles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. One-Pot Synthesis of N-Substituted β-Amino Alcohols from Aldehydes and Isocyanides.

    PubMed

    Cioc, Răzvan C; van der Niet, Daan J H; Janssen, Elwin; Ruijter, Eelco; Orru, Romano V A

    2015-05-18

    A practical two-stage one-pot synthesis of N-substituted β-amino alcohols using aldehydes and isocyanides as starting materials has been developed. This method features mild reaction conditions, broad scope, and general tolerance of functional groups. Based on a less common central carbon-carbon bond disconnection, this protocol complements traditional approaches that involve amines and various carbon electrophiles (epoxides, α-halo ketones, β-halohydrins). Medicinally relevant products can be prepared in a concise and efficient way from simple building blocks, as demonstrated in the synthesis of the antiasthma drug salbutamol. Upgrading the synthesis to an enantioselective variant is also feasible. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A novel and efficient samarium iodide-mediated synthesis of neoflavonoids (4-arycloumarins)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Nagasawa, Kazuo; Ryohke, Hirosi; Ohnishi, Makoto

    1995-12-31

    Bioactive 4-arylcoumarins (4-aryl-2H-1-benzopyran-2-ones) have been recently isolated from the plants belonging to the families like Leguminosae, Guttiferae, and Compositae, some of which are still used as the traditional folk medicine. Despite many methods reported so far, there appears to be of limited success or of no success in some cases (II{sub b-g}) and, therefore, a simpler and more reliable one remains to be highly desired. Thus, a new and sterling protocol is now presented for the synthesis of neoflavonoids, which involves the intramolecular Reformatsky-type reaction via a one electron transfer process with samarium diiodide as a key step.

  8. One-pot green synthesis of doxorubicin loaded-silica nanoparticles for in vivo cancer therapy.

    PubMed

    Jiang, Shan; Hua, Li; Guo, Zilong; Sun, Lin

    2018-09-01

    The present work reveals a new and simple one-pot green method to load doxorubicin (DOX) drugs in silica nanoparticles for efficient in vivo cancer therapy. The synthesis of DOX loaded silica nanoparticles (SiNPs/DOX) is based on the efficient encapsulation of DOX in surfactant Tween 80 micelles which act as a template for the formation of silica nanoparticles. The release profile, cellular uptake behavior, cytotoxicity and antitumor effect of SiNPs/DOX nanoparticles were investigated and compared to free DOX. The silica nanoparticles improved the cellular drug delivery efficiency and exhibited high cytotoxicity, successfully achieving the inhibition of tumor growth. Notably, the tumor size and weight of SiNPs/DOX group was 2-fold and 1.7-fold smaller than that of free DOX group, and 4-fold and 2-fold smaller than that of PBS group. The one-pot green synthesis system may have the potential to be developed as a promising drug delivery system. Copyright © 2018 Elsevier B.V. All rights reserved.

  9. Discovery and gram-scale synthesis of BMS-593214, a potent, selective FVIIa inhibitor

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Priestley, E. Scott; De Lucca, Indawati; Zhou, Jinglan

    A 6-amidinotetrahydroquinoline screening hit was driven to a structurally novel, potent, and selective FVIIa inhibitor through a combination of library synthesis and rational design. An efficient gram-scale synthesis of the active enantiomer BMS-593214 was developed, which required significant optimization of the key Povarov annulation. Importantly, BMS-593214 showed antithrombotic efficacy in a rabbit arterial thrombosis model. A crystal structure of BMS-593214 bound to FVIIa highlights key contacts with Asp 189, Lys 192, and the S2 pocket.

  10. M13 virus-directed synthesis of nanostructured metal oxides for lithium-oxygen batteries.

    PubMed

    Oh, Dahyun; Qi, Jifa; Han, Binghong; Zhang, Geran; Carney, Thomas J; Ohmura, Jacqueline; Zhang, Yong; Shao-Horn, Yang; Belcher, Angela M

    2014-08-13

    Transition metal oxides are promising electrocatalysts for both water oxidations and metal-air batteries. Here, we report the virus-mediated synthesis of cobalt manganese oxide nanowires (NWs) to fabricate high capacity Li-O2 battery electrodes. Furthermore, we hybridized Ni nanoparticles (NPs) on bio Co3O4 NWs to improve the round trip efficiency as well as the cycle life of Li-O2 batteries. This biomolecular directed synthesis method is expected to provide a selection platform for future energy storage electrocatalysts.

  11. Facile, eco-friendly, catalyst-free synthesis of polyfunctionalized quinoxalines.

    PubMed

    Zhang, Yaohong; Luo, Mengqiang; Li, Yan; Wang, Hai; Ren, Xiaorong; Qi, Chenze

    2018-02-01

    A novel, facile and eco-friendly synthesis of quinoxalines from [Formula: see text] and 1,2-diamines was developed. An attractive feature of this protocol is that the desired products could be generated efficiently in water and without any catalyst, which is in accordance with the aim of green chemistry. A plausible mechanism has been proposed.

  12. Sustainable and Continuous Synthesis of Enantiopure l-Amino Acids by Using a Versatile Immobilised Multienzyme System.

    PubMed

    Velasco-Lozano, Susana; da Silva, Eunice S; Llop, Jordi; López-Gallego, Fernando

    2018-02-16

    The enzymatic synthesis of α-amino acids is a sustainable and efficient alternative to chemical processes, through which achieving enantiopure products is difficult. To more address this synthesis efficiently, a hierarchical architecture that irreversibly co-immobilises an amino acid dehydrogenase with polyethyleneimine on porous agarose beads has been designed and fabricated. The cationic polymer acts as an irreversible anchoring layer for the formate dehydrogenase. In this architecture, the two enzymes and polymer colocalise across the whole microstructure of the porous carrier. This multifunctional heterogeneous biocatalyst was kinetically characterised and applied to the enantioselective synthesis of a variety of canonical and noncanonical α-amino acids in both discontinuous (batch) and continuous modes. The co-immobilised bienzymatic system conserves more than 50 % of its initial effectiveness after five batch cycles and 8 days of continuous operation. Additionally, the environmental impact of this process has been semiquantitatively calculated and compared with the state of the art. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. VCP and ATL1 regulate endoplasmic reticulum and protein synthesis for dendritic spine formation

    PubMed Central

    Shih, Yu-Tzu; Hsueh, Yi-Ping

    2016-01-01

    Imbalanced protein homeostasis, such as excessive protein synthesis and protein aggregation, is a pathogenic hallmark of a range of neurological disorders. Here, using expression of mutant proteins, a knockdown approach and disease mutation knockin mice, we show that VCP (valosin-containing protein), together with its cofactor P47 and the endoplasmic reticulum (ER) morphology regulator ATL1 (Atlastin-1), regulates tubular ER formation and influences the efficiency of protein synthesis to control dendritic spine formation in neurons. Strengthening the significance of protein synthesis in dendritic spinogenesis, the translation blocker cyclohexamide and the mTOR inhibitor rapamycin reduce dendritic spine density, while a leucine supplement that increases protein synthesis ameliorates the dendritic spine defects caused by Vcp and Atl1 deficiencies. Because VCP and ATL1 are the causative genes of several neurodegenerative and neurodevelopmental disorders, we suggest that impaired ER formation and inefficient protein synthesis are significant in the pathogenesis of multiple neurological disorders. PMID:26984393

  14. VCP and ATL1 regulate endoplasmic reticulum and protein synthesis for dendritic spine formation.

    PubMed

    Shih, Yu-Tzu; Hsueh, Yi-Ping

    2016-03-17

    Imbalanced protein homeostasis, such as excessive protein synthesis and protein aggregation, is a pathogenic hallmark of a range of neurological disorders. Here, using expression of mutant proteins, a knockdown approach and disease mutation knockin mice, we show that VCP (valosin-containing protein), together with its cofactor P47 and the endoplasmic reticulum (ER) morphology regulator ATL1 (Atlastin-1), regulates tubular ER formation and influences the efficiency of protein synthesis to control dendritic spine formation in neurons. Strengthening the significance of protein synthesis in dendritic spinogenesis, the translation blocker cyclohexamide and the mTOR inhibitor rapamycin reduce dendritic spine density, while a leucine supplement that increases protein synthesis ameliorates the dendritic spine defects caused by Vcp and Atl1 deficiencies. Because VCP and ATL1 are the causative genes of several neurodegenerative and neurodevelopmental disorders, we suggest that impaired ER formation and inefficient protein synthesis are significant in the pathogenesis of multiple neurological disorders.

  15. N-Methylpyrrolidone Hydroperoxide/Cs2 CO3 as an Excellent Reagent System for the Hydroxy-Directed Diastereoselective Epoxidation of Electron-Deficient Olefins.

    PubMed

    Victor, Napoleon John; Gana, Janardhanan; Muraleedharan, Kannoth Manheri

    2015-10-12

    This report introduces N-methylpyrrolidone hydroperoxide (NMPOOH)/base as an excellent reagent system for hydroxy-directed syn selective epoxidation of electron-deficient olefins, characterized by high diastereoselectivity, short reaction times and remarkable chemoselectivity, especially in presence of oxidatively labile nitrogen or sulfur atoms. NMPOOH also proves efficient in the oxidation of electron-deficient aromatic aldehydes, in the removal of oxazolidinone chiral auxiliary, and in the functionalization of alkenes and alkynes, showing wide application potential. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Rapid Vortex Fluidics: Continuous Flow Synthesis of Amides and Local Anesthetic Lidocaine.

    PubMed

    Britton, Joshua; Chalker, Justin M; Raston, Colin L

    2015-07-20

    Thin film flow chemistry using a vortex fluidic device (VFD) is effective in the scalable acylation of amines under shear, with the yields of the amides dramatically enhanced relative to traditional batch techniques. The optimized monophasic flow conditions are effective in ≤80 seconds at room temperature, enabling access to structurally diverse amides, functionalized amino acids and substituted ureas on multigram scales. Amide synthesis under flow was also extended to a total synthesis of local anesthetic lidocaine, with sequential reactions carried out in two serially linked VFD units. The synthesis could also be executed in a single VFD, in which the tandem reactions involve reagent delivery at different positions along the rapidly rotating tube with in situ solvent replacement, as a molecular assembly line process. This further highlights the versatility of the VFD in organic synthesis, as does the finding of a remarkably efficient debenzylation of p-methoxybenzyl amines. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Visual difference metric for realistic image synthesis

    NASA Astrophysics Data System (ADS)

    Bolin, Mark R.; Meyer, Gary W.

    1999-05-01

    An accurate and efficient model of human perception has been developed to control the placement of sample in a realistic image synthesis algorithm. Previous sampling techniques have sought to spread the error equally across the image plane. However, this approach neglects the fact that the renderings are intended to be displayed for a human observer. The human visual system has a varying sensitivity to error that is based upon the viewing context. This means that equivalent optical discrepancies can be very obvious in one situation and imperceptible in another. It is ultimately the perceptibility of this error that governs image quality and should be used as the basis of a sampling algorithm. This paper focuses on a simplified version of the Lubin Visual Discrimination Metric (VDM) that was developed for insertion into an image synthesis algorithm. The sampling VDM makes use of a Haar wavelet basis for the cortical transform and a less severe spatial pooling operation. The model was extended for color including the effects of chromatic aberration. Comparisons are made between the execution time and visual difference map for the original Lubin and simplified visual difference metrics. Results for the realistic image synthesis algorithm are also presented.

  18. a Real-Time Computer Music Synthesis System

    NASA Astrophysics Data System (ADS)

    Lent, Keith Henry

    A real time sound synthesis system has been developed at the Computer Music Center of The University of Texas at Austin. This system consists of several stand alone processors that were constructed jointly with White Instruments in Austin. These processors can be programmed as general purpose computers, but are provided with a number of specialized interfaces including: MIDI, 8 bit parallel, high speed serial, 2 channels analog input (18 bit A/Ds, 48kHz sample rate), and 4 channels analog output (18 bit D/As). In addition, a basic music synthesis language (Music56000) has been written in assembly code. On top of this, a symbolic compiler (PatchWork) has been developed to enable algorithms which run in these processors to be created graphically. And finally, a number of efficient time domain numerical models have been developed to enable the construction, simulation, control, and synthesis of many musical acoustics systems in real time on these processors. Specifically, assembly language models for cylindrical and conical horn sections, dissipative losses, tone holes, bells, and a number of linear and nonlinear boundary conditions have been developed.

  19. Parallel synthesis of ureas and carbamates from amines and CO2 under mild conditions.

    PubMed

    Peterson, Scott L; Stucka, Sabrina M; Dinsmore, Christopher J

    2010-03-19

    A mild and efficient library synthesis technique has been developed for the synthesis of ureas and carbamates from carbamic acids derived from the DBU-catalyzed reaction of amines and gaseous carbon dioxide. Carbamic acids derived from primary amines reacted with Mitsunobu reagents to generate isocyanates in situ which were condensed with primary and secondary amines to afford the desired ureas. Similarly, carbamic acids from secondary amines reacted with alcohols activated with Mitsunobu reagents to form carbamates.

  20. Sonochemical synthesis and structural characterization of a new Zn(II) nanoplate metal-organic framework with removal efficiency of Sudan red and Congo red.

    PubMed

    Abdollahi, Nasrin; Masoomi, Mohammad Yaser; Morsali, Ali; Junk, Peter C; Wang, Jun

    2018-07-01

    A 3-D Zn(II) based metal-organic framework (MOF) of [Zn 4 (oba) 3 (DMF) 2 ] was synthesized using the nonlinear dicarboxylate ligand, 4,4'-oxybis(benzoic acid) (H 2 oba) via sonochemical and solvothermal routes. IR spectroscopy, single-crystal X-ray crystallography, scanning electron microscopy, and X-ray powder diffraction were used to characterize these MOF samples. The effect of different times of irradiation and various concentrations of primary reagents were experimented for obtaining monotonous morphology. The results show that uniform nanoplates can be achieved by increasing the time of irradiation and decreasing the concentration. N 2 adsorption was applied to examine the effect of synthesis method on porosity of the framework. Also Congo red and Sudan red dyes were employed to explore the efficiency of this MOF in removal of the dye pollutants. Copyright © 2018 Elsevier B.V. All rights reserved.