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Sample records for efficient stereoselective synthesis

  1. Stereoselective synthesis of hydroxy stilbenoids and styrenes by atom-efficient olefination with thiophthalides.

    Science.gov (United States)

    Mitra, Prithiba; Shome, Brateen; De, Saroj Ranjan; Sarkar, Anindya; Mal, Dipakranjan

    2012-04-14

    The synthesis of stilbenoids and styryl carboxylic acids is accomplished with high E-stereoselectivity by olefination of aldehydes with thiophthalides under basic conditions. The olefination is highly atom-efficient as it only loses elemental sulfur during the reaction. This olefination, in conjunction with retro Kolbe-Schmitt reaction, allows facile synthesis of E-hydroxystilbenoids with minimal employment of protecting groups. This study also discloses two important findings: formation of i) 4-methylsulfanyl isocoumarins and ii) an 2-arylindenone. This journal is © The Royal Society of Chemistry 2012

  2. Stereoselective synthesis of novel highly substituted isochromanone and isoquinolinone-containing exocyclic tetrasubstituted alkenes.

    Science.gov (United States)

    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.

  3. A sustainable process for gram-scale synthesis of stereoselective ...

    Indian Academy of Sciences (India)

    We have developed a new, simple and sustainable process for stereoselective synthesis of aryl substituted (E)-2-thiocyanatoacrylic acids by nucleophilic substitution and Knoevenagel condensation involving chloroacetic acid, ammonium thiocyanate and aromatic aldehydes at room temperature. The selectivity was ...

  4. Stereoselective total synthesis of the potent anti-asthmatic compound CMI-977 (LDP-977)

    Energy Technology Data Exchange (ETDEWEB)

    Dias, Luiz Carlos; Farina, Lui Strambi; Ferreira, Marco Antonio Barbosa, E-mail: ldias@iqm.unicamp.br [Universidade de Campinas (UNICAMP), SP (Brazil). Instituto de Quimica

    2013-02-15

    A short and efficient stereoselective total synthesis of CMI-977 (LDP-977), a potent and orally active anti-asthmatic compound, was developed. The key steps involve a highly diastereoselective Mukaiyama oxidative cyclization, which provides the trans-THF (tetrahydrofuran) unit and a Seyferth-Gilbert homologation to construct the triple bond in the target molecule. The synthesis of the key chiral building block was performed using Jacobsen hydrolytic kinetic resolution. (author)

  5. Stereoselective total synthesis of the potent anti-asthmatic compound CMI-977 (LDP-977)

    International Nuclear Information System (INIS)

    Dias, Luiz Carlos; Farina, Lui Strambi; Ferreira, Marco Antonio Barbosa

    2013-01-01

    A short and efficient stereoselective total synthesis of CMI-977 (LDP-977), a potent and orally active anti-asthmatic compound, was developed. The key steps involve a highly diastereoselective Mukaiyama oxidative cyclization, which provides the trans-THF (tetrahydrofuran) unit and a Seyferth-Gilbert homologation to construct the triple bond in the target molecule. The synthesis of the key chiral building block was performed using Jacobsen hydrolytic kinetic resolution. (author)

  6. Highly Stereoselective Synthesis of Cyclopentanes bearing Four Stereocenters by a Rhodium Carbene–Initiated Domino Sequence

    Science.gov (United States)

    Parr, Brendan T.; Davies, Huw M. L.

    2014-01-01

    Stereoselective synthesis of a cyclopentane nucleus by convergent annulations constitutes a significant challenge for synthetic chemists. Though a number of biologically relevant cyclopentane natural products are known, more often than not, the cyclopentane core is assembled in a stepwise fashion due to lack of efficient annulation strategies. Herein, we report the rhodium-catalyzed reactions of vinyldiazoacetates with (E)-1,3-disubstituted 2-butenols generate cyclopentanes, containing four new stereogenic centers with very high levels of stereoselectivity (99% ee, >97 : 3 dr). The reaction proceeds by a carbene–initiated domino sequence consisting of five distinct steps: rhodium–bound oxonium ylide formation, [2,3]-sigmatropic rearrangement, oxy-Cope rearrangement, enol–keto tautomerization, and finally an intramolecular carbonyl ene reaction. A systematic study is presented detailing how to control chirality transfer in each of the four stereo-defining steps of the cascade, consummating in the development of a highly stereoselective process. PMID:25082301

  7. Stereoselective synthesis of unsaturated α-amino acids.

    Science.gov (United States)

    Fanelli, Roberto; Jeanne-Julien, Louis; René, Adeline; Martinez, Jean; Cavelier, Florine

    2015-06-01

    Stereoselective synthesis of unsaturated α-amino acids was performed by asymmetric alkylation. Two methods were investigated and their enantiomeric excess measured and compared. The first route consisted of an enantioselective approach induced by the Corey-Lygo catalyst under chiral phase transfer conditions while the second one involved the hydroxypinanone chiral auxiliary, both implicating Schiff bases as substrate. In all cases, the use of a prochiral Schiff base gave higher enantiomeric excess and yield in the final desired amino acid.

  8. Easy Access to Evans’ Oxazolidinones. Stereoselective Synthesis and Antibacterial Activity of a New 2-Oxazolidinone Derivative

    Directory of Open Access Journals (Sweden)

    Gaspar Diaz

    2014-06-01

    Full Text Available An interesting new approach was developed for the synthesis of Evans’ chiral auxiliaries with excellent yields. In turn, another new stereoselective and efficient strategy has also allowed for the preparation of a 2-oxazolidinone derivative in 34% overall yield from the Morita-Baylis-Hillman adduct. The antibacterial activity of this oxazolidinone was tested against Staphylococcus aureus strains isolated from animals with mastitis infections.

  9. Stereoselective synthesis of L-[4-13C]carnitine

    International Nuclear Information System (INIS)

    Unkefer, C.J.; Ehler, D.S.

    1991-01-01

    The stereoselective synthesis of L-[4- 13 C]carnitine was achieved in 5 steps. The label was introduced from K 13 CN into an easily separated diastereomeric pair of 3-deoxy-D-[1- 13 C]aldohexoses. Reductive amination of the labeled aldohexose yielded the corresponding D-1-(dimethylamino)[1- 13 C]alditol which was oxidized in two steps and alkylated with iodomethane to yield L-[4- 13 C]carnitine. The stereochemical integrity at C-2 of the 3-deoxy-D-[1- 13 C]glucose precursor was maintained throughout the synthesis of L-[4- 13 C]carnitine. (author)

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

    Science.gov (United States)

    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

  11. An Expeditious Stereoselective Synthesis of (−)-Pinidinone from Ethyl Acetoacetate

    International Nuclear Information System (INIS)

    Damodar, Kongara; Jun, Jong-Gab

    2016-01-01

    An expeditious stereoselective synthesis of a naturally occurring 2,6-disubstituted piperidine alkaloid, (−)-pinidinone, has been accomplished with an overall yield of 31% in total eight steps. The synthesis involves ethyl acetoacetate as the starting material and the stereoselective α-aminoallylation of aldehyde with (S)-tert-butanesulfinamide, allyl bromide, and indium and Grubbs' olefin cross-metathesis as the pivotal steps.

  12. Stereoselective synthesis of hernandulcin, peroxylippidulcine A, lippidulcines A, B and C and taste evaluation

    Directory of Open Access Journals (Sweden)

    Marco G. Rigamonti

    2015-11-01

    Full Text Available The first stereoselective synthesis of lippidulcines A, B and C has been accomplished starting from (+-hernandulcin, which has been prepared on a multigram scale. The previously assigned absolute configurations have been confirmed. The key steps of this synthesis are based on a modified version of the Kornblum–DeLaMare rearrangement, and on a highly regioselective and stereoselective ketone reduction with the MeCBS reagent. The taste evaluations indicate that none of these sesquiterpenes are sweet, instead the lippidulcine A is a cooling agent with a mint after taste.

  13. Efficient microwave irradiation enhanced stereoselective synthesis ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 122; Issue 4 ... Laboratory, Department of Chemistry, Faculty of Science, Menoufiya University, Shebin Elkom 32511, Menoufiya, Egypt; Cancer Biology Laboratory, Center of Excellency for Advanced Sciences, National Research Center, Dokki 12622, Cairo, Egypt ...

  14. Stereoselective synthesis of a-hydroxy-b-amino acids: the chiral pool approach

    Directory of Open Access Journals (Sweden)

    RADOMIR N. SAICIC

    2004-11-01

    Full Text Available A method for the stereoselective homologation of a-amino acids into syn-a-hydroxy-b-amino acids is described, based on the conversion of stereoisomeric cyanohydrins into trans-oxazolines. The synthetic potential of the method is illustrated in the enantioselective formal synthesis of Bestatin.

  15. A stereoselective synthesis of (+)-physoperuvine using a tandem aza-Claisen rearrangement and ring closing metathesis reaction.

    Science.gov (United States)

    Zaed, Ahmed M; Swift, Michael D; Sutherland, Andrew

    2009-07-07

    A stereoselective synthesis of (+)-physoperuvine, a tropane alkaloid from Physalis peruviana Linne has been developed using a one-pot tandem aza-Claisen rearrangement and ring closing metathesis reaction to form the key amino-substituted cycloheptene ring.

  16. Catalytic stereoselective synthesis of highly substituted indanones via tandem Nazarov cyclization and electrophilic fluorination trapping.

    Science.gov (United States)

    Nie, Jing; Zhu, Hong-Wei; Cui, Han-Feng; Hua, Ming-Qing; Ma, Jun-An

    2007-08-02

    A new catalytic stereoselective tandem transformation via Nazarov cyclization/electrophilic fluorination has been accomplished. This sequence is efficiently catalyzed by a Cu(II) complex to afford fluorine-containing 1-indanone derivatives with two new stereocenters with high diastereoselectivity (trans/cis up to 49/1). Three examples of catalytic enantioselective tandem transformation are presented.

  17. Studies in the stereoselective synthesis of 1,1-disubstituted 1,2,3,4-tetrahydroisoquinolines

    OpenAIRE

    Berg, Michael Arthur George

    1992-01-01

    Isoquinoline alkaloids and analogs play an important role in today's pharmaceutical industry. The need to synthesize single stereoisomers of these alkaloids is important. Many times only a single stereoisomer exhibits the desired activity, while other stereoisomers of the alkaloid exhibit undesired side effects. The stereoselective synthesis of 1, 1-disubstituted 1,2,3,4- tetrahydroisoquinolines using Reissert compound chemistry containing chiral acyl auxiliaries was studied with the ultimate...

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

    Science.gov (United States)

    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.

  19. Enzymatic stereoselective synthesis of B-amino acids

    CSIR Research Space (South Africa)

    Chhiba, V

    2014-06-01

    Full Text Available The use of enzymes for the enantioselective synthesis of single enantiomer ß-subsituted compounds is of interest, as this structural motif occurs commonly in compounds of pharmaceutical importance, such as adrenergic agents, antidiabetics...

  20. A sustainable process for gram-scale synthesis of stereoselective ...

    Indian Academy of Sciences (India)

    RAJAN ABRAHAM

    2018-02-07

    Feb 7, 2018 ... for the additional structure modification.17–20. Acrylic acid derivatives ... mild conditions, and application in synthesizing bio- logically ... cal process for the gram-scale synthesis of streoselective ... ate yield of desired product 2 (58%, Table 1, entry. 2). .... Cross-Coupling and Atom-Economic Addition Reac-.

  1. Stereoselective synthesis of stable-isotope-labeled amino acids

    Energy Technology Data Exchange (ETDEWEB)

    Unkefer, C.J.; Martinez, R.A.; Silks, L.A. III [Los Alamos National Laboratory, NM (United States); Lodwig, S.N. [Centralia College, WA (United States)

    1994-12-01

    For magnetic resonance and vibrational spectroscopies to reach their full potential, they must be used in combination with sophisticated site-specific stable isotope labeling of biological macromolecules. Labeled amino acids are required for the study of the structure and function of enzymes and proteins. Because there are 20 common amino acids, each with its own distinguishing chemistry, they remain a synthetic challenge. The Oppolzer chiral auxiliary provides a general tool with which to approach the synthesis of labeled amino acids. By using the Oppolzer auxiliary, amino acids can be constructed from several small molecules, which is ideal for stable isotope labeling. In addition to directing the stereochemistry at the {alpha}-carbon, the camphorsultam can be used for stereo-specific isotope labeling at prochiral centers in amino acids. By using the camphorsultam auxiliary we have the potential to synthesize virtually any isotopomer of all of the common amino acids.

  2. Stereoselective synthesis of stable-isotope-labeled amino acids

    International Nuclear Information System (INIS)

    Unkefer, C.J.; Martinez, R.A.; Silks, L.A. III; Lodwig, S.N.

    1994-01-01

    For magnetic resonance and vibrational spectroscopies to reach their full potential, they must be used in combination with sophisticated site-specific stable isotope labeling of biological macromolecules. Labeled amino acids are required for the study of the structure and function of enzymes and proteins. Because there are 20 common amino acids, each with its own distinguishing chemistry, they remain a synthetic challenge. The Oppolzer chiral auxiliary provides a general tool with which to approach the synthesis of labeled amino acids. By using the Oppolzer auxiliary, amino acids can be constructed from several small molecules, which is ideal for stable isotope labeling. In addition to directing the stereochemistry at the α-carbon, the camphorsultam can be used for stereo-specific isotope labeling at prochiral centers in amino acids. By using the camphorsultam auxiliary we have the potential to synthesize virtually any isotopomer of all of the common amino acids

  3. Stereoselective Catalytic Synthesis of Active Pharmaceutical Ingredients in Homemade 3D-Printed Mesoreactors.

    Science.gov (United States)

    Rossi, Sergio; Porta, Riccardo; Brenna, Davide; Puglisi, Alessandra; Benaglia, Maurizio

    2017-04-03

    3D-printed flow reactors were designed, fabricated from different materials (PLA, HIPS, nylon), and used for a catalytic stereoselective Henry reaction. The use of readily prepared and tunable 3D-printed reactors enabled the rapid screening of devices with different sizes, shapes, and channel dimensions, aimed at the identification of the best-performing reactor setup. The optimized process afforded the products in high yields, moderate diastereoselectivity, and up to 90 % ee. The method was applied to the continuous-flow synthesis of biologically active chiral 1,2-amino alcohols (norephedrine, metaraminol, and methoxamine) through a two-step sequence combining the nitroaldol reaction with a hydrogenation. To highlight potential industrial applications of this method, a multistep continuous synthesis of norephedrine has been realized. The product was isolated without any intermediate purifications or solvent switches. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. A Stereoselective [3+1] Ring Expansion for the Synthesis of Highly Substituted Methylene Azetidines.

    Science.gov (United States)

    Schmid, Steven C; Guzei, Ilia A; Schomaker, Jennifer M

    2017-09-25

    The reaction of rhodium-bound carbenes with strained bicyclic methylene aziridines results in a formal [3+1] ring expansion to yield highly substituted methylene azetidines with excellent regio- and stereoselectivity. The reaction appears to proceed through an ylide-type mechanism, where the unique strain and structure of the methylene aziridine promotes a ring-opening/ring-closing cascade that efficiently transfers chirality from substrate to product. The resultant products can be elaborated into new azetidine scaffolds containing vicinal tertiary-quaternary and even quaternary-quaternary stereocenters. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. NAA-modified DNA oligonucleotides with zwitterionic backbones: stereoselective synthesis of A-T phosphoramidite building blocks.

    Science.gov (United States)

    Schmidtgall, Boris; Höbartner, Claudia; Ducho, Christian

    2015-01-01

    Modifications of the nucleic acid backbone are essential for the development of oligonucleotide-derived bioactive agents. The NAA-modification represents a novel artificial internucleotide linkage which enables the site-specific introduction of positive charges into the otherwise polyanionic backbone of DNA oligonucleotides. Following initial studies with the introduction of the NAA-linkage at T-T sites, it is now envisioned to prepare NAA-modified oligonucleotides bearing the modification at X-T motifs (X = A, C, G). We have therefore developed the efficient and stereoselective synthesis of NAA-linked 'dimeric' A-T phosphoramidite building blocks for automated DNA synthesis. Both the (S)- and the (R)-configured NAA-motifs were constructed with high diastereoselectivities to furnish two different phosphoramidite reagents, which were employed for the solid phase-supported automated synthesis of two NAA-modified DNA oligonucleotides. This represents a significant step to further establish the NAA-linkage as a useful addition to the existing 'toolbox' of backbone modifications for the design of bioactive oligonucleotide analogues.

  6. Stereoselective, nitro-Mannich/lactamisation cascades for the direct synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles

    Directory of Open Access Journals (Sweden)

    Pavol Jakubec

    2012-04-01

    Full Text Available A versatile nitro-Mannich/lactamisation cascade for the direct stereoselective synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles has been developed. A highly enantioenriched substituted 5-nitropiperidin-2-one was synthesised in a four component one-pot reaction combining an enantioselective organocatalytic Michael addition with the diastereoselective nitro-Mannich/lactamisation cascade. Protodenitration and chemoselective reductive manipulation of the heterocycles was used to install contiguous and fully substituted stereocentres in the synthesis of substituted piperidines.

  7. Synergistic Diazo-OH Insertion/Conia-Ene Cascade Catalysis for the Stereoselective Synthesis of γ-Butyrolactones and Tetrahydrofurans.

    Science.gov (United States)

    Hunter, Arianne C; Schlitzer, Steven C; Sharma, Indrajeet

    2016-11-02

    A novel and highly efficient diazo-OH insertion/Conia-ene cascade reaction of readily available homopropargylic acids and alcohols with diazo carbonyl compounds is described. The cascade reaction involves a synergistic Rh/Ag/Au catalyst cocktail and proceeds instantly with a variety of substituted diazo compounds and acids/alcohols to provide functionalized γ-butyrolactones and tetrahydrofurans with complete regio- and stereoselectivity. The unprecedented rate-enhancement, complete stereoselectivity, and the enabling of new Conia-ene cyclizations suggest a concerted [4+1]-cycloaddition reaction pathway under synergistic (Rh/Ag/Au)-catalysis conditions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Stereoselective synthesis of an iodinated resveratrol analog: Preliminary bioevaluation studies of the radioiodinated species

    Energy Technology Data Exchange (ETDEWEB)

    Dhyani, Manish V.; Kameswaran, Mythili; Korde, Aruna G.; Pandey, Usha [Radiopharmaceuticals Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Chattopadhyay, Subrata [Bio-Organic Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Banerjee, Sharmila, E-mail: sharmila@barc.gov.i [Radiopharmaceuticals Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

    2011-07-15

    Stereoselective synthesis of an E-hydroxystilbene has been carried out using the McMurry reaction. Synthesis of a monoiodinated hydroxystilbene has been carried out by a McMurry cross-coupling reaction. For the purpose of biological evaluation, the facile electrophilic substitution route has been attempted to radioiodinate it with {sup 125}I. The HPLC pattern of the radioiodinated hydroxystilbene, which could be obtained in >90% radiochemical purity, was found to be identical to that of its non-radioactive analog that has been independently prepared using the McMurry cross-coupling route. In vitro cell uptake studies were carried out in breast cancer cells MCF7, overexpressing estrogen receptors. In vivo biodistribution studies in female Swiss mice show a uterine uptake of 0.85{+-}0.4% ID/g at 3 h.p.i. with a uterus to muscle ratio of 2.83. Uptake in the thyroid was insignificant indicating good in vivo stability of the radioiodinated hydroxystilbene.

  9. Stereoselective synthesis of an active metabolite of the potent PI3 kinase inhibitor PKI-179.

    Science.gov (United States)

    Chen, Zecheng; Venkatesan, Aranapakam M; Dos Santos, Osvaldo; Delos Santos, Efren; Dehnhardt, Christoph M; Ayral-Kaloustian, Semiramis; Ashcroft, Joseph; McDonald, Leonard A; Mansour, Tarek S

    2010-03-05

    The synthesis and stereochemical determination of 1-(4-(4-((1R,5R,6R)-6-hydroxy-3-oxa-8-azabicyclo[3.2.1]octan-8-yl)-6-morpholino-1,3,5-triazin-2-yl)phenyl)-3-(pyridin-4-yl)urea (2), an active metabolite of the potent PI3 kinase inhibitor PKI-179 (1), is described. Stereospecific hydroboration of the double bond of 2,5-dihydro-1H-pyrrole 8 gave the 2,3-trans alcohol 9 exclusively. The configuration of the 3-hydroxyl group in 9 was inverted by an oxidation and stereoselective reduction sequence to give the corresponding 2,3-cis isomer 23. Both exo (21) and endo (27) isomers of the metabolite 2 were prepared via a practical synthetic route from 9 and 23, respectively, and the stereochemistry of 2 was determined to be endo. The endo isomer (27) was separated into two enantiomers 28 and 29 by chiral HPLC. Compound 2 was found to be enantiomerically pure and identical to the enantiomer 28. The absolute stereochemistry of the enantiomer 28 was determined by Mosher's method, thus establishing the stereochemistry of the active metabolite 2.

  10. Phospholyl(borane) Amino Acids and Peptides: Stereoselective Synthesis and Fluorescent Properties with Large Stokes Shift.

    Science.gov (United States)

    Arribat, Mathieu; Rémond, Emmanuelle; Clément, Sébastien; Lee, Arie Van Der; Cavelier, Florine

    2018-01-24

    The synthesis of phospholyl(borane) amino acids was stereoselectively achieved by reaction of phospholide anion with iodo α-amino ester derived from l-aspartic acid or l-serine, followed by in situ complexation with borane. Phospholyl(borane) amino acids are easy to store and can be subjected to direct transformation into the corresponding free phospholyl, gold complex, oxide or sulfur derivatives as well as phospholinium salts, thus offering a variety of side chains. After selective deprotection of carboxylic function or amine, C- or N- peptide coupling with an alanine moiety proved the possible incorporation into peptides. Such phospholyl amino acid and peptide derivatives exhibit fluorescent properties with a large Stokes shift (160 nm) and fluorescence up to 535 nm, depending on the phosphole aromaticity and the chemical environment. These phospholyl(borane) amino acids constitute a new class of unnatural amino acids useful for structure-activities relationship studies and appear to be promising fluorophores for the development of labeled peptides.

  11. Studies on the Total Synthesis of Amphidinolide O (II): A Stereoselective Synthesis of C1-C11 Fragment

    Energy Technology Data Exchange (ETDEWEB)

    Jang, Mi Yeon; Kim, Jong Woo; Lee, Duck Hyung [Sogang University, Seoul (Korea, Republic of)

    2005-10-15

    Two ketones and, the C1-C11 fragment of Amphidinolide O, were prepared stereoselectively via 14 and 16 step sequences in 8.7% and 2.0% overall yield, respectively. The amphidinolides were isolated from the marine dinoflagellate Amphidinium sp., which produces a host of secondary metabolites endowed with potent cytotoxicity against various cancer cell lines. Amphidinolide O displayed potent in vitro cytotoxicity against L1210 marine leukemia cells and human epidermoid carcinoma KB cells with 1.7 and 3.6 μg/mL of IC50s, respectively. In addition to our recent reports regarding to the synthesis of C12-C17 and C3-C11 fragments of amphidinolide O, we describe herein a new route to diastereoselective synthesis of C1-C11 fragment of. The retrosynthetic analysis of led to the C1-C11 fragment and C12-C17 fragment. The hemiketal was expected from acyclic precursor 4 which, in turn, would be derived by diastereoselective aldol reaction between ketone and aldehyde.

  12. Zinc mediated activation of terminal alkynes: stereoselective synthesis of alkynyl glycosides.

    Science.gov (United States)

    Tatina, Madhu Babu; Kusunuru, Anil Kumar; Yousuf, Syed Khalid; Mukherjee, Debaraj

    2014-10-28

    Zinc mediated alkynylation reaction was studied for the preparation of C-glycosides from unactivated alkynes. Different glycosyl donors such as glycals and anomeric acetates were tested towards an alkynyl zinc reagent obtained from alkynes using zinc dust and ethyl bromoacetate as an additive. The method provides simple, mild and stereoselective access to alkynyl glycosides both from aromatic and aliphatic acetylenes.

  13. Stereoselective conjugate radical additions: application of a fluorous oxazolidinone chiral auxiliary for efficient tin removal.

    Science.gov (United States)

    Hein, Jason E; Zimmerman, Jake; Sibi, Mukund P; Hultin, Philip G

    2005-06-23

    [reaction: see text] A series of asymmetric free-radical-mediated intermolecular conjugate additions using a fluorous oxazolidinone chiral auxiliary has been completed. The fluorous auxiliary facilitated product isolation using fluorous solid phase extractions (FSPE), effectively removing excess organic and organometallic reagents. Parallel reactions carried out with a similar but nonfluorous norephedrine-derived oxazolidinone demonstrated the superior stereoselectivity and purification obtainable with the fluorous chiral auxiliary.

  14. Palladium-catalyzed arylation of enoates with iodobenzene: stereoselective synthesis of trisubstituted olefins

    Energy Technology Data Exchange (ETDEWEB)

    Fernandes, Talita de A. [Universidade Federal do Rio de Janeiro (UFRJ/LQB), RJ (Brazil). Nucleo de Pesquisas de Produtos Naturais. Laboratorio de Quimica Bioorganica; Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica. Interlab; Silva, Alcides J.M. da; Costa, Paulo R.R., E-mail: prrcosta2011@gmail.com [Universidade Federal do Rio de Janeiro (UFRJ/LQB), RJ (Brazil). Nucleo de Pesquisas de Produtos Naturais. Laboratorio de Quimica Bioorganica; Esteves, Pierre M. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica. Interlab; Eberlin, Marcos N., E-mail: eberlin@iqm.unicamp.br [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Instituto de Quimica. Laboratorio ThoMSon de Espectrometria de Massas; Vaz, Boniek G. [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Instituto de Quimica. Laboratorio ThoMSon de Espectrometria de Massas; Universidade Federal de Goias (UFGO), Goiania, GO (Brazil). Instituto de QuImica

    2013-03-15

    The Heck reaction between E- and Z-enoates and iodobenzene was studied in the presence of Pd(OAc){sub 2}. The stereochemistry in resulting adducts was dependent on the enoate geometry (stereospecific reaction). Best yields were obtained from Z-isomers in acetone using Ag{sub 2} CO{sub 3} as base. The main cationic palladium intermediates possibly involved in the catalytic cycle could be intercepted and characterized by electrospray ionization mass spectrometry (ESI-MS). The stereoselectivity observed was rationalized through the classic mechanism of the Heck reaction. (author)

  15. Palladium-catalyzed arylation of enoates with iodobenzene: stereoselective synthesis of trisubstituted olefins

    International Nuclear Information System (INIS)

    Fernandes, Talita de A.; Universidade Federal do Rio de Janeiro; Silva, Alcides J.M. da; Costa, Paulo R.R.; Esteves, Pierre M.; Eberlin, Marcos N.; Vaz, Boniek G.; Universidade Federal de Goias

    2013-01-01

    The Heck reaction between E- and Z-enoates and iodobenzene was studied in the presence of Pd(OAc) 2 . The stereochemistry in resulting adducts was dependent on the enoate geometry (stereospecific reaction). Best yields were obtained from Z-isomers in acetone using Ag 2 CO 3 as base. The main cationic palladium intermediates possibly involved in the catalytic cycle could be intercepted and characterized by electrospray ionization mass spectrometry (ESI-MS). The stereoselectivity observed was rationalized through the classic mechanism of the Heck reaction. (author)

  16. Wittig Reaction: Domino Olefination and Stereoselectivity DFT Study. Synthesis of the Miharamycins' Bicyclic Sugar Moiety.

    Science.gov (United States)

    Cachatra, Vasco; Almeida, Andreia; Sardinha, João; Lucas, Susana D; Gomes, Ana; Vaz, Pedro D; Florêncio, M Helena; Nunes, Rafael; Vila-Viçosa, Diogo; Calhorda, Maria José; Rauter, Amélia P

    2015-11-20

    2-O-Acyl protected-d-ribo-3-uloses reacted with [(ethoxycarbonyl)methylene]triphenylphosphorane in acetonitrile to afford regio- and stereoselectively 2-(Z)-alkenes in 10-60 min under microwave irradiation. This domino reaction is proposed to proceed via tautomerization of 3-ulose to enol, acyl migration, tautomerization to the 3-O-acyl-2-ulose, and Wittig reaction. Alternatively, in chloroform, regioselective 3-olefination of 2-O-pivaloyl-3-uloses gave (E)-alkenes, key precursors for the miharamycins' bicyclic sugar moiety.

  17. Stereoselective synthesis of 1,3-disubstituted isoindolines via Rh(III)-catalyzed tandem oxidative olefination-cyclization of 4-aryl cyclic sulfamidates.

    Science.gov (United States)

    Son, Se-Mi; Seo, Yeon Ji; Lee, Hyeon-Kyu

    2016-03-21

    Rh(III)-catalyzed tandem ortho C-H olefination of cyclic 4-aryl sulfamidates (1) and subsequent intramolecular cyclization are described. This reaction serves as a method for the direct and stereoselective synthesis of 1,3-disubstituted isoindolines (3) starting with enantiomerically enriched 4-aryl cyclic sulfamidates. In this process, the configurational integrity of the stereogenic center in the starting cyclic sulfamidate is completely retained. In addition, the process generates trans-1,3-disubstituted isoindolines exclusively.

  18. Stereoselective Synthesis of Tetrasubstituted Furylalkenes via Gold-Catalyzed Cross-Coupling of Enynones with Diazo Compounds.

    Science.gov (United States)

    Liu, Pei; Sun, Jiangtao

    2017-07-07

    A stereoselective, gold-catalyzed, cross-coupling reaction of enynones with diazo compounds has been developed, affording 2-alkenylfurans in moderate to good yields with excellent E-stereoselectivity. Upon using diazo compounds as nucleophiles to trap the in situ formed gold furyl carbene, this protocol provides a novel path toward the formation of unsymmetrical tetrasubstituted alkenes.

  19. Use of (S)-trans-gamma-monocyclofarnesol as a useful chiral building block for the stereoselective synthesis of diterpenic natural products.

    Science.gov (United States)

    Serra, Stefano; Cominetti, Alessandra A; Lissoni, Veronica

    2014-03-01

    A comprehensive study of the exploitation of (S)-trans-gamma-monocyclofarnesol as a useful chiral building block for the stereoselective synthesis of natural diterpene derivatives is here described. The farnesol derivative (+)-1 was used as starting material in the preparation of the diterpenes (S)-dehydroambliol-A and (S)-trixagol, as well as for the syntheses of the dinorditerpene (S)-dinortrixagone and of the guanidine-interrupted terpenoid (S)-dotofide. Key steps of the presented syntheses were the cross-coupling between an allyl acetate and a Grignard reagent, the Wittig reaction, the selective preparation ofa diacylguanidine derivative and the alkylation of a sulfone derivative, followed by the reductive removal of the same functional group. It is worth noting that the natural products (+)-8, (+)-12 and (+)-15 were prepared stereoselectively for the first time, thus allowing the unambiguous assignment of their absolute configuration.

  20. Stereoselective synthesis of the Halaven C14-C26 fragment from D-quinic acid: crystallization-induced diastereoselective transformation of an α-methyl nitrile.

    Science.gov (United States)

    Belanger, Francis; Chase, Charles E; Endo, Atsushi; Fang, Francis G; Li, Jing; Mathieu, Steven R; Wilcoxen, Annie Z; Zhang, Huiming

    2015-04-20

    Crystallization-induced diastereoselective transformation (CIDT) of an α-methyl nitrile completes an entirely non-chromatographic synthesis of the halichondrin B C14-C26 stereochemical array. The requisite α-methyl nitrile substrate is derived from D-quinic acid through a series of substrate-controlled stereoselective reactions via a number of crystalline intermediates that benefit from a rigid polycyclic template. Therefore, all four stereogenic centers in the Halaven C14-C26 fragment were derived from the single chiral source D-quinic acid. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Kinetic resolution and stereoselective synthesis of 3-substituted aspartic acids by using engineered methylaspartate ammonia lyases.

    Science.gov (United States)

    Raj, Hans; Szymanski, Wiktor; de Villiers, Jandré; Puthan Veetil, Vinod; Quax, Wim J; Shimamoto, Keiko; Janssen, Dick B; Feringa, Ben L; Poelarends, Gerrit J

    2013-08-19

    Enzymatic amino acid synthesis: Kinetic resolution and asymmetric synthesis of various valuable 3-substituted aspartic acids, which were obtained in fair to good yields with diastereomeric ratio values of up to >98:2 and enantiomeric excess values of up to >99 %, by using engineered methylaspartate ammonia lyases are described. These biocatalytic methodologies for the selective preparation of aspartic acid derivatives appear to be attractive alternatives for existing chemical methods. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Stereoselective total synthesis of Oxylipin from open chain gluco-configured building block.

    Science.gov (United States)

    Borkar, Santosh Ramdas; Aidhen, Indrapal Singh

    2017-04-18

    Total synthesis of naturally occurring Oxylipin has been achieved from open chain gluco-configured building block which is readily assembled from inexpensive and commercially available D-(+)-gluconolactone. Grignard reaction and Wittig olefination reactions are key steps for the requisite CC bond formation. Copyright © 2017. Published by Elsevier Ltd.

  3. A novel stereoselective synthesis of N-heterocycles by intramolecular hydrovinylation

    DEFF Research Database (Denmark)

    Bothe, Ulrich; Rudbeck, H. C.; Tanner, David Ackland

    2001-01-01

    A novel method for the synthesis of bicyclic amines has been developed. Cyclisation of 1,6-dienes by intramolecular hydrovinylation in the presence of catalytic amounts of allylpalladium chloride dimer afforded bicyclic amines in one step. Added phosphines, silver salts, as well as the nature of ...

  4. Stereoselective synthesis of the C79–C97 fragment of symbiodinolide

    Directory of Open Access Journals (Sweden)

    Hiroyoshi Takamura

    2013-09-01

    Full Text Available Symbiodinolide is a polyol marine natural product with a molecular weight of 2860. Herein, a streamlined synthesis of the C79–C97 fragment of symbiodinolide is described. In the synthetic route, a spiroacetalization, a Julia–Kocienski olefination, and a Sharpless asymmetric dihydroxylation were utilized as the key transformations.

  5. Kinetic Resolution and Stereoselective Synthesis of 3-Substituted Aspartic Acids by Using Engineered Methylaspartate Ammonia Lyases

    NARCIS (Netherlands)

    Raj, Hans; Szymanski, Wiktor; Villiers, Jandré de; Puthan Veetil, Vinod; Quax, Wim J.; Shimamoto, Keiko; Janssen, Dick B.; Feringa, Ben L.; Poelarends, Gerrit J.

    2013-01-01

    Kinetic resolution and asymmetric synthesis of various valuable 3-substituted aspartic acids, which were obtained in fair to good yields with diastereomeric ratio values of up to >98:2 and enantiomeric excess values of up to >99 %, by using engineered methylaspartate ammonia lyases are described.

  6. Stereoselective Wittig Olefination as a Macrocyclization Tool. Synthesis of Large Carbazolophanes.

    Science.gov (United States)

    Myśliwiec, Damian; Lis, Tadeusz; Gregoliński, Janusz; Stępień, Marcin

    2015-06-19

    Z-Selective Wittig olefination was applied to the synthesis of large carbazolophanes containing up to eight heteroaromatic subunits. A number of strategies were devised and tested, showing that cyclooligomerization yields can be significantly improved by using one-component schemes involving heterobifunctional reactants. [4]- and [6]Carbazolophanes were characterized in the solid state, revealing compact, highly folded structures. Electronic and steric effects of substitution and chain length on the Wittig olefination rates and Z-selectivities were explored theoretically using DFT calculations.

  7. Structural diversity through intramolecular cycloaddition and modulation of chemical reactivity in excited state. Synthesis and photoreactions of 3-oxa-tricyclo[5.2.2.0(1,5)]undecenones: novel stereoselective route to oxa-triquinanes and oxa-sterpuranes.

    Science.gov (United States)

    Singh, V; Alam, S Q

    2000-11-20

    Synthesis of 11-methyl-3-oxa-tricyclo[5.2.2.0(1,5)]undecenones by intramolecular Diels-Alder reaction of highly labile spiroepoxycyclohexa-2,4-dienones and its photochemical reactions upon triplet (3T) and singlet (1S) excitation leading to a stereoselective route to oxa-triquinane and oxa-sterpurane, respectively, is described.

  8. Stereoselective Synthesis of Functionalized 1,3-Disubstituted Isoindolines via Rh(III)-Catalyzed Tandem Oxidative Olefination-Cyclization of 4-Aryl-cyclic Sulfamidate-5-Carboxylates.

    Science.gov (United States)

    Achary, Raghavendra; Jung, In-A; Son, Se-Mi; Lee, Hyeon-Kyu

    2017-07-21

    A new method for the direct, stereoselective synthesis of highly functionalized 1,3-disubstituted isoindolines 6 from enantiomerically enriched cyclic 4-aryl-sulfamidate-5-carboxylates (5) is described. The process involves sulfamidate directed, Rh(III)-catalyzed tandem ortho C-H olefination of the 4-aryl-sulfamidate-5-carboxylates and subsequent cyclization by aza-Michael addition. In the reaction, which generates trans-1,3-disubstituted isoindolines exclusively, the configurational integrity of the stereogenic center in the starting cyclic sulfamidate is completely retained in the product. Examples are provided which show that the cyclic sulfamidate moiety not only serves as a chiral directing group but also as a versatile handle for further functionalization of the generated isoindoline ring system.

  9. Stereoselective synthesis of functionalized cyclic amino acid derivatives via a [2,3]-Stevens rearrangement and ring-closing metathesis.

    Science.gov (United States)

    Nash, Aaron; Soheili, Arash; Tambar, Uttam K

    2013-09-20

    Unnatural cyclic amino acids are valuable tools in biomedical research and drug discovery. A two-step stereoselective strategy for converting simple glycine-derived aminoesters into unnatural cyclic amino acid derivatives has been developed. The process includes a palladium-catalyzed tandem allylic amination/[2,3]-Stevens rearrangement followed by a ruthenium-catalyzed ring-closing metathesis. The [2,3]-rearrangement proceeds with high diastereoselectivity through an exo transition state. Oppolzer's chiral auxiliary was utilized to access an enantiopure cyclic amino acid by this approach, which will enable future biological applications.

  10. Stereoselective synthesis of highly substituted bicyclic γ-lactones using homoaldol addition of 1-(1-cycloalkenyl)methyl carbamates

    DEFF Research Database (Denmark)

    Özlügedik, M.; Kristensen, Jesper Langgaard; Reuber, J.

    2004-01-01

    Stereoselective addition of aldehydes 4 to metallated 1-(1-cycloalkenyl) methyl N,N-diisopropylcarbamates 1 gave cyclic homoaldol adducts 6. By applying the (-)-sparteine method, enantiomerically enriched products were obtained. These were oxidatively cyclized to diastereomerically pure ¿-lactones...... 8 via the ¿-lactol ethers 7. After deprotonation of ¿-lactones 8 with lithium hexamethyldisilazide, a further substitution was achieved. By trapping the lactone enolates 11 with ß-naphthylmethyl bromide, single diastereomers of ¿-lactones 12 were produced....

  11. Stereoselectivity in ene reactions with 1O2: matrix effects in polymer supports, photo-oxygenation of organic salts and asymmetric synthesis.

    Science.gov (United States)

    Griesbeck, Axel G; Bartoschek, Anna; Neudörfl, Jörg; Miara, Claus

    2006-01-01

    The ene reaction of chiral allylic alcohols is applied as a tool for the investigation of intrapolymer effects by means of the stereoselectivity of the singlet-oxygen addition. The diastereo selectivity strongly depends on the structure of the polymer, the substrate loading degree and also on the degree of conversion demonstrating additional supramolecular effects evolving during the reaction. The efficiency and the stability of polymer-bound sensitizers were evaluated by the ene reaction of singlet oxygen with citronellol. The ene reaction with chiral ammonium salts of tiglic acid was conducted under solution phase conditions or in polystyrene beads under chiral contact ion-pair conditions. The products thus obtained precipitate during the photoreaction as ammonium salts. Moderate asymmetric induction was observed for this procedure for the first time.

  12. Stereoselective Synthesis of 8,12-Furanoeudesmanes from Santonin. Absolute Stereochemistry of Natural Furanoeudesma-1,3-diene and Tubipofurane.

    Science.gov (United States)

    Blay, Gonzalo; Cardona, Luz; García, Begoña; Pedro, José R.; Sánchez, Juan J.

    1996-05-31

    Ketobutenolide 3, easily obtained from santonin (1), has been transformed into two natural furanoeudesmanes 4 and 5, isolated from Commiphora molmol and Tubipora musica, respectively. trans- And cis-decalin systems were obtained by stereoselective reduction of the C(4)-C(5) double bond in 3 in the following way: hydrogenation of 3 over Pd/C followed by acidic treatment gave the cis isomer 10 as the major product; selective hydrogenation of the C(1)-C(2) double bond with the Wilkinson's catalyst followed by reduction with NaTeH yielded mainly the trans isomer 9. Compounds 9 and 10 were transformed into 4 and 5 in parallel sequences. Optical rotation and CD measurements of the synthetic products revealed that the stereochemistry of both natural products should be revised to their enantiomeric form.

  13. Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

    Directory of Open Access Journals (Sweden)

    Jakub Saadi

    2016-06-01

    Full Text Available Starting from γ-ketoesters with an o-iodobenzyl group we studied a palladium-catalyzed cyclization process that stereoselectively led to bi- and tricyclic compounds in moderate to excellent yields. Four X-ray crystal structure analyses unequivocally defined the structure of crucial cyclization products. The relative configuration of the precursor compounds is essentially transferred to that of the products and the formed hydroxy group in the newly generated cyclohexane ring is consistently in trans-arrangement with respect to the methoxycarbonyl group. A transition-state model is proposed to explain the observed stereochemical outcome. This palladium-catalyzed Barbier-type reaction requires a reduction of palladium(II back to palladium(0 which is apparently achieved by the present triethylamine.

  14. Large-scale synthesis of tert-butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate by a stereoselective carbonyl reductase with high substrate concentration and product yield.

    Science.gov (United States)

    Liu, Zhi-Qiang; Hu, Zhong-Liang; Zhang, Xiao-Jian; Tang, Xiao-Ling; Cheng, Feng; Xue, Ya-Ping; Wang, Ya-Jun; Wu, Lin; Yao, Dan-Kai; Zhou, Yi-Teng; Zheng, Yu-Guo

    2017-05-01

    To biosynthesize the (3R,5S)-CDHH in an industrial scale, a newly synthesized stereoselective short chain carbonyl reductase (SCR) was successfully cloned and expressed in Escherichia coli. The fermentation of recombinant E. coli harboring SCR was carried out in 500 L and 5000 L fermenters, with biomass and specific activity of 9.7 g DCW/L, 15749.95 U/g DCW, and 10.97 g DCW/L, 19210.12 U/g DCW, respectively. The recombinant SCR was successfully applied for efficient production of (3R,5S)-CDHH. The scale-up synthesis of (3R,5S)-CDHH was performed in 5000 L bioreactor with 400 g/L of (S)-CHOH at 30°C, resulting in a space-time yield of 13.7 mM/h/g DCW, which was the highest ever reported. After isolation and purification, the yield and d.e. of (3R,5S)-CDHH reached 97.5% and 99.5%, respectively. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:612-620, 2017. © 2017 American Institute of Chemical Engineers.

  15. Spiro(phosphoamidite) ligand (SIPHOS)/Cu(OTf)2-catalyzed highly regio-and stereo-selective hydroborations of internal alkynes with diborane in water

    Institute of Scientific and Technical Information of China (English)

    Qing-Qing Xuan; Ya-Hui Wei; Qiu-Ling Song

    2017-01-01

    The highly regio-and stereoselective hydroborations of unactivated internal alkynes with diboron compound catalyzed by Cu(OTf)2 with spiro(phosphoamidite) as ligand in the presence of Cs2CO3 in water was developed.This protocol was applied efficiently in the aqueous synthesis of multi-substituted vinylboranes.

  16. Synthesis of all eight stereoisomeric 6-deoxy-l-hexopyranosyl donors - trends in using stereoselective reductions or mitsunobu epimerizations

    DEFF Research Database (Denmark)

    Frihed, Tobias; Pedersen, Christian Marcus; Bols, Mikael

    2014-01-01

    The synthesis of all eight rare but biologically important 6deoxy-L-hexoses as their thioglycoside glycosyl donors starting from the commercially available L-rhamnose or L-fucose is reported. The synthesis of all eight 6-deoxy-L-hexoses was accomplished using a variety of epimerization methods, w...

  17. Regio- and stereoselective synthesis of (+)-6-ketoeuryfuran, (+)-6-ketowinterin, and (-)-7-ketoeuryfuran from accessible labdane diterpenoids (+)-larixol and (-)-sclareol

    NARCIS (Netherlands)

    Vlad, P.E.; Ciocarlan, A.; Edu, C.; Aricu, A.; Biriiac, A.; Coltsa, M.; Ambrosio, D' M.; Deleanu, C.; Nicolescu, A.; Shova, S.; Vornicu, N.; Groot, de Æ.

    2013-01-01

    Starting from (+)-larixol and (-)-sclareol, new syntheses of (+)-6-ketoeuryfuran, (+)-6-ketowinterin, and (-)-7-ketoeuryfuran have been elaborated in high yields. (+)-6-Ketowinterin was synthesized for the first time. Both euryfurans are excellent starting materials for the synthesis of important

  18. Stereoselective Synthesis of(Z)-4-(2-Bromovinyl)benzenesulfonyl Azide and Its Synthetic Utility for the Transformation to(2)-N-[4-(2-Bromovinyl)benzenesulfonyl]imidates

    Institute of Scientific and Technical Information of China (English)

    ZHANG Wensheng; KUANG Chunxiang; YANG Qing

    2009-01-01

    A novel method for the stereoselective synthesis of(Z)-4-(2-bromovinyl)benzenesulfonyl azide by simultaneous azidation and debrorninative decarboxylation of anti-2,3-dibromo-3-(4-chlorosulfonylphenyl)propanoic acid using NaN3 only was developed.Facile transformation of(Z)-4-(2-bromovinyl)benzenesulfonyl azide to(Z)-N-[4(2-bromovinyl)benzenesulfonyl]imidates was also achieved by Cu-catalyzed three-component coulping of (Z)-4-(2-bromovinyi)benzenesulfonyl azide,terminal alkynes and alcohols/phenols.

  19. Stereoselective synthesis, X-ray analysis, computational studies and biological evaluation of new thiazole derivatives as potential anticancer agents.

    Science.gov (United States)

    Mabkhot, Yahia N; Alharbi, Mohammed M; Al-Showiman, Salim S; Ghabbour, Hazem A; Kheder, Nabila A; Soliman, Saied M; Frey, Wolfgang

    2018-05-11

    The synthesis of new thiazole derivatives is very important because of their diverse biological activities. Also , many drugs containing thiazole ring in their skeletons are available in the market such as Abafungin, Acotiamide, Alagebrium, Amiphenazole, Brecanavir, Carumonam, Cefepime, and Cefmatilen. Ethyl cyanoacetate reacted with phenylisothiocyanate, chloroacetone, in two different basic mediums to afford the thiazole derivative 6, which reacted with dimethylformamide- dimethyl acetal in the presence of DMF to afford the unexpected thiazole derivative 11. The structures of the thiazoles 6 and 11 were optimized using B3LYP/6-31G(d,p) method. The experimentally and theoretically geometric parameters agreed very well. Also, the natural charges at the different atomic sites were predicted. HOMO and LUMO demands were discussed. The anticancer activity of the prepared compounds was evaluated and showed moderate activity. Synthesis of novel thiazole derivatives was done. The structure was established using X-ray and spectral analysis. Optimized molecular structures at the B3LYP/6-31G(d,p) level were investigated. Thiazole derivative 11 has more electropositive S-atom than thiazole 6. The HOMO-LUMO energy gap is lower in the former compared to the latter. The synthesized compounds showed moderate anticancer activity.

  20. Stereoselective synthesis and pharmacological evaluation of [4.3.3]propellan-8-amines as analogs of adamantanamines.

    Science.gov (United States)

    Torres-Gómez, Héctor; Lehmkuhl, Kirstin; Frehland, Bastian; Daniliuc, Constantin; Schepmann, Dirk; Ehrhardt, Christina; Wünsch, Bernhard

    2015-08-01

    Amantadine (1) exerts its anti-Parkinson effects by inhibition of the NMDA associated cation channel and its antiviral activity by inhibition of the M2 protein channel of influenza A viruses. Herein the synthesis, NMDA receptor affinity and anti-influenza activity of analogous propellanamines 3 are reported. The key steps in the synthesis of the diastereomeric propellanamines syn-3 and anti-3 are diastereoselective reduction of the ketone 7 with L-Selectride to give anti-11, Mitsunobu inversion of the alcohol anti-13 into syn-13, and SN2 substitution of diastereomeric mesylates syn-14 and anti-14 with NaN3. The affinity of the propellanamines syn-3 and anti-3 to the PCP binding site of the NMDA receptor is similar to that of amantadine (Ki=11 μM). However, both propellanamines syn-3 and anti-3 do not exhibit activity against influenza A viruses. Compared to amantadine (1), the structurally related propellanamines syn-3 and anti-3 retain the NMDA antagonistic activity but loose the antiviral activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. Stereocontrolled generation of nucleophilic (Z)- or (E)-α-fluoroalkenylchromium reagents via carbon-fluorine bond activation: highly stereoselective synthesis of (E)- or (Z)-β-fluoroallylic alcohols.

    Science.gov (United States)

    Nihei, Takashi; Yokotani, Saya; Ishihara, Takashi; Konno, Tsutomu

    2014-02-14

    Highly nucleophilic (Z)- or (E)-α-fluoroalkenylchromium species could be generated in a stereoselective manner via C-F bond activation of CBrF2-containing molecules, and they reacted smoothly with various aldehydes to give (E)- or (Z)-β-fluoroallylic alcohol derivatives in high yields, respectively.

  2. A stereoselective, catalytic strategy for the in-flow synthesis of advanced precursors of rasagiline and tamsulosin.

    Science.gov (United States)

    Brenna, Davide; Pirola, Margherita; Raimondi, Laura; Burke, Anthony J; Benaglia, Maurizio

    2017-12-01

    The diastereoselective, trichlorosilane-mediate reduction of imines, bearing different and removable chiral auxiliaries, in combination either with achiral bases or catalytic amounts of chiral Lewis bases, was investigated to afford immediate precursors of chiral APIs (Active Pharmaceutical Ingredients). The carbon-nitrogen double bond reduction was successfully performed in batch and in flow mode, in high yields and almost complete stereocontrol. By this metal-free approach, the formal synthesis of rasagiline and tamsulosin was successfully accomplished in micro(meso) flow reactors, under continuous flow conditions. The results of these explorative studies represent a new, important step towards the development of automated processes for the preparation of enantiopure biologically active compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Efficient Synthesis of Network Updates

    Science.gov (United States)

    2015-06-17

    mal Languages ]: Mathematical Logic—Temporal logic; C.2.3 [Computer-communication Networks]: Network Operations— Network Management Keywords synthesis...problem, and prove this algorithm to be correct (§4). • We present an incremental LTL model checker for loop-free models (§5). • We describe an OCaml ...canned” properties, we use a specification language that is expressive enough to encode these properties and others, as well as conjunctions

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

    Science.gov (United States)

    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. Minireview of Stereoselective Brain Imaging

    DEFF Research Database (Denmark)

    Smith, Donald F.; Jakobsen, Steen

    2014-01-01

    Stereoselectivity is a fundamental principle in living systems. Stereoselectivity reflects the dependence of molecular processes on the spatial orientation of constituent atoms. Stereoselective processes govern many aspects of brain function and direct the course of many psychotropic drugs. Today......, modern imaging techniques such as SPECT and PET provide a means for studying stereoselective processes in the living brain. Chemists have prepared numerous radiolabelled stereoisomers for use in SPECT and PET in order to explore various molecular processes in the living brain of anesthetized laboratory...... animals and awake humans. The studies have demonstrated how many aspects of neurotransmission consist of crucial stereoselective events that can affect brain function in health and disease. Here, we present a brief account of those findings in hope of stimulating further interest in the vital topic....

  6. Asymmetric reduction of ketopantolactone using a strictly (R)-stereoselective carbonyl reductase through efficient NADPH regeneration and the substrate constant-feeding strategy.

    Science.gov (United States)

    Zhao, Man; Gao, Liang; Zhang, Li; Bai, Yanbin; Chen, Liang; Yu, Meilan; Cheng, Feng; Sun, Jie; Wang, Zhao; Ying, Xiangxian

    2017-11-01

    To characterize a recombinant carbonyl reductase from Saccharomyces cerevisiae (SceCPR1) and explore its use in asymmetric synthesis of (R)-pantolactone [(R)-PL]. The NADPH-dependent SceCPR1 exhibited strict (R)-enantioselectivity and high activity in the asymmetric reduction of ketopantolactone (KPL) to (R)-PL. Escherichia coli, coexpressing SceCPR1 and glucose dehydrogenase from Exiguobacterium sibiricum (EsGDH), was constructed to fulfill efficient NADPH regeneration. During the whole-cell catalyzed asymmetric reduction of KPL, the spontaneous hydrolysis of KPL significantly affected the yield of (R)-PL, which was effectively alleviated by the employment of the substrate constant-feeding strategy. The established whole-cell bioreduction for 6 h afforded 458 mM (R)-PL with the enantiomeric excess value of >99.9% and the yield of 91.6%. Escherichia coli coexpressing SceCPR1 and EsGDH efficiently catalyzed the asymmetric synthesis of (R)-PL through the substrate constant-feeding strategy.

  7. Stereoselective synthesis of 5-alkoxycarbonyl-4 alkyl-2-anino-3-cyano-6-methyl-4H-pyranes 3 via asymmetric Michael addition to aceptors-gamma-stereogenics; Sintesis esteroselective de 5-alcoxicarbonil-4-alquil-2-amino-3-ciano-6-metil-4H-piranos via adicion Michael sobre aceptores-gama-esterogenicos

    Energy Technology Data Exchange (ETDEWEB)

    Martinez-Grau, A.; Jimenez, B.; Martin, N.; Seoane, C.; Marco, J.L. [Departamento de Quimica Organica, Facultad de Quimica, Universidad Complutense, Madrid (Spain)

    1994-12-31

    The stereoselective synthesis of 5-alkoxycarbonyl-4-alkyl-2-amino-3-cyano-6-methyl-4H-pyrans 3 via asymmetric Michael addition of malononitrile to gamma-stereogenic alpha-acetylacrylates 2 obtained by Knoevenagel reaction of acetylacetates to quiral alpha-hydroxyaldehydes 1 is described. The resulting 2-amino-4H-pyrans 3 have been obtained in moderate yield and good diastereoselectivity. 15 refs.

  8. Stereoselective Reduction of Imines with Trichlorosilane Using Solid-Supported Chiral Picolinamides

    Directory of Open Access Journals (Sweden)

    Sílvia D. Fernandes

    2016-09-01

    Full Text Available The stereoselective reduction of imines with trichlorosilane catalyzed by chiral Lewis bases is a well-established procedure for the synthesis of enantio-enriched amines. Five supported cinchona-based picolinamides have been prepared and their activity tested in a model reaction. The comparison of different supporting materials revealed that polystyrene gave better results than silica in terms of stereoselectivity. The applicability of the solid-supported catalyst of choice to the reduction of different imines was also demonstrated. Additionally, for the first time, a catalytic reactor containing a polymer-immobilized chiral picolinamide has been employed for the stereoselective reduction of imines with trichlorosilane under continuous flow conditions.

  9. New chiral phosphinephosphinite ligands: Application to stereoselective synthesis of a key intermediate of 1{beta}-methyl carbapenems by Rh(I)-catalyzed asymmetric hydroformylation

    Energy Technology Data Exchange (ETDEWEB)

    Saito, Takao; Yoshida, Akifumi; Matsumura, Kazuhiko [Takasago International Corp., Kanagawa (Japan)] [and others

    1995-12-31

    Transition metal catalyzed asymmetric hydroformylation is an attractive and highly useful homologation process for organic synthesis. Recently, the authors reported that the Rh(I) complexes of phosphinephosphite BINAPHOS are highly efficient catalysts for enantioselective hydroformylation of a variety of olefins. This time, the authors have designed and synthesized new chiral phosphinephosphinite ligands having binaphthyl backbone, (R)-2-diarylphosphino-2{prime}-diarylphosphinoxy-1,1{prime}-binaphthy1 (hereafter abbreviated (R)-BIPNITE). The Rh(I) complexes of these ligands are effective catalysts for the asymmetric hydroformylation of 4-vinylazetidin-2-one to give the corresponding oxo-aldehyde 3{beta} as the major product in very high diastereoselectivities and in good regioselectivities. Interestingly, modifications of the aryl substituents in phosphine and phosphinite moieties afforded higher selectivities. Aldehyde 3{beta} was easily oxidized with NaClO{sub 2} to 4, a key intermediate of 1{beta}-methyl carbapenems. Thus, the present method provides a new practical route to a versatile key intermediate for the synthesis of carbapenem antibiotics.

  10. Directed Evolution of Carbonyl Reductase from Rhodosporidium toruloides and Its Application in Stereoselective Synthesis of tert-Butyl (3R,5S)-6-Chloro-3,5-dihydroxyhexanoate.

    Science.gov (United States)

    Liu, Zhi-Qiang; Wu, Lin; Zhang, Xiao-Jian; Xue, Ya-Ping; Zheng, Yu-Guo

    2017-05-10

    tert-Butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate ((3R,5S)-CDHH) is a key intermediate of atorvastatin and rosuvastatin synthesis. Carbonyl reductase RtSCR9 from Rhodosporidium toruloides exhibited excellent activity toward tert-butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate ((S)-CHOH). For the activity of RtSCR9 to be improved, random mutagenesis and site-saturation mutagenesis were performed. Three positive mutants were obtained (mut-Gln95Asp, mut-Ile144Lys, and mut-Phe156Gln). These mutants exhibited 1.94-, 3.03-, and 1.61-fold and 1.93-, 3.15-, and 1.97-fold improvement in the specific activity and k cat /K m , respectively. Asymmetric reduction of (S)-CHOH by mut-Ile144Lys coupled with glucose dehydrogenase was conducted. The yield and enantiomeric excess of (3R,5S)-CDHH reached 98 and 99%, respectively, after 8 h bioconversion in a single batch reaction with 1 M (S)-CHOH, and the space-time yield reached 542.83 mmol L -1 h -1 g -1 wet cell weight. This study presents a new carbonyl reductase for efficient synthesis of (3R,5S)-CDHH.

  11. Enhanced Stereoselectivity of a Cu(II) Complex Chiral Auxiliary in the Synthesis of Fmoc-L-γ-carboxyglutamic Acid | Center for Cancer Research

    Science.gov (United States)

    Bridging bioinorganic chemistry with asymmetric synthesis: a naturally occurring metalloprotein is used for the structure-based evolution of chiral auxiliaries that prove to be effective in the synthesis of Fmoc-L-γ-carboxyglutamic acid.

  12. An Efficient, Green Chemical Synthesis of the Malaria Drug ...

    African Journals Online (AJOL)

    Purpose: To provide a robust, efficient synthesis of the malaria drug piperaquine for potential use in resource-poor settings. Methods: We used in-process analytical technologies (IPAT; HPLC) and a program of experiments to develop a synthesis of piperaquine that avoids the presence of a toxic impurity in the API and is ...

  13. An Improved, Highly Efficient Method for the Synthesis of Bisphenols

    Directory of Open Access Journals (Sweden)

    L. S. Patil

    2011-01-01

    Full Text Available An efficient synthesis of bisphenols is described by condensation of substituted phenols with corresponding cyclic ketones in presence of cetyltrimethylammonium chloride and 3-mercaptopropionic acid as a catalyst in extremely high purity and yields.

  14. Palladium-catalyzed regio- and stereoselective cross-addition of terminal alkynes to ynol ethers and synthesis of 1,4-enyn-3-ones.

    Science.gov (United States)

    Babu, Madala Hari; Dwivedi, Vikas; Kant, Ruchir; Reddy, Maddi Sridhar

    2015-03-16

    Conjugated enynes, enol ethers, and enynones are versatile building blocks that can be elaborated by a wide variety of synthetic transformations. The selective synthesis of such units is a prerequisite for their effective utilization. The synthesis of conjugated 2-phenoxyenynes through a palladium-catalyzed cross-addition of terminal alkynes to phenylethynyl ethers (hydroalkynylation) is now presented. The reaction is highly regio-, stereo-, and chemoselective, and shows excellent tolerance toward functional groups. The addition further features very mild reaction conditions (room temperature) and an inexpensive catalytic system (without a ligand and with a cheaply available Pd catalyst). The thus synthesized enynyl ethers with allylic hydroxy tethers, which survived the reaction, were shown to be ready precursors for valuable 1-en-4-yn-3-ones. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Cross-Aldol Reaction of Activated Carbonyls with Nitrosocarbonyl Intermediates: Stereoselective Synthesis toward α-Hydroxy-β-amino Esters and Amides.

    Science.gov (United States)

    Mallik, Sumitava; Bhajammanavar, Vinod; Ramakrishna, Isai; Baidya, Mahiuddin

    2017-07-21

    A practical and flexible strategy toward α-hydroxy-β-amino esters and amides, which are important biological motifs, based on an organocatalytic cross-aldol reaction of in situ-generated nitrosocarbonyl intermediates followed by hydrogenation is presented. The protocol features operational simplicity, high yields, a wide substrate scope, and high regio- and diastereoselectivity profiles. The utility of this method was showcased through the synthesis of bestatin analogues and indole formation.

  16. Ionic liquid mediated stereoselective synthesis of alanine linked hybrid quinazoline-4(3H)-one derivatives perturbing the malarial reductase activity in folate pathway.

    Science.gov (United States)

    Patel, Tarosh S; Bhatt, Jaimin D; Vanparia, Satish F; Patel, Urmila H; Dixit, Ritu B; Chudasama, Chaitanya J; Patel, Bhavesh D; Dixit, Bharat C

    2017-12-15

    Grimmel's method was optimized as well as modified leading to the cyclization and incorporation of alanine linked sulphonamide in 4-quinazolin-(3H)-ones. Further, the generation of heterocyclic motif at position-3 of 4-quinazolinones was explored by synthesis of imines, which unfortunately led to an isomeric mixture of stereoisomers. The hurdle of diastereomers encountered on the path was eminently rectified by development of new rapid and reproducible methodology involving the use of imidazolium based ionic liquid as solvents as well as catalyst for cyclization as well as synthesis of imines in situ at position-3 leading to procurement of single E-isomer as the target hybrid heterocyclic molecules. The purity and presence of single isomer was also confirmed by HPLC and spectroscopic techniques. Further, the synthesized sulphonamide linked 4-quinazolin-(3H)-ones hybrids were screened for their antimalarial potency rendering potent entities (4b, 4c, 4 l, 4 t and 4u). The active hybrids were progressively screened for enzyme inhibitory efficacy against presumed receptor Pf-DHFR and h-DHFR computationally as well as in vitro, proving their potency as dihydrofolate reductase inhibitors. The ADME properties of these active molecules were also predicted to enhance the knowhow of the oral bioavailability, indicating good bioavailability of the active entities. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Cooperative catalysis designing efficient catalysts for synthesis

    CERN Document Server

    Peters, René

    2015-01-01

    Written by experts in the field, this is a much-needed overview of the rapidly emerging field of cooperative catalysis. The authors focus on the design and development of novel high-performance catalysts for applications in organic synthesis (particularly asymmetric synthesis), covering a broad range of topics, from the latest progress in Lewis acid / Br?nsted base catalysis to e.g. metal-assisted organocatalysis, cooperative metal/enzyme catalysis, and cooperative catalysis in polymerization reactions and on solid surfaces. The chapters are classified according to the type of cooperating acti

  18. Studies on the Model Synthesis of the Brassinolide and Dolicholide Side Chains

    Institute of Scientific and Technical Information of China (English)

    Li Zeng PENG; Feng Zhi ZHANG; Tian Sheng MEI; Yu Lin LI

    2003-01-01

    A stereoselective synthesis of brassinolide and dolicholide, which involves constructionof the side chain enantiomers by a highly stereoselective aldol reaction of aldehyde 5 with theanion of α-silyloxy ketone 6 is described.

  19. New stereoselective intramolecular

    Science.gov (United States)

    Alajarin; Vidal; Tovar; Ramirez De Arellano MC; Cossio; Arrieta; Lecea

    2000-11-03

    Efficient 1,4-asymmetric induction has been achieved in the highly stereocontrolled intramolecular [2 + 2] cycloadditions between ketenimines and imines, leading to 1,2-dihydroazeto[2, 1-b]quinazolines. The chiral methine carbon adjacent to the iminic nitrogen controls the exclusive formation of the cycloadducts with relative trans configuration at C2 and C8. The stepwise mechanistic model, based on theoretical calculations, fully supports the stereochemical outcome of these cycloadditions.

  20. Efficient synthesis of phosphonodepsipeptides derived from norleucine

    Czech Academy of Sciences Publication Activity Database

    Pícha, Jan; Buděšínský, Miloš; Hančlová, Ivona; Šanda, Miloslav; Fiedler, Pavel; Vaněk, Václav; Jiráček, Jiří

    2009-01-01

    Roč. 65, č. 31 (2009), s. 6090-6103 ISSN 0040-4020 R&D Projects: GA ČR GA203/06/1405; GA MŠk(CZ) LC06077 Institutional research plan: CEZ:AV0Z40550506 Keywords : phosphonate * pseudopeptide * inhibitor * synthesis * norleucine Subject RIV: CC - Organic Chemistry Impact factor: 3.219, year: 2009

  1. Stereoselectivity of sodium borohydride reduction of saturated steroidal ketones utilizing conditions of Luche reduction

    Czech Academy of Sciences Publication Activity Database

    Šťastná, Eva; Černý, Ivan; Pouzar, Vladimír; Chodounská, Hana

    2010-01-01

    Roč. 75, č. 10 (2010), s. 721-725 ISSN 0039-128X R&D Projects: GA ČR(CZ) GA203/08/1498; GA MŠk(CZ) LC06077 Institutional research plan: CEZ:AV0Z40550506 Keywords : steroid * synthesis * stereoselectivity Subject RIV: CC - Organic Chemistry Impact factor: 3.106, year: 2010

  2. An Efficient Catalyst for the Synthesis of Schiff Bases

    International Nuclear Information System (INIS)

    Fareed, G.; Afza, N.; Kalhoro, M.A.

    2013-01-01

    An efficient high yielding synthesis of Schiff bases (1-17) is derived from condensation of 2-fluorenamine and 4-amino phenol with a variety of aldehydes catalyzed by dodecatungstosilicic acid P/sub 2/O/sub 5/ under solvent free conditions at room temperature. The catayst is found to be more efficient in terms of ease of reaction workup and high yields. This methodology contributes to an energy efficient, facile and environamental friendly synthesis for the preparation of Schiff bases. The structures of afforded Schiff bases were characterized by spectroscopic data and elemental analysis. (author)

  3. Stereoselective synthesis of diazaspiro[5.5]undecane derivatives via base promoted [5+1] double Michael addition of N,N-dimethylbarbituric acid to diaryliedene acetones

    Directory of Open Access Journals (Sweden)

    Mohammad Shahidul Islam

    2017-01-01

    Full Text Available The nitrogen containing spiro-heterocycle is one of the privileged synthetic motif that constitutes various naturally occurring molecules and displays a broad range of pharmaceutical and biological activities. A new methodology was developed for the synthesis of 2,4-diazaspiro[5.5]undecane-1,3,5,9-tetraones spiro-heterocyclic derivatives via cascade cyclization of [5+1] double Michael addition reaction of N,N-dimethylbarbituric acid with the derivatives of diaryldivinylketones in the presence of diethylamine at ambient temperature. The developed protocol is highly capable of furnishing diazaspiro[5.5]undecane derivatives 3a–m in excellent yields (up to 98%, from easily accessible symmetric and non-symmetric divinylketones 2a–m, containing aryl and heteroaryl substituents. The diazaspiro-heterocyclic structure was mainly elucidated by NMR and X-ray crystallographic techniques. The single-crystal X-ray studies revealed that, the cyclohexanone unit of spirocycles often prefers a chair conformation rather than twisted conformation. The intermolecular hydrogen bonding and CArH⋯π, π–π stacking interactions driving forces are mainly responsible for the crystal packing.

  4. Mg2FeH6 Synthesis Efficiency Map

    Directory of Open Access Journals (Sweden)

    Katarzyna Witek

    2018-02-01

    Full Text Available The influences of the processing parameters on the Mg2FeH6 synthesis yield were studied. Mixtures of magnesium hydride (MgH2 and iron (Fe were mechanically milled in a planetary ball mill under argon for 0.5-, 1-, 2- and 3-h periods and subsequently sintered at temperatures from 300–500 ∘ C under hydrogen. The reaction yield, phase content and hydrogen storage properties of the received materials were investigated. The morphologies of the powders after synthesis were studied by SEM. The synthesis effectiveness map was presented. The obtained results prove that synthesis parameters, such as the milling time and synthesis temperature, greatly influence the reaction yield and material properties and show that extended mechanical milling may not be beneficial to the reaction efficiency.

  5. Ultrasound-assisted synthesis of β-amino ketones via a Mannich reaction catalyzed by Fe3O4 magnetite nanoparticles as an efficient, recyclable and heterogeneous catalyst

    Directory of Open Access Journals (Sweden)

    Naghi Saadatjoo

    2017-02-01

    The present methodology offers several advantages, such as good yields, short reaction times and a recyclable catalyst with a very easy work up. In addition, the obtained results indicated that MNPs can be used as an effective and inexpensive catalyst for stereoselective synthesis of β-amino carbonyl by a one-pot three component condensation of aldehydes, ketones and amines.

  6. Concepts for stereoselective acrylate insertion

    KAUST Repository

    Neuwald, Boris

    2013-01-23

    Various phosphinesulfonato ligands and the corresponding palladium complexes [{((PaO)PdMeCl)-μ-M}n] ([{( X1-Cl)-μ-M}n], (PaO) = κ2- P,O-Ar2PC6H4SO2O) with symmetric (Ar = 2-MeOC6H4, 2-CF3C6H4, 2,6-(MeO)2C6H3, 2,6-(iPrO)2C 6H3, 2-(2′,6′-(MeO)2C 6H3)C6H4) and asymmetric substituted phosphorus atoms (Ar1 = 2,6-(MeO)2C6H 3, Ar2 = 2′-(2,6-(MeO)2C 6H3)C6H4; Ar1 = 2,6-(MeO)2C6H3, Ar2 = 2-cHexOC 6H4) were synthesized. Analyses of molecular motions and dynamics by variable temperature NMR studies and line shape analysis were performed for the free ligands and the complexes. The highest barriers of ΔGa = 44-64 kJ/mol were assigned to an aryl rotation process, and the flexibility of the ligand framework was found to be a key obstacle to a more effective stereocontrol. An increase of steric bulk at the aryl substituents raises the motional barriers but diminishes insertion rates and regioselectivity. The stereoselectivity of the first and the second methyl acrylate (MA) insertion into the Pd-Me bond of in situ generated complexes X1 was investigated by NMR and DFT methods. The substitution pattern of the ligand clearly affects the first MA insertion, resulting in a stereoselectivity of up to 6:1 for complexes with an asymmetric substituted phosphorus. In the consecutive insertion, the stereoselectivity is diminished in all cases. DFT analysis of the corresponding insertion transition states revealed that a selectivity for the first insertion with asymmetric (P aO) complexes is diminished in the consecutive insertions due to uncooperatively working enantiomorphic and chain end stereocontrol. From these observations, further concepts are developed. © 2012 American Chemical Society.

  7. A Large Scale Formal Synthesis of CoQ10: Highly Stereoselective Friedel-Crafts Allylation Reaction of Tetramethoxytoluene with (E)-4-Chloro-2-methyl-1-phenylsulfonyl-2-butene in the Presence of Montmorillonite K-10

    International Nuclear Information System (INIS)

    Lee, Sang Who; Lee, Hee Bong; Kim, Bong Chan; Sadaiah, Kadivendi; Lee, Kyuwoong; Shin, Hyunik

    2013-01-01

    We disclosed that MK-10 is a highly effective catalyst for the Friedel-Crafts reaction of 6 and 7 in terms of yield and of stereoselectivity. Although there are numerous applications of clays in Friedel-Crafts reaction, there is very limited example which demonstrated its effect on the stereoselectivity. In that context, our result is significant and further expansion in this direction is highly envisioned. Ubiquinone, as its name represents, exists ubiquitously in human body, particularly in the heart. It mediates the electron transfer process in mitochondria and also exerts strong antioxidant effect in its reduced form. In clinical trial, it showed beneficial effect on heart-related diseases such as myocardial infarction, angina, and other related symptoms to cause decreased mortality compared to the placebo group

  8. A Large Scale Formal Synthesis of CoQ{sub 10}: Highly Stereoselective Friedel-Crafts Allylation Reaction of Tetramethoxytoluene with (E)-4-Chloro-2-methyl-1-phenylsulfonyl-2-butene in the Presence of Montmorillonite K-10

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sang Who; Lee, Hee Bong; Kim, Bong Chan; Sadaiah, Kadivendi; Lee, Kyuwoong; Shin, Hyunik [LG Life Sciences, Ltd., Daejeon (Korea, Republic of)

    2013-04-15

    We disclosed that MK-10 is a highly effective catalyst for the Friedel-Crafts reaction of 6 and 7 in terms of yield and of stereoselectivity. Although there are numerous applications of clays in Friedel-Crafts reaction, there is very limited example which demonstrated its effect on the stereoselectivity. In that context, our result is significant and further expansion in this direction is highly envisioned. Ubiquinone, as its name represents, exists ubiquitously in human body, particularly in the heart. It mediates the electron transfer process in mitochondria and also exerts strong antioxidant effect in its reduced form. In clinical trial, it showed beneficial effect on heart-related diseases such as myocardial infarction, angina, and other related symptoms to cause decreased mortality compared to the placebo group.

  9. Alum an Efficient Catalyst for Erlenmeyer Synthesis

    African Journals Online (AJOL)

    NICO

    this paper we describe the use of alum as a catalyst in the. Erlenmeyer reaction, under solvent-free condition using ultra- sonic irradiation. The application of solvent-free reaction conditions in organic chemistry has been explored extensively within the last decade. It was shown to be an efficient technique for various organic.

  10. Efficient synthesis of benzothiazine and acrylamide compounds

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Ana Maria Alves; Walfrido, Simone Torres Padua; Leite, Lucia Fernanda Costa; Lima, Maria Carmo Alves; Galdino, Suely Lins; Pitta, Ivan Rocha [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Dept. de Antibioticos; Barbosa Filho, Jose Maria [Universidade Federal da Paraiba (UFPB), Joao Pessoa, PB (Brazil); Simone, Carlos Alberto de; Ellena, Javier Alcides, E-mail: irpitta@gmail.co [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Inst. de Fisica

    2010-07-01

    This article describes the synthesis of the new (2Z)-2-(4-methoxybenzylidene)-6-nitro-4H -benzo[1,4]thiazine-3-one, (2Z)-2-(4-methoxybenzylidene)-4-methyl-6-nitro-4H-benzo[1,4]thiazine-3-one, (2Z)-6-amino-2-(4-methoxybenzylidene)-4H -benzo[1,4]thiazine-3-one, (2Z)-6-butylamino-2-(4-methoxybenzylidene)-4-methyl-4H-benzo[1,4] -thiazine-3-one and (2E)-N-alkyl-N-(2-hydroxy-5-nitrophenyl) -3-phenylacrylamides and the spectroscopic data. The arylidenebenzothiazine compounds were prepared using the Knoevenagel condensation with substituted benzaldehydes in the presence of sodium methoxide in DMF. The presence of a nitro substituent in the 4-position, water and a slightly acid reaction medium in this condensation caused the rupture of the benzothiazine ring and subsequent formation of the phenylacrylamide compounds. A crystallographic data was presented for (2E)-3-(4-bromophenyl)-N-dodecyl-N -(2-hydroxy-5-nitrophenyl) acrylamide. (author)

  11. Efficient synthesis of benzothiazine and acrylamide compounds

    International Nuclear Information System (INIS)

    Souza, Ana Maria Alves; Walfrido, Simone Torres Padua; Leite, Lucia Fernanda Costa; Lima, Maria Carmo Alves; Galdino, Suely Lins; Pitta, Ivan Rocha; Simone, Carlos Alberto de; Ellena, Javier Alcides

    2010-01-01

    This article describes the synthesis of the new (2Z)-2-(4-methoxybenzylidene)-6-nitro-4H -benzo[1,4]thiazine-3-one, (2Z)-2-(4-methoxybenzylidene)-4-methyl-6-nitro-4H-benzo[1,4]thiazine-3-one, (2Z)-6-amino-2-(4-methoxybenzylidene)-4H -benzo[1,4]thiazine-3-one, (2Z)-6-butylamino-2-(4-methoxybenzylidene)-4-methyl-4H-benzo[1,4] -thiazine-3-one and (2E)-N-alkyl-N-(2-hydroxy-5-nitrophenyl) -3-phenylacrylamides and the spectroscopic data. The arylidenebenzothiazine compounds were prepared using the Knoevenagel condensation with substituted benzaldehydes in the presence of sodium methoxide in DMF. The presence of a nitro substituent in the 4-position, water and a slightly acid reaction medium in this condensation caused the rupture of the benzothiazine ring and subsequent formation of the phenylacrylamide compounds. A crystallographic data was presented for (2E)-3-(4-bromophenyl)-N-dodecyl-N -(2-hydroxy-5-nitrophenyl) acrylamide. (author)

  12. An efficient synthesis of quinolines under solvent-free conditions

    Indian Academy of Sciences (India)

    Unknown

    An efficient synthesis of quinolines under solvent-free conditions. 201 was then irradiated with microwaves in a microwave oven (Samsung model# CE118KF) at 1050W (70% of total power) for 5 minutes (3 + 2 with an inter- mission of 5 minutes). The reaction mixture was cooled at room temperature and rendered basic (pH.

  13. An Efficient Synthesis of Enantiopure (R-heteroarylpyrimidine Analogs

    Directory of Open Access Journals (Sweden)

    Guo-Ming Zhao

    2013-09-01

    Full Text Available An efficient synthesis of enantiopure (R-heteroarylpyrimidine analogs is described here, which involves introduction of a chiral group, formation and separation of diasteroisomers and final transformation of an amide to an ester. The absolute configuration of the enantiopure HAPs is confirmed by X-ray analysis of their intermediates.

  14. Efficient Synthesis of 1-Sulfonyl-1,2,3-triazoles

    Science.gov (United States)

    Raushel, Jessica; Fokin, Valery V.

    2010-01-01

    An efficient room temperature method for the synthesis of 1-sulfonyl-1,2,3-triazoles from in situ generated copper(I) acetylides and sulfonyl azides is described. Copper(I) thiophene-2-carboxylate (CuTC) catalyst produces the title compounds under both non-basic anhydrous and aqueous conditions in good yields. PMID:20931987

  15. Novel efficient process for methanol synthesis by CO2 hydrogenation

    NARCIS (Netherlands)

    Kiss, Anton Alexandru; Pragt, J.J.; Vos, H.J.; Bargeman, Gerrald; de Groot, M.T.

    2016-01-01

    Methanol is an alternative fuel that offers a convenient solution for efficient energy storage. Complementary to carbon capture activities, significant effort is devoted to the development of technologies for methanol synthesis by hydrogenation of carbon dioxide. While CO2 is available from plenty

  16. A rapid stereoselective synthesis of fluorinated carbohydrates

    International Nuclear Information System (INIS)

    Adam, M.J.; Neeser, J-R.; Hall, L.D.; Pate, B.D.

    1983-01-01

    Acetyl hypofluorite has been added to six unsaturated carbohydrates which contain the vinyl ether moiety. All reactions were rapid (less than 5 min.) at -78 degrees C and gave, with one exception, high yields of isomerically pure products. The hypofluorite was shown to add exclusively in a cis mode and with a strong preference for a particular 'face' of the double bond. As well as the syntheses, NMR data and preferred conformations for the fluorinated products are also discussed

  17. Structural Amendment and Stereoselective Synthesis of Mutisianthol.

    Science.gov (United States)

    Ho, Tse-Lok; Lee, Kwang-Yuan; Chen, Chun-Kuei

    1997-05-16

    cis-1-(5-Acetoxy-3,6-dimethyl-1-indanyl)-2-methyl-1-propene synthesized from 3,6-dimethyl-1-indanone was found to be different from mutisianthol by spectral comparison. The presence of a high-field signal in the NMR spectrum of the final product and various intermediates, characteristic of the cis-1,3-dialkylindanes but absent in the spectrum of the natural terpene, suggests a revision of the structure of mutisianthol to the trans isomer. The trans-indane which was subsequently obtained indeed exhibits data fully agreeable with mutisianthol. A similar stereochemical revision for jungianol is also indicated.

  18. CuI/Pd0 cooperative dual catalysis: tunable stereoselective construction of tetra-substituted alkenes.

    Science.gov (United States)

    Vercruysse, Sébastien; Cornelissen, Loïc; Nahra, Fady; Collard, Laurent; Riant, Olivier

    2014-02-10

    This paper describes a tunable and stereoselective dual catalytic system that uses copper and palladium reagents. This cooperative silylcupration and palladium-catalyzed allylation readily affords trisubstituted alkenylsilanes. Fine-tuning the reaction conditions allows selective access to one stereoisomer over the other. This new methodology tolerates different substituents on both coupling partners with high levels of stereoselectivity. The one-pot reaction involving a Cu(I)/Pd(0) cooperative dual catalyst directly addresses the need to develop more time-efficient and less-wasteful synthetic pathways. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Combining multi-catalysis and multi-component systems for the development of one-pot asymmetric reactions: stereoselective synthesis of highly functionalized bicyclo[4.4.0]decane-1,6-diones.

    Science.gov (United States)

    Ramachary, Dhevalapally B; Sakthidevi, Rajasekar

    2008-07-21

    We have developed a direct amine/acid-catalyzed stereoselective hydrogenation of a variety of Wieland-Miescher (W-M) ketones, Hajos-Parrish (H-P) ketones and their analogs with organic hydrides (Hantzsch esters) as the hydrogen source. This astonishingly simple and biomimetic approach was used to construct highly functionalized chiral bicyclo[4.4.0]decane-1,6-diones in a diastereoselective fashion. This is an example of the development of a new technology by the combination of multiple catalysts and components in one pot to deliver highly functionalized chiral molecules.

  20. Photoredox-Catalyzed Stereoselective Conversion of Alkynes into Tetrasubstituted Trifluoromethylated Alkenes.

    Science.gov (United States)

    Tomita, Ren; Koike, Takashi; Akita, Munetaka

    2015-10-26

    A regio- and stereoselective synthesis of trifluoromethylated alkenes bearing four different substituents has been developed. Stereocontrolled sulfonyloxytrifluoromethylation of unsymmetric internal alkynes with an electrophilic CF3 reagent, namely the triflate salt of the Yagupol'skii-Umemoto reagent, in the presence of an Ir photoredox catalyst under visible-light irradiation afforded trifluoromethylalkenyl triflates with well-predictable stereochemistry resulting from anti addition of the trifluoromethyl and triflate groups. Subsequent palladium-catalyzed cross-couplings led to tetrasubstituted trifluoromethylated alkenes in a highly stereoselective manner. The present method is the first example of a facile one-pot synthesis of tetrasubstituted trifluoromethylated alkenes from simple alkynes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. A multi-enzymatic cascade reaction for the stereoselective production of γ-oxyfunctionalyzed amino acids

    Directory of Open Access Journals (Sweden)

    Junichi eEnoki

    2016-04-01

    Full Text Available A stereoselective three-enzyme cascade for synthesis of diasteromerically pure γ-oxyfunctionalized α-amino acids was developed. By coupling a dynamic kinetic resolution using an N-acylamino acid racemase and an L-selective aminoacylase from Geobacillus thermoglucosidasius with a stereoselective isoleucine dioxygenase from Bacillus thuringiensis, diastereomerically pure oxidized amino acids were produced from racemic N-acetylamino acids. The three enzymes differ in their optimal temperature and pH-spectra. Their different metal cofactor dependencies lead to inhibitory effects. Under optimized conditions, racemic N-acetylmethionine was quantitatively converted into L-methionine-(S-sulfoxide with 97% conversion and 95% de. The combination of these three different biocatalysts allows the direct synthesis of diastereopure oxyfunctionalized amino acids from inexpensive racemic starting material.

  2. Stereoselective Carbonyl Olefination with Fluorosulfoximines: Facile Access to Z or E Terminal Monofluoroalkenes.

    Science.gov (United States)

    Liu, Qinghe; Shen, Xiao; Ni, Chuanfa; Hu, Jinbo

    2017-01-09

    Terminal monofluoroalkenes are important structural motifs in the design of bioactive compounds, such as homeostasis regulators and mechanism-based enzyme inhibitors. However, it is difficult to control the stereoselectivity of known carbonyl olefination reactions, and olefin metathesis is limited to disubstituted terminal monofluoroalkenes. Although sulfoximines have been used extensively in organic synthesis, reports on their use in carbonyl olefination reactions have not appeared to date. Herein, we report highly stereoselective carbonyl monofluoroolefination with a fluorosulfoximine reagent. The potential of this method is demonstrated by the synthesis of MDL 72161 and by the late-stage monofluoromethylenation of complex molecules, such as haloperidol and steroid derivatives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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.

  4. Energy efficiency in nanoscale synthesis using nanosecond plasmas.

    Science.gov (United States)

    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.

  5. Regio and stereoselectivity in ionic cycloadditions

    Indian Academy of Sciences (India)

    WINTEC

    Though the reactions have both electrostatic control and frontier orbital control the former dominates in the initial stages of the reaction. Keywords. Stereoselectivity; ionic cycloaddition; density functional theory; acridizinium ion; methyl vinyl ether; 2,3-dimethylisoquinolinium ion. 1. Introduction. In polar or ionic cycloadditions ...

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

    Science.gov (United States)

    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.

  7. Catalogue of Energy Efficiency Measures for France - Synthesis report

    International Nuclear Information System (INIS)

    2013-10-01

    ADEME wished to learn about existing effective energy efficiency measures implemented outside of France, whether cross-sectoral or targeted at a specific sector (industry, transport, buildings or agriculture). The objective of this survey was to determine whether any of these measures could be applied in France, with the goal of holding down the growth of energy consumption. This survey has led to the writing of a catalog of 53 two-page fact sheets describing the measures identified as interesting for France. These measures were analysed via classic criteria of evaluation such as cost-efficiency or impact, allowing to highlight the most successful measures for the French territory. ADEME presents you a synthesis of this survey in this document

  8. Marine Microorganisms as Source of Stereoselective Esterases and Ketoreductases: Kinetic Resolution of a Prostaglandin Intermediate

    KAUST Repository

    De Vitis, Valerio; Guidi, Benedetta; Contente, Martina Letizia; Granato, Tiziana Mariarita; Conti, Paola; Molinari, Francesco; Crotti, Elena; Mapelli, Francesca; Borin, Sara S.; Daffonchio, Daniele; Romano, Diego

    2014-01-01

    A screening among bacterial strains isolated from water-brine interface of the deep hypersaline anoxic basins (DHABs) of the Eastern Mediterranean was carried out for the biocatalytical resolution of racemic propyl ester of anti-2-oxotricyclo[2.2.1.0]heptan-7-carboxylic acid (R,S)-1, a key intermediate for the synthesis of d-cloprostenol. Bacillus horneckiae 15A gave highly stereoselective reduction of (R,S)-1, whereas Halomonas aquamarina 9B enantioselectively hydrolysed (R,S)-1; in both cases, enantiomerically pure unreacted (R)-1 could be easily recovered and purified at molar conversion below 57–58 %, showing the potential of DHAB extremophile microbiome and marine-derived enzymes in stereoselective biocatalysis.

  9. Marine Microorganisms as Source of Stereoselective Esterases and Ketoreductases: Kinetic Resolution of a Prostaglandin Intermediate

    KAUST Repository

    De Vitis, Valerio

    2014-09-30

    A screening among bacterial strains isolated from water-brine interface of the deep hypersaline anoxic basins (DHABs) of the Eastern Mediterranean was carried out for the biocatalytical resolution of racemic propyl ester of anti-2-oxotricyclo[2.2.1.0]heptan-7-carboxylic acid (R,S)-1, a key intermediate for the synthesis of d-cloprostenol. Bacillus horneckiae 15A gave highly stereoselective reduction of (R,S)-1, whereas Halomonas aquamarina 9B enantioselectively hydrolysed (R,S)-1; in both cases, enantiomerically pure unreacted (R)-1 could be easily recovered and purified at molar conversion below 57–58 %, showing the potential of DHAB extremophile microbiome and marine-derived enzymes in stereoselective biocatalysis.

  10. Beating Bias in the Directed Evolution of Proteins: Combining High-Fidelity on-Chip Solid-Phase Gene Synthesis with Efficient Gene Assembly for Combinatorial Library Construction.

    Science.gov (United States)

    Li, Aitao; Acevedo-Rocha, Carlos G; Sun, Zhoutong; Cox, Tony; Xu, Jia Lucy; Reetz, Manfred T

    2018-02-02

    Saturation mutagenesis (SM) constitutes a widely used technique in the directed evolution of selective enzymes as catalysts in organic chemistry and in the manipulation of metabolic paths and genomes, but the quality of the libraries is far from optimal due to the inherent amino acid bias. Herein, it is shown how this fundamental problem can be solved by applying high-fidelity solid-phase chemical gene synthesis on silicon chips followed by efficient gene assembly. Limonene epoxide hydrolase was chosen as the catalyst in the model desymmetrization of cyclohexene oxide with the stereoselective formation of (R,R)- and (S,S)-cyclohexane-1,2-diol. A traditional combinatorial PCR-based SM library, produced by simultaneous randomization at several residues by using a reduced amino acid alphabet, and the respective synthetic library were constructed and compared. Statistical analysis at the DNA level with massive sequencing demonstrates that, in the synthetic approach, 97 % of the theoretically possible DNA mutants are formed, whereas the traditional SM library contained only about 50 %. Screening at the protein level also showed the superiority of the synthetic library; many highly (R,R)- and (S,S)-selective variants being discovered are not found in the traditional SM library. With the prices of synthetic genes decreasing, this approach may point the way to future directed evolution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Regio- and stereoselective iodoacyloxylations of alkynes.

    Science.gov (United States)

    Priebbenow, Daniel L; Gable, Robert W; Baell, Jonathan

    2015-05-01

    A new method for the regioselective and stereoselective iodoacyloxylation of alkynes has been developed. This protocol utilizes a combination of an iodobenzene dicarboxylate and iodine to functionalize a series of activated and unactivated alkynes in an entirely selective and predictable fashion. The resultant iodo-enol esters were subsequently coupled with boronic acids to afford tetrasubstituted alkene derivatives, which could be further converted to the corresponding 1,1-disubstituted acetophenone.

  12. Stereoselective synthesis of ( E)-4-(imidazo[1,2- a]pyrid-2-yl)-3-(4-methylphenylsulfonyl)but-3-en-2-one. X-ray crystal structure and conformational analysis

    Science.gov (United States)

    Roche, D.; Force, L.; Carpy, A.; Gardette, D.; Madesclaire, M.

    1998-06-01

    The title compound, gem-ketovinylsulfone 3, was obtained stereoselectively (de > 98%) by the action of the α-anion from p-tolylsulfonylacetone 1 on imidazol[1,2- a]pyridine-2-carbaldehyde 2 in chelation-controlled conditions in the presence of a Lewis acid (ZnCl 2). The X-ray crystal structure of 3 [C 18H 16N 2O 3S: Mt = 340.4, orthorhombic, Pbca, a = 12.208(3) Å, b = 18.848(4) Å, c = 14.566(11) Å, V = 3.351(3) Å3, Z = 8, Dcalc = 1.349 g cm -3, λ( CuKα) = 1.54178 Å, μ = 1.83 mm -1, F(000) = 1424, T = 293 K, R = 0.061 for 2.046 observed reflections] was determined, and confirmed the ( E) configuration. Despite the conjugate position of the vinyl double bond, quasi-coplanar with the imidazopyridine heterocycle, there is no evidence of p-electron delocalization. The crystal cohesion is ensured by a dense network of van der Waals contacts. The conformational analysis of the ( E) and ( Z) stereoisomers was performed by molecular dynamics simulation, and showed the ( E) isomer to be 9.1 kJ mol -1 more stable than the ( Z) isomer.

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

    International Nuclear Information System (INIS)

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

    2012-01-01

    Introduction: 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). Methods: 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. Results: Compound [ 18 F]4 was obtained from precursor compound 3 with an average specific activity of 16 GBq/μmol within 45 min 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. Conclusion: An efficient synthesis for [ 18 F]4 was established. In vivo characteristics were determined and demonstrated the pharmacokinetic behaviour of [ 18 F]4.

  14. An efficient synthesis of D-galactose-based multivalent neoglycoconjugates

    Energy Technology Data Exchange (ETDEWEB)

    Andrade, S.F. de; Souza Filho, J.D. de [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Inst. de Ciencias Exatas. Dept. de Quimica; Alves, Ricardo J., E-mail: ricardodylan@farmacia.ufmg.br [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Fac. de Farmacia; Figueiredo, Rute C. [Universidade Federal de Ouro Preto (UFOP), MG (Brazil)

    2012-11-15

    In this work, the synthesis of dimeric, trimeric and tetrameric D-galactose-based neoglycoconjugates is reported. The monosaccharide ligand was prepared in 5 straightforward steps from D-galactose using the Doebner modification of the Knoevenagel reaction for chain elongation. The ligand was coupled to 1,4-butanediamine, tris-(2-ethylamino)amine, pentaerythrityltetramine and PAMAM dendrimers (1,4-butanodiamine core G0 and 1,12-dodecanediamine core G0). The unprotected glycodendrimers were purified by size-exclusion chromatography (SEC). This was the only step in which a chromatographic method was employed throughout the synthetic route. This is a new and efficient strategy for the preparation of neoglycoconjugates. (author)

  15. Knorr-Rabe partial reduction of pyrroles: Application to the synthesis of indolizidine alkaloids

    Directory of Open Access Journals (Sweden)

    Ryan John H

    2008-01-01

    Full Text Available Abstract Background The Birch reduction of electron rich pyrroles does not occur readily. However, dissolving metal reduction with zinc under acidic conditions gives 3-pyrrolines (2,5-dihydropyrroles in reasonable yield. This dissolving metal reduction was first reported by Knorr and Rabe in 1901 but since then has only been reported for the reduction of electron rich pyrroles. Results The partial reduction of bicyclic α-ketopyrrole derivatives has been performed under dissolving metal conditions with zinc and hydrochloric acid to give excellent yields of hexahydroindolizidines. This reduction method has been utilised for the diastereoselective synthesis of 5-alkylindolizidines and the stereoselectivity obtained is opposite to that of catalytic hydrogenation. Conclusion An efficient stereoselective synthesis of indolizidine alkaloids has been developed from α-ketopyrrole intermediates using a modified version of Knorr and Rabe's pyrrole reduction.

  16. Visible-Light-Initiated Na2-Eosin Y Catalyzed Highly Regio- and Stereoselective Difunctionalization of Alkynes with Alkyl Bromides.

    Science.gov (United States)

    Wang, Kuai; Meng, Ling-Guo; Wang, Lei

    2016-08-19

    A highly regioselective and stereoselective addition of alkyl bromides (amino-brominated aromatic β,β-dicyanoalkenes) to arylacetylenes by photoredox catalysis was developed. This difunctionalization of arylacetylenes was accomplished under ambient and metal-free conditions to produce alkenyl bromides in high efficiency with a wide range of group tolerance.

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

    Science.gov (United States)

    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.

  18. Highly Stereoselective Gold-Catalyzed Coupling of Diazo Reagents and Fluorinated Enol Silyl Ethers to Tetrasubstituted Alkenes.

    Science.gov (United States)

    Liao, Fu-Min; Cao, Zhong-Yan; Yu, Jin-Sheng; Zhou, Jian

    2017-02-20

    We report a highly stereoselective synthesis of all-carbon or fluorinated tetrasubstituted alkenes from diazo reagents and fluorinated enol silyl ethers, using C-F bond as a synthetic handle. Cationic Au I catalysis plays a key role in this reaction. Remarkable fluorine effects on the reactivity and selectivity was also observed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Regio- and stereoselective carbometallation reactions of N-alkynylamides and sulfonamides

    Directory of Open Access Journals (Sweden)

    Yury Minko

    2013-03-01

    Full Text Available The carbocupration reactions of heterosubstituted alkynes allow the regio- and stereoselective formation of vinyl organometallic species. N-Alkynylamides (ynamides are particularly useful substrates for the highly regioselective carbocupration reaction, as they lead to the stereodefined formation of vinylcopper species geminated to the amide moiety. The latter species are involved in numerous synthetically useful transformations leading to valuable building blocks in organic synthesis. Here we describe in full the results of our studies related to the carbometallation reactions of N-alkynylamides.

  20. An efficient one-pot synthesis of carbazole fused benzoquinolines ...

    Indian Academy of Sciences (India)

    KRIPALAYA RATHEESH ARYA

    2018-03-28

    org/ 10.1007/ ..... 1(a-d). 2. 3(a-d). 120°C. 1,3 a: R1 = R2 = R3 = H b: R1 = CH3, R2 = R3 = H c: R1 = R2 = H ..... moted green Friedländer synthesis: a versatile new malic ... and Curini M 2011 An alternative quinoline synthesis by.

  1. Highly regio- and diastereoselective, acidic clay supported intramolecular nitrile oxide-alkene cycloaddition on D-ribose derived nitriles: an efficient synthetic route to isoxazoline fused five and six membered carbocycles.

    Science.gov (United States)

    Panda, Amarendra; Das, Sulagna; Pal, Shantanu

    2014-10-29

    An efficient synthetic route to isoxazoline fused carbocycles from carbohydrate scaffolds that comprise of free hydroxyl group(s) is described with high regio- and stereoselectivity. Montmorillonite K-10/chloramine T oxidation and in situ intramolecular nitrile oxide-alkene cycloaddition (INOC) of D-ribose derived oximes have been developed for the diversity oriented synthesis of isoxazoline fused five and six membered carbocycles. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Nickel nanoparticles: A highly efficient catalyst for one pot synthesis ...

    Indian Academy of Sciences (India)

    and KANIKA VIJ. Department of Chemistry, University of Delhi, Delhi 110 007, India ... Keywords. PVP-stabilized Ni nanoparticles; ethylene glycol; tetraketones; biscoumarins; ... ing interest in using nickel nanoparticles in organic synthesis ...

  3. Simple, Efficient and Green Synthesis of Oximes under Ultrasound ...

    African Journals Online (AJOL)

    NICO

    Faculty of Chemistry, Bu-Ali Sina University, Hamadan 65174, Iran. ... The condensation of aldehydes and ketones with hydroxylamine hydrochloride gives oximes in 81–95 ... Oximes are important in organic synthesis not only for protec-.

  4. Enzymatic biodiesel synthesis. Key factors affecting efficiency of the process

    Energy Technology Data Exchange (ETDEWEB)

    Szczesna Antczak, Miroslawa; Kubiak, Aneta; Antczak, Tadeusz; Bielecki, Stanislaw [Institute of Technical Biochemistry, Faculty of Biotechnology and Food Sciences, Technical University of Lodz, Stefanowskiego 4/10, 90-924 Lodz (Poland)

    2009-05-15

    Chemical processes of biodiesel production are energy-consuming and generate undesirable by-products such as soaps and polymeric pigments that retard separation of pure methyl or ethyl esters of fatty acids from glycerol and di- and monoacylglycerols. Enzymatic, lipase-catalyzed biodiesel synthesis has no such drawbacks. Comprehension of the latter process and an appreciable progress in production of robust preparations of lipases may soon result in the replacement of chemical catalysts with enzymes in biodiesel synthesis. Engineering of enzymatic biodiesel synthesis processes requires optimization of such factors as: molar ratio of substrates (triacylglycerols: alcohol), temperature, type of organic solvent (if any) and water activity. All of them are correlated with properties of lipase preparation. This paper reports on the interplay between the crucial parameters of the lipase-catalyzed reactions carried out in non-aqueous systems and the yield of biodiesel synthesis. (author)

  5. An efficient domino one-pot synthesis of novel spirofuran ...

    Indian Academy of Sciences (India)

    AFSHIN YAZDANI-ELAH-ABADI

    Abstract. A simple and convenient multi-component domino reaction has been described for the synthesis of novel ... interest due to their pharmaceutical and biological activ- ..... We gratefully acknowledge financial support from the Research.

  6. On synthesis and optimization of steam system networks. 1. Sustained boiler efficiency

    CSIR Research Space (South Africa)

    Majozi, T

    2010-08-01

    Full Text Available situations. This paper presents a process integration technique for network synthesis using conceptual and mathematical analysis without compromising boiler efficiency. It was found that the steam flow rate to the HEN could be reduced while maintaining boiler...

  7. Stereoselective Preparation of N-Alkyl Dipeptide Analogues via Dynamic Kinetic Resolution of α-Halo Acyl Amino Esters

    International Nuclear Information System (INIS)

    Shin, Eun Kyoung; Chang, Ji Yeon; Kim, Hyun Jung; Kim, Yong Tae; Park, Yong Sun

    2006-01-01

    We have shown that dynamic kinetic resolution of α-bromo and α-chloro amides in nucleophilic substitution reaction can be successfully applied towards the preparation of various N-terminal functionalized dipeptide analogues. The stereochemical aspects of the results showed that stereoselectivity depends critically on the structures of amine nucleophiles. This mild and practical method can be run on a multi-gram scale without any special precautions and should be applicable to stereoselective syntheses of various peptidomimetics. Extension of this synthetic methodology to dynamic resolution of N-(α-haloacetyl) peptides in the stereospecific nucleophilic substitution (S N 2) could be an attractive synthetic strategy for asymmetric syntheses of peptide analogues. Recently it has been shown from our group that the chiral information of adjacent amino acid residue is efficiently transferred to the new C-N bond formation at α-halo carbon center for asymmetric syntheses of di-, tri- and tetrapeptide analogues. The α-halo stereogenic center of undergoes rapid epimerization in the presence of diisopropylethylamine (DIEA) and tetrabutylammonium iodide (TBAI), and (αS) reacts with the nucleophile preferentially to provide the dipeptide analogue (αR). The mechanistic investigation showed that this is a case of dynamic kinetic resolution, in which the stereoselectivity is determined by the difference in the diastereomeric transition state energies for the reaction with the nucleophiles. Herein we describe our recent progress to extend the scope of the methodology to stereoselective preparation of N-terminal functionalized dipeptide analogues with various amine nucleophiles

  8. An Efficient, Green Chemical Synthesis of the Malaria Drug ...

    African Journals Online (AJOL)

    Results : A green-chemical synthesis of piperaquine is described that proceeds in 92 – 93 % overall yield. ... Keywords: ACTs, Dihydroartemisinin Piperaquine, Dihydroartemisinin, Green Chemistry, Malaria, ..... Mathers CD, Ezzati M, Lopez AD. ... Medicines Programme [Homepage on the Internet]. Geneva ... An Alternative.

  9. Highly Efficient Method for Solvent-Free Synthesis of Diarylmethane ...

    African Journals Online (AJOL)

    NICO

    2011-02-25

    Feb 25, 2011 ... aFaculty of Chemistry, Bu-Ali Sina University, P.O. Box 651783868, Hamedan, Iran. ... Arylmethanes are useful compounds in organic synthesis and industry1 ... ketones,9,10 catalytic condensation of the Grignard reagent with.

  10. Effective and efficient FPGA synthesis through general functional decomposition

    NARCIS (Netherlands)

    Jozwiak, L.; Slusarczyk, A.S.; Chojnacki, A.

    2003-01-01

    In this paper, a new information-driven circuit synthesis method is discussed that targets LUT-based FPGAs and FPGA-based reconfigurable system-on-a-chip platforms. The method is based on the bottom–up general functional decomposition and theory of information relationship measures that we

  11. Enantiomeric metabolic interactions and stereoselective human methadone metabolism.

    Science.gov (United States)

    Totah, Rheem A; Allen, Kyle E; Sheffels, Pamela; Whittington, Dale; Kharasch, Evan D

    2007-04-01

    Methadone is administered as a racemate, although opioid activity resides in the R-enantiomer. Methadone disposition is stereoselective, with considerable unexplained variability in clearance and plasma R/S ratios. N-Demethylation of methadone in vitro is predominantly mediated by cytochrome P450 CYP3A4 and CYP2B6 and somewhat by CYP2C19. This investigation evaluated stereoselectivity, models, and kinetic parameters for methadone N-demethylation by recombinant CYP2B6, CYP3A4, and CYP2C19, and the potential for interactions between enantiomers during racemate metabolism. CYP2B6 metabolism was stereoselective. CYP2C19 was less active, and stereoselectivity was opposite that for CYP2B6. CYP3A4 was not stereoselective. With all three isoforms, enantiomer N-dealkylation rates in the racemate were lower than those of (R)-(6-dimethyamino-4,4-diphenyl-heptan-3-one) hydrochloride (R-methadone) or (S)-(6-dimethyamino-4,4-diphenyl-heptan-3-one) hydrochloride (S-methadone) alone, suggesting an enantiomeric interaction and mutual metabolic inhibition. For CYP2B6, the interaction between enantiomers was stereoselective, with S-methadone as a more potent inhibitor of R-methadone N-demethylation than R-of S-methadone. In contrast, enantiomer interactions were not stereoselective with CYP2C19 or CYP3A4. For all three cytochromes P450, methadone N-demethylation was best described by two-site enzyme models with competitive inhibition. There were minor model differences between cytochromes P450 to account for stereoselectivity of metabolism and enantiomeric interactions. Changes in plasma R/S methadone ratios observed after rifampin or troleandomycin pretreatment in humans in vivo were successfully predicted by CYP2B6- but not CYP3A4-catalyzed methadone N-demethylation. CYP2B6 is a predominant catalyst of stereoselective methadone metabolism in vitro. In vivo, CYP2B6 may be a major determinant of methadone metabolism and disposition, and CYP2B6 activity and stereoselective metabolic

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

    Science.gov (United States)

    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.

  13. Efficient Asymmetric Synthesis of S,S-2-methylsulfanyl-2-methylsulfinyl-1-indanone

    OpenAIRE

    Derisvaldo Rosa Paiva; Roberto da Silva Gomes

    2013-01-01

    Diastereoselective synthesis of SS-2-methylsulfanyl-2-methylsulfinyl-1-indanol by reduction of SS-2-methylsulfanyl-2-methylsulfinyl-1-indanone optically enriched demonstrating to be highly efficiency using the sulfanyl group as asymmetric induction control agent during an addition reaction to carbonyl group.The 2-methylsulfinyl-1-indanone was obtained for the first time in one unique step without further oxidation steps. The synthesis of SR, SS of 2-methylsulphinyl-1-indanone optically enrich...

  14. Significance and challenges of stereoselectivity assessing methods in drug metabolism

    Directory of Open Access Journals (Sweden)

    Zhuowei Shen

    2016-02-01

    Full Text Available Stereoselectivity in drug metabolism can not only influence the pharmacological activities, tolerability, safety, and bioavailability of drugs directly, but also cause different kinds of drug–drug interactions. Thus, assessing stereoselectivity in drug metabolism is of great significance for pharmaceutical research and development (R&D and rational use in clinic. Although there are various methods available for assessing stereoselectivity in drug metabolism, many of them have shortcomings. The indirect method of chromatographic methods can only be applicable to specific samples with functional groups to be derivatized or form complex with a chiral selector, while the direct method achieved by chiral stationary phases (CSPs is expensive. As a detector of chromatographic methods, mass spectrometry (MS is highly sensitive and specific, whereas the matrix interference is still a challenge to overcome. In addition, the use of nuclear magnetic resonance (NMR and immunoassay in chiral analysis are worth noting. This review presents several typical examples of drug stereoselective metabolism and provides a literature-based evaluation on current chiral analytical techniques to show the significance and challenges of stereoselectivity assessing methods in drug metabolism.

  15. Stereoselectivity of presynaptic autoreceptors modulating dopamine release

    International Nuclear Information System (INIS)

    Arbilla, S.; Langer, S.Z.

    1981-01-01

    The effects of the (R)- and (S)-enantiomers of sulpiride and butaclamol were studied on the spontaneous and field stimulation-evoked release of total radioactivity from slices of rabbit caudate nucleus prelabelled with [ 3 H]dopamine. (S)-Sulpiride in concentrations ranging from 0.01-1μM enhanced the electrically evoked release of [ 3 H]dopamine while (R)-sulpiride was 10 times less potent than (S)-sulpiride. Exposure to (S)-butaclamol (0.1-1 μM) but not to (R)-butaclamol (0.1-10μM) enhanced the field-stimulated release of [ 3 H]dopamine. The facilitatory effects of (S)- and (R)-sulpiride and (S)-butaclamol on the stimulated release of the labelled neurotransmitter were observed under conditions in which these drugs did not modify the spontaneous outflow of radioactivity. Only the active enantiomers of sulpiride and butaclamol antagonized the inhibition by apomorphine (1μM) of the stimulated release of [ 3 H]dopamine. Our results indicate that the presynaptic inhibitory dopamine autoreceptors modulating the stimulation-evoked release of [ 3 H]dopamine in the caudate nucleus are, like the classical postsynaptic dopamine receptors, chemically stereoselective. (Auth.)

  16. Palladium-catalyzed aerobic regio- and stereo-selective olefination reactions of phenols and acrylates via direct dehydrogenative C(sp2)-O cross-coupling.

    Science.gov (United States)

    Wu, Yun-Bin; Xie, Dan; Zang, Zhong-Lin; Zhou, Cheng-He; Cai, Gui-Xin

    2018-04-26

    An efficient olefination protocol for the oxidative dehydrogenation of phenols and acrylates has been achieved using a palladium catalyst and O2 as the sole oxidant. This reaction exhibits high regio- and stereo-selectivity (E-isomers) with moderate to excellent isolated yields and a wide substrate scope (32 examples) including ethyl vinyl ketone and endofolliculina.

  17. Stereoselective inhibition of thromboxane-induced coronary vasoconstriction by 1,4-dihydropyridine calcium channel antagonists

    International Nuclear Information System (INIS)

    Eltze, M.; Boer, R.; Sanders, K.H.; Boss, H.; Ulrich, W.R.; Flockerzi, D.

    1990-01-01

    The biological activity of the (+)-S- and (-)-R-enantiomers of niguldipine, of the (-)-S- and (+)-R-enantiomers of felodipine and nitrendipine, and of rac-nisoldipine and rac-nimodipine was investigated in vitro and in vivo. Inhibition of coronary vasoconstriction due to the thromboxane A2 (TxA2)-mimetic U-46619 in guinea pig Langendorff hearts, displacement of (+)-[ 3 H]isradipine from calcium channel binding sites of guinea pig skeletal muscle T-tubule membranes, and blood pressure reduction in spontaneously hypertensive rats were determined. The enantiomers were obtained by stereoselective synthesis. Cross-contamination was less than 0.5% for both S- and R-enantiomers of niguldipine and nitrendipine and less than 1% for those of felodipine. From the doses necessary for a 50% inhibition of coronary vasoconstriction, stereoselectivity ratios for (+)-(S)-/(-)-(R)-niguldipine, (-)-(S)-/(+)-(R)-felodipine, and (-)-(S)-/(+)-(R)-nitrendipine of 28, 13, and 7, respectively, were calculated. The potency ratio rac-nisoldipine/rac-nimodipine was 3.5. Ratios obtained from binding experiments and antihypertensive activity were (+)-(S)-/(-)-(R)-niguldipine = 45 and 35, (-)-(S)-/(+)-(R)-felodipine = 12 and 13, (-)-(S)-/(+)-(R)-nitrendipine = 8 and 8, and rac-nisoldipine/rac-nimodipine = 8 and 7, respectively. Highly significant correlations were found between the in vitro potency of the substances to prevent U-46619-induced coronary vasoconstriction and their affinity for calcium channel binding sites as well as their antihypertensive activity

  18. Ozone Synthesis Efficiency Upgrading in the Pulsed Point-to-Plane Gas Discharge

    International Nuclear Information System (INIS)

    Golota, V.I.; Zavada, L.M.; Kotyukov, O.V.; Polyakov, A.V.; Pugach, S.G.

    2006-01-01

    Results are reported from the studies into electrodynamic characteristics of the barrierless point-to-plane gas discharge as a HV pulse of positive polarity is applied to the point electrode. The efficiency of ozone synthesis has been determined as a function of the length and repetition frequency of the HV pulse. It has been demonstrated that the electrodynamic characteristics of the discharge and the efficiency of ozone synthesis in oxygen-containing gas mixtures essentially depend on the parameters of HV power supply. The HV switch HTS-300 (BEHLKE Electronic GmbH) was used for HV pulse shaping

  19. catalysed indolylation and pyrrolylation of isatins: Efficient synthesis ...

    Indian Academy of Sciences (India)

    Abstract. An efficient and cheap synthetic approach to 3,3-di(indolyl)oxindoles and 3,3-di(pyrrolyl) oxindoles has been developed via Zn(OTf)2 catalysed indolylation and pyrrolylation of isatins. A preliminary biochemical assay of the synthesized molecules in rodent models were performed to estimate the serum glutamate ...

  20. Total synthesis of mycalamide A.

    Science.gov (United States)

    Sohn, Jeong-Hun; Waizumi, Nobuaki; Zhong, H Marlon; Rawal, Viresh H

    2005-05-25

    This communication describes a concise and efficient total synthesis of mycalamide A by the convergent coupling of pederic acid unit with the mycalamine unit. The left-half, (+)-7-benzoylpederic acid, was synthesized from (2R,3R)-3-methylpent-4-en-2-ol in seven steps and 34.6% overall yield through a route that features a one-step Pd(II)-catalyzed tandem Wacker/Heck cyclization reaction to prepare the tetrahydropyran ring system. The right-half, the mycalamine unit, was synthesized in 21 steps and 10.5% overall yield from diethyl d-tartrate. Effective, stereoselective methods were developed for the assembly of the two parts to yield either mycalamide A or C(10)-epi-mycalamide A.

  1. Novel and Efficient Synthesis of the Promising Drug Candidate Discodermolide

    Science.gov (United States)

    2010-02-01

    of its production may require its wide use as a livestock antibiotic , a market that seems to have disappeared. Therefore, as a purely practical...building block 9. Thus, chiral syn, anti stereotriad building blocks, useful for the preparation of polypropionate antibiotics , may be efficiently accessed... antibiotics that are used in human and veterinary medicine. In this paper, we illustrate the potential of a deconstruction-reconstruction strategy for the

  2. Sulfated polyborate: A mild, efficient catalyst for synthesis of N-tert ...

    Indian Academy of Sciences (India)

    Rapid, efficient and inexpensive method for synthesis of N-tert-butyl/N-trityl protected amides via Ritter reaction of nitriles with tertiary alcohols in the presence of a sulfated polyborate catalyst under solvent-free conditions is described. The catalyst has the advantage of Lewis as well as Bronsted acidity and recyclability ...

  3. Boric acid as a mild and efficient catalyst for one-pot synthesis of 1

    Indian Academy of Sciences (India)

    Abstract. An efficient green chemistry method has been developed for the synthesis of 1-amidoalkyl-2-naphthol derivatives via a one-pot three-component condensation of 2-naphthol, aldehydes and amide in the presence of boric acid as a mild catalyst.

  4. Tannic acid Catalyzed an Efficient Synthesis of 2,4,5-Triaryl-1H-Imidazole

    Directory of Open Access Journals (Sweden)

    Shitole Nana Vikram

    2013-05-01

    Full Text Available Tannic acid (C76H52O46 has been found to be an efficient catalyst for one-pot synthesis of 2,4,5-triaryl substituted imidazoles by the reaction of an arylaldehyde, benzyl/benzoin and an ammonium acetate. The short reaction time and excellent yields making this protocol practical and economically attractive.

  5. Simple and efficient Knoevenagel synthesis of (E)-2-((1H-indol-3-yl ...

    Indian Academy of Sciences (India)

    Simple and efficient Knoevenagel synthesis of (E)-2-((1H-indol-3-yl) ... there has been a growing interest in Knoevenagel prod- ucts because many of them have ..... providing financial support and to the authorities of. Jawaharlal Nehru ...

  6. An Efficient Green Synthesis of 3-Amino-1 H -chromenes Catalyzed ...

    African Journals Online (AJOL)

    An Efficient Green Synthesis of 3-Amino-1 H -chromenes Catalyzed by ZnO Nanoparticles Thin-film. ... South African Journal of Chemistry ... The mild reaction conditions, reusability of the catalyst, easy work-up and high yields of products make the present protocol sustainable and advantageous compared to conventional ...

  7. Principles of asymmetric synthesis

    CERN Document Server

    Gawley, Robert E; Aube, Jeffrey

    2012-01-01

    The world is chiral. Most of the molecules in it are chiral, and asymmetric synthesis is an important means by which enantiopure chiral molecules may be obtained for study and sale. Using examples from the literature of asymmetric synthesis, this book presents a detailed analysis of the factors that govern stereoselectivity in organic reactions. After an explanation of the basic physical-organic principles governing stereoselective reactions, the authors provide a detailed, annotated glossary of stereochemical terms. A chapter on "Practical Aspects of Asymmetric Synthesis" provides a critical overview of the most common methods for the preparation of enantiomerically pure compounds, techniques for analysis of stereoisomers using chromatographic, spectroscopic, and chiroptical methods. The authors then present an overview of the most important methods in contemporary asymmetric synthesis organized by reaction type. Thus, there are four chapters on carbon-carbon bond forming reactions, one chapter on reductions...

  8. Regio- and stereoselective hydrosilylation of immobilized terminal alkynes

    DEFF Research Database (Denmark)

    Pedersen, Palle Jacob; Henriksen, Jonas; Gotfredsen, Charlotte Held

    2008-01-01

    Regio- and stereoselective hydrosilylation of terminal alkynes on solid support using diisopropyl hydrosilanes yielding b-(E)-vinyl silanes with excellent selectivity is reported. The hydrosilylation is catalyzed by Pt(DVDS)/P(iBuNCH2CH2)3N (DVDS = 1,3-divinyl-1,1,3,3-tetramethyl-disiloxane), in ...

  9. High stereoselectivity on low temperature Diels-Alder reactions

    Directory of Open Access Journals (Sweden)

    Invernize Paulo

    2005-12-01

    Full Text Available Abstract We have found that some of the usually poor dienophiles (2-cycloenones can undergo Diels-Alder reaction at -78°C with unusually high stereoselectivity in the presence of niobium pentachloride as a Lewis acid catalyst. A remarkable difference in reaction rates for unsubstituted and α- or β-methyl substituted 2-cycloenones was also observed.

  10. Nitrocyclopropanes: synthesis and properties

    Energy Technology Data Exchange (ETDEWEB)

    Averina, Elena B; Yashin, N V; Kuznetsova, Tamara S; Zefirov, Nikolai S [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation)

    2009-10-31

    State-of-the-art data on the methods of synthesis, properties and transformations of nitro- and- dinitrocyclopropanes of different structure is generalized and described systematically. The attention is focused on stereoselective cyclopropanation methods, new approaches to the synthesis of natural products and their synthetic analogues with diversified biological activities, in particular, of aminocyclopropane acids based on nitrocyclopropanes, and the formation of structures of energetic compounds.

  11. Simple and Efficient Procedure for Synthesis of N'-Arylamidines Using Trimethylaluminum

    International Nuclear Information System (INIS)

    Korbad, Balaji L.; Lee, Sanghyeup

    2013-01-01

    In conclusion, we have developed simple and efficient procedure for the synthesis of N'-arylamidines using tri-methylaluminum, nitriles and aryl amines under mild condition. Aliphatic, aromatic nitriles were reacted well with a variety of aromatic amine to afford corresponding amidines in good to high yields. Amidines are an important class of compounds that have wide range of application in the fields of catalyst design, material science, medicinal chemistry and also shown the promising anti-inflammatory and analgesic activity. They are valuable synthons for synthesis of various heterocyclic compounds. In addition, recent studies have demonstrated their capacity to fix carbon dioxide

  12. Efficient Asymmetric Synthesis of S,S-2-methylsulfanyl-2-methylsulfinyl-1-indanone

    Directory of Open Access Journals (Sweden)

    Derisvaldo Rosa Paiva

    2013-05-01

    Full Text Available Diastereoselective synthesis of SS-2-methylsulfanyl-2-methylsulfinyl-1-indanol by reduction of SS-2-methylsulfanyl-2-methylsulfinyl-1-indanone optically enriched demonstrating to be highly efficiency using the sulfanyl group as asymmetric induction control agent during an addition reaction to carbonyl group.The 2-methylsulfinyl-1-indanone was obtained for the first time in one unique step without further oxidation steps. The synthesis of SR, SS of 2-methylsulphinyl-1-indanone optically enriched in good yield and good enantiomeric excess determined by nuclear magnetic resonance technique employing the Kagan reagent as chiral shift agent.

  13. Highly Efficient Procedure for the Synthesis of Fructone Fragrance Using a Novel Carbon based Acid

    Directory of Open Access Journals (Sweden)

    Xuezheng Liang

    2010-08-01

    Full Text Available The novel carbon based acid has been synthesized via one-step hydrothermal carbonization of furaldehyde and hydroxyethylsulfonic acid. A highly efficient procedure for the synthesis of fructone has been developed using the novel carbon based acid. The results showed that the catalyst possessed high activity for the reaction, giving a yield of over 95%. The advantages of high activity, stability, reusability and low cost for a simple synthesis procedure and wide applicability to various diols and β-keto esters make this novel carbon based acid one of the best choices for the reaction.

  14. An efficient synthesis and spectroscopic characterization of Schiff bases containing 9,10-anthracenedione moiety

    Directory of Open Access Journals (Sweden)

    Fareed Ghulam

    2013-01-01

    Full Text Available A new method has been developed for the synthesis of novel Schiff bases containg anthraquinone moiety using dodeca-Tungstosilicic acid/P2O5 under solvent free conditions at room temperature. The reaction was completed in 1-3 minutes with excellent yields. This method was found to be more efficient, easy and hazardous free for the synthesis of azomethines. The development of these type of methadologies in synthetic chemistry may contribute to green chemistry. The structures of synthesized novel Schiff bases was elucidated using 1H-NMR, 13C-NMR, LCMS, FTIR and CHN analysis.

  15. Stereoselective synthesis of 2,3-disubstituted dihydrobenzofuran ...

    Indian Academy of Sciences (India)

    of these natural products are constituents of traditional medicines and ... prevalent in many of the natural products. All these .... milder trifluoroacetic acid failed to promote the alkyne .... happens in such a way so as to minimize steric repul-.

  16. Stereoselective Synthesis of 2,3-Disubstituted Dihydrobenzofuran ...

    Indian Academy of Sciences (India)

    gharpure1

    High resolution mass measurements were carried out using Micromass Q-ToF ... and combined organic layer was washed with brine and dried (anhyd. Na2SO4). Evaporation of the solvent and purification of the residue on a silica gel column using ethyl .... furnished the benzofuran 6c (63 mg, 60 %) as a viscous liquid.

  17. Efficient Synthesis and Bioactivity of Novel Triazole Derivatives.

    Science.gov (United States)

    Hu, Boyang; Zhao, Hanqing; Chen, Zili; Xu, Chen; Zhao, Jianzhuang; Zhao, Wenting

    2018-03-21

    Triazole pesticides are organic nitrogen-containing heterocyclic compounds, which contain 1,2,3-triazole ring. In order to develop potential glucosamine-6-phosphate synthase (GlmS) inhibitor fungicides, forty compounds of triazole derivatives were synthesized in an efficient way, thirty nine of them were new compounds. The structures of all the compounds were confirmed by high resolution mass spectrometer (HRMS), ¹H-NMR and 13 C-NMR. The fungicidal activities results based on means of mycelium growth rate method indicated that some of the compounds exhibited good fungicidal activities against P. CapasiciLeonian , Sclerotinia sclerotiorum (Lib.) de Bary, Pyricularia oryzae Cav. and Fusarium oxysporum Schl. F.sp. vasinfectum (Atk.) Snyd. & Hans. at the concentration of 50 µg/mL, especially the inhibitory rates of compounds 1-d and 1-f were over 80%. At the same time, the preliminary studies based on the Elson-Morgan method indicated that the compounds exhibited some inhibitory activity toward glucosamine-6-phosphate synthase (GlmS). These compounds will be further studied as potential antifungal lead compounds. The structure-activity relationships (SAR) were discussed in terms of the effects of the substituents on both the benzene and the sugar ring.

  18. Efficient Synthesis and Bioactivity of Novel Triazole Derivatives

    Directory of Open Access Journals (Sweden)

    Boyang Hu

    2018-03-01

    Full Text Available Triazole pesticides are organic nitrogen-containing heterocyclic compounds, which contain 1,2,3-triazole ring. In order to develop potential glucosamine-6-phosphate synthase (GlmS inhibitor fungicides, forty compounds of triazole derivatives were synthesized in an efficient way, thirty nine of them were new compounds. The structures of all the compounds were confirmed by high resolution mass spectrometer (HRMS, 1H-NMR and 13C-NMR. The fungicidal activities results based on means of mycelium growth rate method indicated that some of the compounds exhibited good fungicidal activities against P. CapasiciLeonian, Sclerotinia sclerotiorum (Lib. de Bary, Pyricularia oryzae Cav. and Fusarium oxysporum Schl. F.sp. vasinfectum (Atk. Snyd. & Hans. at the concentration of 50 µg/mL, especially the inhibitory rates of compounds 1-d and 1-f were over 80%. At the same time, the preliminary studies based on the Elson-Morgan method indicated that the compounds exhibited some inhibitory activity toward glucosamine-6-phosphate synthase (GlmS. These compounds will be further studied as potential antifungal lead compounds. The structure-activity relationships (SAR were discussed in terms of the effects of the substituents on both the benzene and the sugar ring.

  19. One-pot synthesis of 2H-pyrans by indium(III) chloride-catalyzed reactions. efficient synthesis of pyranocoumarins, pyranophenalenones, and pyranoquinolinones

    International Nuclear Information System (INIS)

    Lee, Yong Rok; Kim, Do Hoon; Shim, Jae Jin; Kim, Seog K.; Park, Jung Hag; Cha, Jin Soon; Lee, Chong Soon

    2002-01-01

    An efficient synthesis of 2H-pyrans is achieved by indium (III) chloride-catalyzed reactions of 1,3-dicarbonyl compounds with a variety of α.β-unsaturated aldehydes in moderates yields. This method has been applied to the synthesis of pyranocoumarins, pyranophenaleneones, and pyranoquinolinone alkaloids

  20. One-pot synthesis of 2H-pyrans by indium(III) chloride-catalyzed reactions. efficient synthesis of pyranocoumarins, pyranophenalenones, and pyranoquinolinones

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Yong Rok; Kim, Do Hoon; Shim, Jae Jin; Kim, Seog K.; Park, Jung Hag; Cha, Jin Soon; Lee, Chong Soon [Yeungnam Univ., Kyongsan (Korea, Republic of)

    2002-08-01

    An efficient synthesis of 2H-pyrans is achieved by indium (III) chloride-catalyzed reactions of 1,3-dicarbonyl compounds with a variety of {alpha}.{beta}-unsaturated aldehydes in moderates yields. This method has been applied to the synthesis of pyranocoumarins, pyranophenaleneones, and pyranoquinolinone alkaloids.

  1. Improved stereoselective bioreduction of t-butyl 6-cyano-(5R)-hydroxy-3-oxohexanoate by Rhodotorula glutinis through heat treatment.

    Science.gov (United States)

    Luo, Xi; Wang, Ya-Jun; Zheng, Yu-Guo

    2016-11-01

    Optically pure t-butyl 6-cyano-(3R, 5R)-dihydroxyhexanoate ((R)-1b) is the key precursor for atorvastatin calcium, the most widely used cholesterol-lowering drug. In this work, a strain ZJB-09224 capable of asymmetrically reducing t-butyl 6-cyano-(5R)-hydroxy-3-oxohexanoate (1a) to corresponding optically pure (R)-1b was successfully isolated from soil sample, identified belonging to Rhodotorula glutinis based on the morphology, physiological tests, and the 18S rDNA sequence analysis. It was found that heat treatment of cell suspension at 45 °C for 25 Min significantly improved R. glutinis ZJB-09224 stereoselectivity. The asymmetric bioreduction of 1a was most efficient at pH 7.5, 35 °C, 50 mM (15.0 g L -1 ) substrate concentration, 40.0 g DCW L -1 cell loading size, 0.54 M (60.0 g L -1 ) sodium lactate acting as co-substrate. Under these optimal conditions, 0.046 M (R)-1b was produced with de (diastereomeric excess) value of 99.2% after 40 H conversion. Moreover, R. glutinis ZJB-09224 has a broad substrate spectrum, making it a potential tool for some valuable chiral alcohol pharmaceutical intermediates synthesis. © 2015 International Union of Biochemistry and Molecular Biology, Inc.

  2. Stereoselective phytotoxicity of HCH mediated by photosynthetic and antioxidant defense systems in Arabidopsis thaliana.

    Science.gov (United States)

    Zhang, Qiong; Zhou, Cong; Zhang, Quan; Qian, Haifeng; Liu, Weiping; Zhao, Meirong

    2013-01-01

    Hexachlorocyclohexane (HCH) has been used for plant protection and sanitation world-widely, and its isomers have been detected in water, soil, and air as well as in vegetation. As a sink for lipophilic pollutants, vegetation is very important for the degradation and fate of organic contamination; however, little was known about their phytotoxicity and mechanisms of toxic effect. In this study, the stereoselective phototoxicity of four isomers (α, β, γ, and δ) of HCHs mediated by independent as well as interconnecting systems of photosynthesis and enzymatic antioxidant defense system in Arabidopsis thaliana were assessed. Our results revealed that all the HCHs not only stimulated the activities of catalase (CAT) and peroxidase (POD), but also inhibited the activity of superoxide dismutase (SOD). In photosynthesis system, the photosynthetic efficiency of PSI and PSII were all down regulated. Meanwhile, results from both systems showed that δ-HCH was the most toxic one, while α-HCH the least in Arabidopsis thaliana. For the first time, stereoselective effects of different isomers of HCH in plant were demonstrated. And the results suggest that it requires further research to fully elucidate the environmental toxicity and their mechanisms.

  3. Stereoselective phytotoxicity of HCH mediated by photosynthetic and antioxidant defense systems in Arabidopsis thaliana.

    Directory of Open Access Journals (Sweden)

    Qiong Zhang

    Full Text Available BACKGROUND: Hexachlorocyclohexane (HCH has been used for plant protection and sanitation world-widely, and its isomers have been detected in water, soil, and air as well as in vegetation. As a sink for lipophilic pollutants, vegetation is very important for the degradation and fate of organic contamination; however, little was known about their phytotoxicity and mechanisms of toxic effect. In this study, the stereoselective phototoxicity of four isomers (α, β, γ, and δ of HCHs mediated by independent as well as interconnecting systems of photosynthesis and enzymatic antioxidant defense system in Arabidopsis thaliana were assessed. PRINCIPAL FINDINGS: Our results revealed that all the HCHs not only stimulated the activities of catalase (CAT and peroxidase (POD, but also inhibited the activity of superoxide dismutase (SOD. In photosynthesis system, the photosynthetic efficiency of PSI and PSII were all down regulated. Meanwhile, results from both systems showed that δ-HCH was the most toxic one, while α-HCH the least in Arabidopsis thaliana. CONCLUSIONS: For the first time, stereoselective effects of different isomers of HCH in plant were demonstrated. And the results suggest that it requires further research to fully elucidate the environmental toxicity and their mechanisms.

  4. Visualization of Stereoselective Supramolecular Polymers by Chirality-Controlled Energy Transfer.

    Science.gov (United States)

    Sarkar, Aritra; Dhiman, Shikha; Chalishazar, Aditya; George, Subi J

    2017-10-23

    Chirality-driven self-sorting is envisaged to efficiently control functional properties in supramolecular materials. However, the challenge arises because of a lack of analytical methods to directly monitor the enantioselectivity of the resulting supramolecular assemblies. Presented herein are two fluorescent core-substituted naphthalene-diimide-based donor and acceptor molecules with minimal structural mismatch and they comprise strong self-recognizing chiral motifs to determine the self-sorting process. As a consequence, stereoselective supramolecular polymerization with an unprecedented chirality control over energy transfer has been achieved. This chirality-controlled energy transfer has been further exploited as an efficient probe to visualize microscopically the chirality driven self-sorting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Stereoselective Conversion of Glucosides into Xylosides

    DEFF Research Database (Denmark)

    Pedersen, Martin Jæger

    was preferred because of its novelty and versatility. As proof of concept, the building blocks were applied to the synthesis of oligoxylans. Furthermore, the method proved to be an alternative route for selective equatorial deuterium labeling of D-xylose by stereo retention, whereas radical methods mainly...... in excellent purity. This thesis describes the work on a new preparative synthesis method of D-xylose and D-xylobiose building blocks through carbohydrate interconversion of D-glucose and D-cellobiose. A range of methods for the transformation was investigated and the method of dehydrogenative decarbonylation...

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

    Science.gov (United States)

    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.

  7. Synthesis of (R-Dihydropyridones as Key Intermediates for an Efficient Access to Piperidine Alkaloids

    Directory of Open Access Journals (Sweden)

    Serkos A Haroutounian

    2007-04-01

    Full Text Available The efficient transformation of D-glucal to (2R-hydroxymethyldihydro-pyridinone 5 in seven steps and 35 % overall yield is reported. Dihydropyridone 5 constitutes a versatile chiral building block for the synthesis of various piperidine alkaloids. In this regard, 5 was converted to piperidinol 13 and piperidinone 15, that may be further elaborated for the syntheses of (+-desoxoprosophylline (1 and deoxymannojirimycin (3 or D-mannolactam (4, respectively.

  8. An Efficient Method for the N-Bromosuccinimide Catalyzed Synthesis of Indolyl-Nitroalkanes

    Directory of Open Access Journals (Sweden)

    Ching-Fa Yao

    2009-10-01

    Full Text Available An efficient and practical method for the synthesis of indolyl-nitroalkane derivatives catalyzed by N-bromosuccinimide is described. The generality of this method was demonstrated by synthesizing an array of diverse 3-substituted indole derivatives by the reaction of different β-nitrostyrenes with various substituted indoles. Simple reaction conditions accompanied by good yields of indolyl-nitroalkanes are the merits of this methodology.

  9. Interspecies In Vitro Evaluation of Stereoselective Protein Binding for 3,4-Methylenedioxymethamphetamine

    Directory of Open Access Journals (Sweden)

    Wan Raihana Wan Aasim

    2017-01-01

    Full Text Available Abuse of 3,4-methylenedioxymethamphetamine (MDMA is becoming more common worldwide. To date, there is no information available on stereoselectivity of MDMA protein binding in humans, rats, and mice. Since stereoselectivity plays an important role in MDMA’s pharmacokinetics and pharmacodynamics, in this study we investigated its stereoselectivity in protein binding. The stereoselective protein binding of rac-MDMA was investigated using two different concentrations (20 and 200 ng/mL in human plasma and mouse and rat sera using an ultrafiltration technique. No significant stereoselectivity in protein binding was observed in both human plasma and rat serum; however, a significant stereoselective binding (p<0.05 was observed in mouse serum. Since the protein binding of MDMA in mouse serum is considerably lower than in humans and rats, caution should be exercised when using mice for in vitro studies involving MDMA.

  10. Highly efficient and eco-friendly gold-catalyzed synthesis of homoallylic ketones

    KAUST Repository

    Gómez-Suárez, Adrián

    2014-08-01

    We report a new catalytic protocol for the synthesis of γ,δ-unsaturated carbonyl units from simple starting materials, allylic alcohols and alkynes, via a hydroxalkoxylation/Claisen rearrangement sequence. This new process is more efficient (higher TON and TOF) and more eco-friendly (increased mass efficiency) than the previous state-of-the-art technique. In addition, this method tolerates both terminal and internal alkynes. Moreover, computational studies have been carried out in order to shed light on how the Claisen rearrangement is initiated. © 2014 American Chemical Society.

  11. Highly efficient and eco-friendly gold-catalyzed synthesis of homoallylic ketones

    KAUST Repository

    Gó mez-Suá rez, Adriá n; Gasperini, Danila; Vummaleti, Sai V. C.; Poater, Albert; Cavallo, Luigi; Nolan, Steven P.

    2014-01-01

    We report a new catalytic protocol for the synthesis of γ,δ-unsaturated carbonyl units from simple starting materials, allylic alcohols and alkynes, via a hydroxalkoxylation/Claisen rearrangement sequence. This new process is more efficient (higher TON and TOF) and more eco-friendly (increased mass efficiency) than the previous state-of-the-art technique. In addition, this method tolerates both terminal and internal alkynes. Moreover, computational studies have been carried out in order to shed light on how the Claisen rearrangement is initiated. © 2014 American Chemical Society.

  12. A mild and efficient procedure for the synthesis of ethers from various alkyl halides

    Directory of Open Access Journals (Sweden)

    Mosstafa Kazemi

    2013-10-01

    Full Text Available A simple, mild and practical procedure has been developed for the synthesis of symmetrical and unsymmetrical ethers by using DMSO, TBAI in the presence of K2CO3. We extended the utility of Potassium carbonate as an efficient base for the preparation of ethers. A wide range of alkyl aryl and dialkyl ethers are synthezied from treatment of aliphatic alcohols and phenols with various alkyl halides in the prescence of efficient base Potassium carbonate. Secondary alkyl halides were easily converted to corresponding ethers in releatively good yields . This is a mild, simple and practical procedure for the preparation of ethers in high yields and suitable times under mild condition.

  13. Endophytic fungi as models for the stereoselective biotransformation of thioridazine.

    Science.gov (United States)

    Borges, Keyller Bastos; Borges, Warley De Souza; Pupo, Mônica Tallarico; Bonato, Pierina Sueli

    2007-12-01

    The stereoselective kinetic biotransformation of thioridazine, a phenothiazine neuroleptic drug, by endophytic fungi was investigated. In general, the sulfur of lateral chain (position 2) or the sulfur of phenothiazinic ring (position 5) were oxidated yielding the major human metabolites thioridazine-2-sulfoxide and thioridazine-5-sulfoxide. The quantity of metabolites biosynthesized varied among the 12 endophytic fungi evaluated. However, mono-2-sulfoxidation occurred in higher ratio and frequency. Among the 12 fungi evaluated, 4 of them deserve prominence for presenting an evidenced stereoselective biotransformation: Phomopsis sp. (TD2), Glomerella cingulata (VA1), Diaporthe phaseolorum (VR4), and Aspergillus fumigatus (VR12). Both enantiomers of thioridazine were consumed by the fungi; however, the 2-sulfoxidation yielded preferentially the R configuration at the sulfur atom.

  14. Evolution of a practical total synthesis of ciguatoxin CTX3C.

    Science.gov (United States)

    Inoue, Masayuki; Hirama, Masahiro

    2004-12-01

    More than 20 000 people suffer annually from ciguatera seafood poisoning in subtropical and tropical regions. The extremely low content of the causative neurotoxins, designated as ciguatoxins, in fish has hampered their isolation, detailed biological study, and preparation of anti-ciguatoxin antibodies for detecting these toxins. Ciguatoxins consist of 12 trans-fused polycyclic ethers, ranging from six- to nine-membered, and include a spirally attached five-membered cyclic ether at one end. The large (3 nm in length) and complicated molecular structure of ciguatoxins has impeded chemists from completing their total synthesis. In 2001, we achieved the first total synthesis of ciguatoxin CTX3C by assembly of four structural fragments. Since then, protocols to combine the fragments have significantly improved in terms of overall stereoselectivity, efficiency, and practicality. In this Account, we describe recently evolved methodologies for the total synthesis of CTX3C.

  15. Stereoselective effects of MDMA on inhibition of monoamine uptake

    International Nuclear Information System (INIS)

    Steele, T.D.; Nichols, D.E.; Yim, G.K.W.

    1986-01-01

    The R(-)-isomers of hallucinogenic phenylisopropylamines are most active, whereas the S(+)-enantiomers of amphetamine (AMPH) and methylenedioxymethamphetamine (MDMA) are more potent centrally. To determine if MDMA exhibits stereoselective effects at the biochemical level that resemble either those of amphetamine or the potent hallucinogen 2,5-dimethoxy-4-methylamphetamine (DOM), the ability of the isomers of MDMA, AMPH and DOM to inhibit uptake of radiolabelled monoamines into synaptosomes was measured. AMPH was more potent than MDMA in inhibiting uptake of 3 H-norepinephrine (NE) into hypothalamic synaptosomes and 3 H-dopamine (DA) into striatal synaptosomes. The S(+)-isomer was more active in each case. MDMA was more potent than AMPH in inhibiting uptake of 3 H-serotonin (5-HT) into hippocampal synaptosomes and exhibited a high degree of stereoselectivity, in favor of the S(+)-isomer. DOM showed only minimal activity in inhibiting uptake of any monoamine (IC 50 > 10 -5 M). These results suggest that MDMA exhibits stereoselective effects similar to those of amphetamine on monoamine uptake inhibition, a parameter that is unrelated to the mechanism of action of the hallucinogen DOM

  16. An Efficient Synthesis of 1-Alkyl-2-phenyl-4-quinolones from 2-Halobenzoic Acids

    International Nuclear Information System (INIS)

    Song, Yoon Ju; Choi, Jin Sun; Lee, Jae In

    2013-01-01

    The present method offers an efficient synthesis of 1-alkyl-2-phenyl-4-quinolones from 2-haloben-zoic acids. It has the advantages with respect to (i) synthesis of 2 equiv of alkynones 5 from 1 equiv of 4,6-pyrimidyl di(2-halobenzoates) 3, (ii) synthesis of versatile 1-alkyl-2-phenyl-4-quinolones in high overall yields, and (iii) use of readily available and cheap starting materials. Therefore, this method could be utilized as a practical synthesis of 1-alkyl-2-phenyl-4-quinolones. Several methods have been developed to synthesize 1-alkyl-2-phenyl-4-quinolones from 2'-substituted acetophenones, anilines, and 2-halobenzoyl chlorides as starting materials. The reaction of N-methylisatoic anhydride with the lithium enolate of an 4'-methoxyacetophenone afforded the 1-methyl-2-phenyl-4-quinolone in a short sequence, but the yield was low. N-(2-Acetylphenyl)benzamides, prepared by Friedel-Crafts acylation of N-phenyl benzamides with acetyl chloride or benzoylation of 2'-aminoacetophenones with benzoyl chlorides,8 were cyclized with potassium t-butoxide to yield 2-aryl-4-quinolones, which were further alkylated with alkyl iodides to give 1-alkyl-2-aryl-4-quinolones

  17. An Efficient Synthesis of 1-Alkyl-2-phenyl-4-quinolones from 2-Halobenzoic Acids

    Energy Technology Data Exchange (ETDEWEB)

    Song, Yoon Ju; Choi, Jin Sun; Lee, Jae In [Duksung Women' s Univ., Seoul (Korea, Republic of)

    2013-10-15

    The present method offers an efficient synthesis of 1-alkyl-2-phenyl-4-quinolones from 2-haloben-zoic acids. It has the advantages with respect to (i) synthesis of 2 equiv of alkynones 5 from 1 equiv of 4,6-pyrimidyl di(2-halobenzoates) 3, (ii) synthesis of versatile 1-alkyl-2-phenyl-4-quinolones in high overall yields, and (iii) use of readily available and cheap starting materials. Therefore, this method could be utilized as a practical synthesis of 1-alkyl-2-phenyl-4-quinolones. Several methods have been developed to synthesize 1-alkyl-2-phenyl-4-quinolones from 2'-substituted acetophenones, anilines, and 2-halobenzoyl chlorides as starting materials. The reaction of N-methylisatoic anhydride with the lithium enolate of an 4'-methoxyacetophenone afforded the 1-methyl-2-phenyl-4-quinolone in a short sequence, but the yield was low. N-(2-Acetylphenyl)benzamides, prepared by Friedel-Crafts acylation of N-phenyl benzamides with acetyl chloride or benzoylation of 2'-aminoacetophenones with benzoyl chlorides,8 were cyclized with potassium t-butoxide to yield 2-aryl-4-quinolones, which were further alkylated with alkyl iodides to give 1-alkyl-2-aryl-4-quinolones.

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

    Directory of Open Access Journals (Sweden)

    Bisht Surendra S

    2006-12-01

    Full Text Available Abstract 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.

  19. One-Pot Enzymatic Synthesis of D-Arylalanines Using Phenylalanine Ammonia Lyase and L-Amino Acid Deaminase.

    Science.gov (United States)

    Zhu, Longbao; Feng, Guoqiang; Ge, Fei; Song, Ping; Wang, Taotao; Liu, Yi; Tao, Yugui; Zhou, Zhemin

    2018-06-08

    The phenylalanine ammonia-lyase (AvPAL) from Anabaena variabilis catalyzes the amination of substituent trans-cinnamic acid (t-CA) to produce racemic D,L-enantiomer arylalanine mixture owing to its low stereoselectivity. To produce high optically pure D-arylalanine, a modified AvPAL with high D-selectivity is expected. Based on the analyses of catalytic mechanism and structure, the Asn347 residue in the active site was proposed to control stereoselectivity. Therefore, Asn347 was mutated to construct mutant AvPAL-N347A, the stereoselectivity of AvPAL-N347A for D-enantiomer arylalanine was 2.3-fold higher than that of wild-type AvPAL (WtPAL). Furthermore, the residual L-enantiomer product in reaction solution could be converted into the D-enantiomer product through stereoselective oxidation by PmLAAD and nonselective reduction by reducing agent NH 3 BH 3 . At optimal conditions, the conversion rate of t-CA and optical purity (enantiomeric excess (ee D )) of D-phenylalanine reached 82% and exceeded 99%, respectively. The two enzymes displayed activity toward a broad range of substrate and could be used to efficiently synthesize D-arylalanine with different groups on the phenyl ring. Among these D-arylalanines, the yield of m-nitro-D-phenylalanine was highest and reached 96%, and the ee D exceeded 99%. This one-pot synthesis using AvPAL and PmLAAD has prospects for industrial application.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  2. Guided synthesis of accumulative solutions for the conceptual design of an efficient stove working with biomass

    International Nuclear Information System (INIS)

    Álvarez Cabrales, Alexis; Gaskins Espinosa, Benjamín Gabriel; Pérez Rodríguez, Roberto; Simeón Monet, Rolando Esteban

    2014-01-01

    The conceptual design is closely related to a product functional structure and the search of solution principles for its definition. This work exposes an accumulative method for the traceability of the functional structure that implements the guided conceptual synthesis of solutions in the preliminary analysis of this designing process stage. The method constitutes a contribution to Pahls and Beitzs classic design model. In it, the functional information system is manipulated, providing the designer with a help so that he can examine the different solutions that are obtained, giving him the possibility of selecting the most convenient one. The guided analysis of the accumulative solutions synthesis is illustrated by means of the conceptual design of an efficient stove working with biomass. (author)

  3. Efficiency and fidelity of cell-free protein synthesis by transfer RNA from aged mice

    Energy Technology Data Exchange (ETDEWEB)

    Foote, R.S.; Stulberg, M.P.

    1980-01-01

    Transfer RNAs (tRNAs) from heart, kidney, liver, and spleen of mature (10 to 12 months old) and aged (29 months old) C57BL/6 mice were tested for their ability to translate encephalomyocarditis viral RNA in a tRNA-dependent cell-free system derived from mouse ascites tumor cells. The rates of in vitro protein synthesis were compared as a function of tRNA concentration, and the fidelity of translation was examined by sodium dodecyl sulfate gel electrophoresis and isoelectric focusing of the viral polypeptides synthesized in vitro. No significant age-related differences in either the efficiency or fidelity of synthesis were discovered, indicating that alternations in tRNAs are probably not involved in the cellular aging of these tissues.

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

    Science.gov (United States)

    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.

  5. A simple synthesis of 2-keto-3-deoxy-D-erythro-hexonic acid isopropyl ester, a key sugar for the bacterial population living under metallic stress.

    Science.gov (United States)

    Grison, Claire M; Renard, Brice-Loïc; Grison, Claude

    2014-02-01

    2-Keto-3-deoxy-D-erythro-hexonic acid (KDG) is the key intermediate metabolite of the Entner Doudoroff (ED) pathway. A simple, efficient and stereoselective synthesis of KDG isopropyl ester is described in five steps from 2,3-O-isopropylidene-D-threitol with an overall yield of 47%. KDG isopropyl ester is studied as an attractive marker of a functional Entner Doudoroff pathway. KDG isopropyl ester is used to promote growth of ammonium producing bacterial strains, showing interesting features in the remediation of heavy-metal polluted soils. Copyright © 2013 Elsevier Inc. All rights reserved.

  6. Transition-metal-free synthesis of N-(1-alkenyl)imidazoles by potassium phosphate-promoted addition reaction of alkynes to imidazoles.

    Science.gov (United States)

    Lu, Linhua; Yan, Hong; Liu, Defu; Rong, Guangwei; Mao, Jincheng

    2014-01-01

    The addition reaction of alkynes to N-heterocycles by simply heating in DMSO with potassium phosphate is reported. Good yields with high stereoselectivity could be achieved for a range of substrates. The scope is quite general for both amines and phenylacetylenes. In addition, internal alkynes and α-bromostyrene were also examined in this reaction. This process is efficient and useful for the synthesis of (Z)-N-(1-alkenyl)imidazoles and related Z products. Thus, the reaction is useful because of the importance of the imidazole scaffold. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Stereoselective virtual screening of the ZINC database using atom pair 3D-fingerprints.

    Science.gov (United States)

    Awale, Mahendra; Jin, Xian; Reymond, Jean-Louis

    2015-01-01

    Tools to explore large compound databases in search for analogs of query molecules provide a strategically important support in drug discovery to help identify available analogs of any given reference or hit compound by ligand based virtual screening (LBVS). We recently showed that large databases can be formatted for very fast searching with various 2D-fingerprints using the city-block distance as similarity measure, in particular a 2D-atom pair fingerprint (APfp) and the related category extended atom pair fingerprint (Xfp) which efficiently encode molecular shape and pharmacophores, but do not perceive stereochemistry. Here we investigated related 3D-atom pair fingerprints to enable rapid stereoselective searches in the ZINC database (23.2 million 3D structures). Molecular fingerprints counting atom pairs at increasing through-space distance intervals were designed using either all atoms (16-bit 3DAPfp) or different atom categories (80-bit 3DXfp). These 3D-fingerprints retrieved molecular shape and pharmacophore analogs (defined by OpenEye ROCS scoring functions) of 110,000 compounds from the Cambridge Structural Database with equal or better accuracy than the 2D-fingerprints APfp and Xfp, and showed comparable performance in recovering actives from decoys in the DUD database. LBVS by 3DXfp or 3DAPfp similarity was stereoselective and gave very different analogs when starting from different diastereomers of the same chiral drug. Results were also different from LBVS with the parent 2D-fingerprints Xfp or APfp. 3D- and 2D-fingerprints also gave very different results in LBVS of folded molecules where through-space distances between atom pairs are much shorter than topological distances. 3DAPfp and 3DXfp are suitable for stereoselective searches for shape and pharmacophore analogs of query molecules in large databases. Web-browsers for searching ZINC by 3DAPfp and 3DXfp similarity are accessible at www.gdb.unibe.ch and should provide useful assistance to drug

  8. Study on Parallel Processing for Efficient Flexible Multibody Analysis based on Subsystem Synthesis Method

    Energy Technology Data Exchange (ETDEWEB)

    Han, Jong-Boo; Song, Hajun; Kim, Sung-Soo [Chungnam Nat’l Univ., Daejeon (Korea, Republic of)

    2017-06-15

    Flexible multibody simulations are widely used in the industry to design mechanical systems. In flexible multibody dynamics, deformation coordinates are described either relatively in the body reference frame that is floating in the space or in the inertial reference frame. Moreover, these deformation coordinates are generated based on the discretization of the body according to the finite element approach. Therefore, the formulation of the flexible multibody system always deals with a huge number of degrees of freedom and the numerical solution methods require a substantial amount of computational time. Parallel computational methods are a solution for efficient computation. However, most of the parallel computational methods are focused on the efficient solution of large-sized linear equations. For multibody analysis, we need to develop an efficient formulation that could be suitable for parallel computation. In this paper, we developed a subsystem synthesis method for a flexible multibody system and proposed efficient parallel computational schemes based on the OpenMP API in order to achieve efficient computation. Simulations of a rotating blade system, which consists of three identical blades, were carried out with two different parallel computational schemes. Actual CPU times were measured to investigate the efficiency of the proposed parallel schemes.

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

    Science.gov (United States)

    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.

  10. Stereoselective Hydrogenation and Ozonolysis of Iridoids. Conversion into Carbocyclic Nucleoside Analogues

    DEFF Research Database (Denmark)

    Franzyk, Henrik; Stermitz, Frank R.

    1999-01-01

    Stereoselective hydrogenation of the iridoids geniposide (9) and aucubin (19) was achieved by using the 1-methyl-1-methoxyethyl ether (MIP) as protecting group for the allylic alcohol, as it enhanced the stereoselectivity and prevented undesired hydrogenolysis. Ozonolysis of the hydrogenation...

  11. Transition metal oxide nanopowder and ionic liquid: an efficient system for the synthesis of diorganyl selenides, selenocysteine and derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Narayanaperumal, Senthil; Gul, Kashif; Kawasoko, Cristiane Y.; Singh, Devender; Dornelles, Luciano; Rodrigues, Oscar E.D. [Universidade Federal de Santa Maria (UFSC), RS (Brazil). Dept. de Quimica. LabSelen-NanoBio; Braga, Antonio L. [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Dept. de Quimica. LabSelen

    2010-07-01

    We have developed an efficient method for the synthesis of diorganyl selenides and {beta}-seleno amines using Zn, catalytic amounts of ZnO nanopowder, as a catalyst and ionic liquid as a recyclable solvent. This ZnO/ionic liquid system shows high efficiency in catalyzing these transformations with the formation of the desired products in high yields. (author)

  12. Highly Efficient Synthesis of 2-Aryl-3-methoxyacrylates via Suzuki-Miyaura Coupling Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hyung Ho; Lee, Chun Ho; Song, Young Seob; Park, No Kyun; Kim, Bum Tae; Heo, Jung Nyoung [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of)

    2006-02-15

    We have developed a highly efficient and convergent synthesis of 2-aryl-3-methoxyacrylates via the Suzuki-Miyaura coupling reaction of α-iodo-β-methoxy-acrylate with arylboronic acids. The biological activities of 2-aryl-3-methoxyacrylate derivatives will be reported in due course. The Suzuki-Miyaura coupling reaction provides a convenient access to the carbon-carbon bond formation with high efficiency. Recently, a number of 2-aryl-3-methoxy-acrylates served as a key scaffold for the development of biologically active pharmaceuticals and agrochemicals. Especially, the discovery of the naturally-occurring fungicides, such as strobilurin A and oudemansin A, possessing a β-methoxyacrylate moiety was immediately seized great attention by industrial research groups to open a new era of the strobilurin family including azoxy-strobin and picoxystrobin.

  13. Development of Highly Efficient Grafting Technique and Synthesis of Natural Polymer-Based Graft Adsorbent

    Energy Technology Data Exchange (ETDEWEB)

    Ueki, Y; Seko, N; Tamada, M [Japan Atomic Energy Agency, Quantum Beam Science Directorate, Takasaki (Japan)

    2012-09-15

    In the framework of the CRP, Japan has focused on the development of fibrous adsorbents for removal of toxic metal ions and recovery of significant metal ions from industrial wastewater and streaming water. Graft polymerization was carried out by using gamma irradiation facility and electron beam accelerator. Emulsion grafting is a novel topic for synthesis of metal ion adsorbents which are prepared from fibrous trunk polymers such as polyethylene fibre and biodegradable nonwoven fabrics. The emulsion grafting, where monomer micelles are dispersed in water in the presence of surfactant, is a highly efficient and economic grafting technique as compared to general organic solvent system. The resultant cotton-based adsorbent has high adsorption efficiency and high adsorption capacity for Hg, besides, it is biodegradable. Polylactic acid can also be used as a trunk material for the grafting. (author)

  14. Synthetic Progress toward Azadirachtins. 2. Enantio- and Diastereoselective Synthesis of the Right-Wing Fragment of 11-epi-Azadirachtin I.

    Science.gov (United States)

    Tan, Ceheng; Chen, Wei; Mu, Xinpeng; Chen, Qi; Gong, Jianxian; Luo, Tuoping; Yang, Zhen

    2015-05-15

    A stereoselective three-component coupling reaction of allylzinc bromide, silyl glyoxylate, and a β-lactone has been developed. This has been successfully applied to the enantio- and diastereoselective synthesis of the fully functionalized furopyran moiety of azadirachtins.

  15. A coenzyme-independent decarboxylase/oxygenase cascade for the efficient synthesis of vanillin.

    Science.gov (United States)

    Furuya, Toshiki; Miura, Misa; Kino, Kuniki

    2014-10-13

    Vanillin is one of the most widely used flavor compounds in the world as well as a promising versatile building block. The biotechnological production of vanillin from plant-derived ferulic acid has attracted much attention as a new alternative to chemical synthesis. One limitation of the known metabolic pathway to vanillin is its requirement for expensive coenzymes. Here, we developed a novel route to vanillin from ferulic acid that does not require any coenzymes. This artificial pathway consists of a coenzyme-independent decarboxylase and a coenzyme-independent oxygenase. When Escherichia coli cells harboring the decarboxylase/oxygenase cascade were incubated with ferulic acid, the cells efficiently synthesized vanillin (8.0 mM, 1.2 g L(-1) ) via 4-vinylguaiacol in one pot, without the generation of any detectable aromatic by-products. The efficient method described here might be applicable to the synthesis of other high-value chemicals from plant-derived aromatics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Synthesis and Evaluation of Tetramethylguanidinium-Polyethylenimine Polymers as Efficient Gene Delivery Vectors

    Directory of Open Access Journals (Sweden)

    Manohar Mahato

    2014-01-01

    Full Text Available Previously, we demonstrated that 6-(N,N,N′,N′-tetramethylguanidinium chloride-hexanoyl-polyethylenimine (THP polymers exhibited significantly enhanced transfection efficiency and cell viability. Here, in the present study, we have synthesized a series of N,N,N′,N′-tetramethylguanidinium-polyethylenimine (TP1-TP5 polymers via a single-step reaction involving peripheral primary amines of bPEI and varying amounts of 2-(1H-benzotriazol-1-yl-1,1,3,3-tetramethyluronium hexafluorophosphate (HBTU. These polymers were found to interact efficiently with negatively charged pDNA and formed stable complexes in the size range of ~240–450 nm. Acid-base titration profiles revealed improved buffering capacity of TP polymers as compared to bPEI. Transfection and cytotoxicity assays performed with TP/pDNA complexes on HEK293, CHO, and HeLa cells showed significantly higher transfection efficiency and cell viability with one of the complexes, TP2/pDNA complex, exhibited the highest transfection efficiency (~1.4–2.3-fold outcompeting native bPEI and the commercially available transfection reagent, Lipofectamine 2000. Compared to previously reported THP polymers, the transfection efficiency of TP/pDNA complexes was found to be lower, as examined by flow cytometry. These results highlight the importance of the hydrophobic C-6 linker in THP polymers in forming compact nanostructures with pDNA, which might lead to efficient uptake and internalization of the complexes; however, the projected TP polymers offer an advantage of their rapid and economical one-step synthesis.

  17. Synthesis and evaluation of tetramethylguanidinium-polyethylenimine polymers as efficient gene delivery vectors.

    Science.gov (United States)

    Mahato, Manohar; Yadav, Santosh; Kumar, Pradeep; Sharma, Ashwani Kumar

    2014-01-01

    Previously, we demonstrated that 6-(N,N,N',N'-tetramethylguanidinium chloride)-hexanoyl-polyethylenimine (THP) polymers exhibited significantly enhanced transfection efficiency and cell viability. Here, in the present study, we have synthesized a series of N,N,N',N'-tetramethylguanidinium-polyethylenimine (TP1-TP5) polymers via a single-step reaction involving peripheral primary amines of bPEI and varying amounts of 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HBTU). These polymers were found to interact efficiently with negatively charged pDNA and formed stable complexes in the size range of ~240-450 nm. Acid-base titration profiles revealed improved buffering capacity of TP polymers as compared to bPEI. Transfection and cytotoxicity assays performed with TP/pDNA complexes on HEK293, CHO, and HeLa cells showed significantly higher transfection efficiency and cell viability with one of the complexes, TP2/pDNA complex, exhibited the highest transfection efficiency (~1.4-2.3-fold) outcompeting native bPEI and the commercially available transfection reagent, Lipofectamine 2000. Compared to previously reported THP polymers, the transfection efficiency of TP/pDNA complexes was found to be lower, as examined by flow cytometry. These results highlight the importance of the hydrophobic C-6 linker in THP polymers in forming compact nanostructures with pDNA, which might lead to efficient uptake and internalization of the complexes; however, the projected TP polymers offer an advantage of their rapid and economical one-step synthesis.

  18. Total Synthesis of balanol, Part 2

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Kelly, Nicholas; Tedenborg, Lars

    1997-01-01

    A convergent enantioselective total synthesis of the natural product (-)-balanol (1) is described. In addition to benzophenone fragment 8, key intermediates are chiral bicyclic aziridine 3 and the corresponding epoxide 4, both of which undergo highly regio- and stereoselective nucleophilic ring...

  19. Synthesis of pterostilbene by Julie Olefination

    Science.gov (United States)

    A simple, stereoselective route for the synthesis of the biologically active compounds trans-pterostilbene and tetramethoxy stilbene from the readily available starting materials 3,5-dimethoxy benzyl alcohol and 4-hydroxy benzaldehyde was developed using Julia olefination as a key reaction....

  20. Stereoselective aminoacylation of a dinucleoside monophosphate by the imidazolides of DL-alanine and N-(tert-butoxycarbonyl)-DL-alanine

    Science.gov (United States)

    Profy, A. T.; Usher, D. A.

    1984-01-01

    The aminoacylation of diinosine monophosphate was studied experimentally. When the acylating agent was the imidazolide of N-(tert-butoxycarbonyl)-DL-alanine, a 40 percent enantiomeric excess of the isomer was incorporated at the 2' site and the positions of equilibrium for the reversible 2'-3' migration reaction differed for the D and L enantiomers. The reactivity of the nucleoside hydroxyl groups was found to decrease on the order 2'(3') less than internal 2' and less than 5', and the extent of the reaction was affected by the concentration of the imidazole buffer. Reaction of IpI with imidazolide of unprotected DL-alanine, by contrast, led to an excess of the D isomer at the internal 2' site. Finally, reaction with the N-carboxy anhydride of DL-alanine occurred without stereoselection. These results are found to be relevant to the study of the evolution of optical chemical activity and the origin of genetically directed protein synthesis.

  1. Chiral thiazoline and thiazole building blocks for the synthesis of peptide-derived natural products.

    Science.gov (United States)

    Just-Baringo, Xavier; Albericio, Fernando; Alvarez, Mercedes

    2014-01-01

    Thiazoline and thiazole heterocycles are privileged motifs found in numerous peptide-derived natural products of biological interest. During the last decades, the synthesis of optically pure building blocks has been addressed by numerous groups, which have developed a plethora of strategies to that end. Efficient and reliable methodologies that are compatible with the intricate and capricious architectures of natural products are a must to further develop their science. Structure confirmation, structure-activity relationship studies and industrial production are fields of paramount importance that require these robust methodologies in order to successfully bring natural products into the clinic. Today's chemist toolbox is assorted with many powerful methods for chiral thiazoline and thiazole synthesis. Ranging from biomimetic approaches to stereoselective alkylations, one is likely to find a suitable method for their needs.

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

    Science.gov (United States)

    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.

  3. Highly efficient isocyanate-free microwave-assisted synthesis of [6]-oligourea

    KAUST Repository

    Qaroush, Abdussalam K.

    2013-01-01

    A new eco-friendly, isocyanate-free, energy-saving method for the production of [6]-oligourea, utilizing a green carbonylating agent, viz. propylene carbonate, is reported. It comprises an organocatalyzed, microwave-assisted, solvent-free synthesis. Two modes of microwave-assisted synthesis, viz. dynamic and fixed energy modes, were applied. Upon optimization, the dynamic mode gave 79% yields of [6]-oligourea. On the other hand, almost quantitative yields were obtained using the fixed mode, within 20 min, at 10 W and with the same catalyst loading. Combination of both organocatalysis and microwave energy input appears to be a key issue for the efficiency of the reaction, with the fixed energy mode being best suited. It should be noted that all data reported are reproducible (due to the homogeneous microwave technology used by CEM Discover S-Class of microwave reactors). To the best of our knowledge, this is the best eco-friendly synthetic approach for the preparation of the title oligomers. It paves the way for using more of the biorenewable and sustainable chemicals as a feedstock for the production of polyureas. The oligomer produced was analyzed by EA, ATR-FTIR, XRD, 1H and 13CNMR. Furthermore, thermal properties of the resulting [6]-oligourea were analyzed using TGA and DSC. © The Royal Society of Chemistry 2013.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  6. One-Step Facile Synthesis of a Simple Hole Transport Material for Efficient Perovskite Solar Cells

    KAUST Repository

    Chen, Hu

    2016-04-04

    A hole transporting material was designed for use in perovskite solar cells, with a facile one-step synthesis from inexpensive, com-mercially available reagents. The molecule comprises a central fluorinated phenyl core with pendant aryl amines, namely, 3,6-difluoro-N1,N1,N2,N2,N4,N4,N5,N5-octakis(4-methoxyphenyl)benzene-1,2,4,5-tetraamine (DFTAB). A power conversion efficiency of up to 10.4% was achieved in a mesoporous perovskite device architecture. The merits of a simple and potentially low cost syn-thetic route as well as promising performance in perovskite devices, encourages further development of this materials class as new low-cost hole transporting materials for the scale up of perovskite solar cells.

  7. Rearrangement of 5-trimethylsilylthebaine on treatment with L-selectride: an efficient synthesis of (+)-bractazonine.

    Science.gov (United States)

    Chen, Weibin; Wu, Huifang; Bernard, Denzil; Metcalf, Matthew D; Deschamps, Jeffrey R; Flippen-Anderson, Judith L; MacKerell, Alexander D; Coop, Andrew

    2003-03-07

    Treatment of 5-trimethylsilylthebaine with L-Selectride gave rise to a rearrangement to 10-trimethylsilylbractazonine through migration of the phenyl group, whereas treatment of thebaine with strong Lewis acids is known to lead to a similar rearrangement through migration of the alkyl bridge to give, after reduction, (+)-neodihydrothebaine. It is suggested that the rearrangement of the alkyl group of thebaine is favored due to the formation of a tertiary benzylic cation. However, for 5-trimethylsilylthebaine, the lithium ion of L-Selectride acts as the Lewis acid and the beta-silyl effect dominates in the stabilization of any positive charge. This rearrangement provides a clear example of the greater relative migratory aptitude of phenyl groups over alkyl groups, and provides an efficient synthesis of (+)-bractazonine from thebaine.

  8. Efficient Synthesis of Single-Chain Polymer Nanoparticles via Amide Formation

    Directory of Open Access Journals (Sweden)

    Ana Sanchez-Sanchez

    2015-01-01

    Full Text Available Single-chain technology (SCT allows the transformation of individual polymer chains to folded/collapsed unimolecular soft nanoparticles. In this work we contribute to the enlargement of the SCT toolbox by demonstrating the efficient synthesis of single-chain polymer nanoparticles (SCNPs via intrachain amide formation. In particular, we exploit cross-linking between active methylene groups and isocyanate moieties as powerful “click” chemistry driving force for SCNP construction. By employing poly(methyl methacrylate- (PMMA- based copolymers bearing β-ketoester units distributed randomly along the copolymer chains and bifunctional isocyanate cross-linkers, SCNPs were successfully synthesized at r.t. under appropriate reaction conditions. Characterization of the resulting SCNPs was carried out by means of a combination of techniques including size exclusion chromatography (SEC, infrared (IR spectroscopy, proton nuclear magnetic resonance (1H NMR spectroscopy, dynamic light scattering (DLS, and elemental analysis (EA.

  9. Efficient Information and Data Management in Synthesis and Design of Processing Netorks

    DEFF Research Database (Denmark)

    Quaglia, Alberto; Sin, Gürkan; Gani, Rafiqul

    industrial use of EWO, therefore, methods and tools for efficient information and data management need to be developed. In this contribution, we present a systematic data architecture, which is integrated in our framework for synthesis and design of processing networks (Quaglia et al., submitted). The data...... studies. The case studies are selected from different industrial segments, such as food processing (soybean processing network), water and wastewater management (refinery wastewater treatment and reuse; municipal water treatment) and biorefinery....... a large number (typically 1000-100,000) of data (Quaglia et. al, submitted). As a result, EWO problem formulation is a time and resource intensive task. Moreover, compilation errors results in faulty problem specifications, and may compromise the quality of the obtained solution. In order to enable...

  10. One-Step Facile Synthesis of a Simple Hole Transport Material for Efficient Perovskite Solar Cells

    KAUST Repository

    Chen, Hu; Bryant, Daniel; Troughton, Joel; Kirkus, Mindaugas; Neophytou, Marios; Miao, Xiaohe; Durrant, James R.; McCulloch, Iain

    2016-01-01

    A hole transporting material was designed for use in perovskite solar cells, with a facile one-step synthesis from inexpensive, com-mercially available reagents. The molecule comprises a central fluorinated phenyl core with pendant aryl amines, namely, 3,6-difluoro-N1,N1,N2,N2,N4,N4,N5,N5-octakis(4-methoxyphenyl)benzene-1,2,4,5-tetraamine (DFTAB). A power conversion efficiency of up to 10.4% was achieved in a mesoporous perovskite device architecture. The merits of a simple and potentially low cost syn-thetic route as well as promising performance in perovskite devices, encourages further development of this materials class as new low-cost hole transporting materials for the scale up of perovskite solar cells.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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).

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

    Science.gov (United States)

    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...

  14. PEG-400 as an efficient and recyclable reaction medium for the synthesis of polyhydroquinolines via Hantzsch reaction

    Directory of Open Access Journals (Sweden)

    Shitole Nana Vikram

    2013-01-01

    Full Text Available Polyhydroquinoline derivatives have been prepared efficiently in a one-pot synthesis via Hantzsch condensation using PEG-400 as reaction medium. The present method does not involve any hazardous organic solvents or toxic catalysts. The present methodology offers several advantages such as simple procedure, excellent yields with shorter reaction times and purification of products by non-chromatographic methods.

  15. Fast and efficient green synthesis of thiosulfonate S-esters by microwave-supported permanganate oxidation of symmetrical disulfides

    DEFF Research Database (Denmark)

    Thi, Luu Thi Xuan; Thi Nguyen, Thao-Tran; Le, Thach Ngoc

    2015-01-01

    Potassium permanganate absorbed on copper(II) sulfate pentahydrate has been found to be an efficient, inexpensive, and green oxidation agent for the synthesis of “symmetrical” thiosulfonate S-esters by oxidation of the corresponding symmetrical disulfides. The oxidation reactions were carried out...

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

    Science.gov (United States)

    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.

  17. Zirconyl (IV Nitrate as Efficient and Reusable Solid Lewis Acid Catalyst for the Synthesis of Benzimidazole Derivatives

    Directory of Open Access Journals (Sweden)

    Pratapsinha B. Gorepatil

    2013-01-01

    Full Text Available The present paper introduces a simple and efficient method for the synthesis of substituted benzimidazoles by heterocyclization of different o-phenylenediamines and substituted aromatic carboxylic acid/aldehyde in the presence of zirconyl nitrate as catalyst in ethanol under reflux, which produced excellent yield of corresponding benzimidazoles in a short reaction time with reusability of catalyst.

  18. I2/K2CO3: An efficient catalyst for the synthesis of 5-aryl-2,6-dicyano ...

    Indian Academy of Sciences (India)

    Abstract. Molecular iodine in the presence of potassium carbonate has been found to be an efficient and eco- friendly catalyst for the synthesis of polysubstituted dicyanoanilines from aldehydes, acetone and malononitrile under solvent-free thermal condition. The experimental procedure is simple, includes shorter reaction ...

  19. Evaluation of an automated double-synthesis module: efficiency and reliability of subsequent radiosyntheses of FHBG and FLT

    International Nuclear Information System (INIS)

    Niedermoser, Sabrina; Pape, Manuela; Gildehaus, Franz Josef; Wängler, Carmen; Hartenbach, Markus; Schirrmacher, Ralf; Bartenstein, Peter; Wängler, Björn

    2012-01-01

    We optimized the synthesis methods for 3′-deoxy-3′-[ 18 F]fluorothymidine ([ 18 F]FLT) and 9-(4-[ 18 F]fluoro-3-[hydroxymethyl]butyl)guanine) ([ 18 F]FHBG) and automated them on an Explora General Nucleophilic double-synthesis module. Furthermore, the synthesis efficiency and reliability and the formation of cross-contaminations of the products when preparing two consecutive batches were evaluated. Whereas the preinstalled FLT synthesis conditions required substantial modification in reaction and neutralization conditions to achieve radiochemical yields of up to 60% within 70±10 min including high-performance liquid chromatography purification, the synthesis of FHBG had to be implemented to the module to obtain competitive radiochemical yields of up to 40% in an overall synthesis time of 60±10 min. The radiochemical purities obtained were ≥99% and ≥96% for the synthesis of [ 18 F]FLT and [ 18 F]FHBG, respectively. No significant changes in yield or purity could be observed between both batch productions. We found that the yields and purities also did not change when performing FLT after FHBG syntheses and vice versa. Hence, we developed a synthesis setup that offers the opportunity to perform two subsequent syntheses of either [ 18 F]FLT, [ 18 F]FHBG or [ 18 F]FLT after [ 18 F]FHBG without decrease in radiochemical yields and purities. Also, no cross-contaminations were observed, which can be attributed to the use of separate product delivery tubes, purification columns and an automated intermediate cleaning program. These results open up the possibility of producing consecutively either two equal 18 F-fluorinated tracers or two different ones in high yields on the same synthesis module.

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

    Science.gov (United States)

    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.

  1. Stereoselective potencies and relative toxicities of coniine enantiomers.

    Science.gov (United States)

    Lee, Stephen T; Green, Benedict T; Welch, Kevin D; Pfister, James A; Panter, Kip E

    2008-10-01

    Coniine, one of the major toxic alkaloids present in poison hemlock ( Conium maculatum), occurs in two optically active forms. A comparison of the relative potencies of (+)- and (-)-coniine enantiomers has not been previously reported. In this study, we separated the enantiomers of coniine and determined the biological activity of each enantiomer in vitro and in vivo. The relative potencies of these enantiomers on TE-671 cells expressing human fetal nicotinic neuromuscular receptors had the rank order of (-)-coniine > (+/-)-coniine > (+)-coniine. A mouse bioassay was used to determine the relative lethalities of (-)-, (+/-)-, and (+)-coniine in vivo. The LD 50 values of the coniine enantiomers were 7.0, 7.7, and 12.1 mg/kg for the (-)-, (+/-)-, and (+)- forms of coniine, respectively. The results from this study demonstrate that there is a stereoselective difference in the in vitro potencies of the enantiomers of coniine that directly correlates with the relative toxicities of the enantiomers in vivo.

  2. Stereoselective inhibition of the hERG1 potassium channel

    Directory of Open Access Journals (Sweden)

    Liliana eSintra Grilo

    2010-11-01

    Full Text Available A growing number of drugs have been shown to prolong cardiac repolarization, predisposing individuals to life-threatening ventricular arrhythmias known as Torsades de Pointes. Most of these drugs are known to interfere with the human ether à-gogo related gene 1 (hERG1 channel, whose current is one of the main determinants of action potential duration. Prolonged repolarization is reflected by lengthening of the QT interval of the electrocardiogram, as seen in the suitably named drug-induced long QT syndrome. Chirality (presence of an asymmetric atom is a common feature of marketed drugs, which can therefore exist in at least two enantiomers with distinct three-dimensional structures and possibly distinct biological fates. Both the pharmacokinetic and pharmacodynamic properties can differ between enantiomers, as well as also between individuals who take the drug due to metabolic polymorphisms. Despite the large number of reports about drugs reducing the hERG1 current, potential stereoselective contributions have only been scarcely investigated. In this review, we present a non-exhaustive list of clinically important molecules which display chiral toxicity that may be related to hERG1-blocking properties. We particularly focus on methadone cardiotoxicity, which illustrates the importance of the stereoselective effect of drug chirality as well as individual variations resulting from pharmacogenetics. Furthermore, it seems likely that, during drug development, consideration of chirality in lead optimization and systematic assessment of the hERG1 current block with all enantiomers could contribute to the reduction of the risk of drug-induced LQTS.

  3. Modular synthesis of the pyrimidine core of the manzacidins by divergent Tsuji–Trost coupling

    Directory of Open Access Journals (Sweden)

    Sebastian Bretzke

    2016-06-01

    Full Text Available The design, development and application of an efficient procedure for the concise synthesis of the 1,3-syn- and anti-tetrahydropyrimidine cores of manzacidins are reported. The intramolecular allylic substitution reaction of a readily available joint urea-type substrate enables the facile preparation of both diastereomers in high yields. The practical application of this approach is demonstrated in the efficient and modular preparation of the authentic heterocyclic cores of manzacidins, structurally unique bromopyrrole alkaloids of marine origin. Additional features of this route include the stereoselective generation of the central amine core with an appending quaternary center by an asymmetric addition of a Grignard reagent to a chiral tert-butanesulfinyl ketimine following an optimized Ellman protocol and a cross-metathesis of a challenging homoallylic urea substrate, which proceeds in good yields in the presence of an organic phosphoric acid.

  4. Recent advances in efficient and selective synthesis of di-, tri-, and tetrasubstituted alkenes via Pd-catalyzed alkenylation-carbonyl olefination synergy.

    Science.gov (United States)

    Negishi, Ei-ichi; Huang, Zhihong; Wang, Guangwei; Mohan, Swathi; Wang, Chao; Hattori, Hatsuhiko

    2008-11-18

    Although generally considered competitive, the alkenylation and carbonyl olefination routes to alkenes are also complementary. In this Account, we focus on these approaches for the synthesis of regio- and stereodefined di- and trisubstituted alkenes and a few examples of tetrasubstituted alkenes. We also discuss the subset of regio- and stereodefined dienes and oligoenes that are conjugated. Pd-catalyzed cross-coupling using alkenyl metals containing Zn, Al, Zr, and B (Negishi coupling and Suzuki coupling) or alkenyl halides and related alkenyl electrophiles provides a method of alkenylation with the widest applicability and predictability, with high stereo- and regioselectivity. The requisite alkenyl metals or alkenyl electrophiles are most commonly prepared through highly selective alkyne addition reactions including (i) conventional polar additions, (ii) hydrometalation, (iii) carbometalation, (iv) halometalation, and (v) other heteroatom-metal additions. Although much more limited in applicability, the Heck alkenylation offers an operationally simpler, viable alternative when it is highly selective and satisfactory. A wide variety of carbonyl olefination reactions, especially the Wittig olefination and its modifications represented by the E-selective HWE olefination and the Z-selective Still-Gennari olefination, collectively offer the major alternative to the Pd-catalyzed alkenylation. However, the carbonyl olefination method fundamentally suffers from more limited stereochemical options and generally lower stereoselectivity levels than the Pd-catalyzed alkenylation. In a number of cases, however, very high (>98%) stereoselectivity levels have been attained in the syntheses of both E and Z isomers. The complementarity of the alkenylation and carbonyl olefination routes provide synthetic chemists with valuable options. While the alkenylation involves formation of a C-C single bond to a CC bond, the carbonyl olefination converts a CO bond to a CC bond. When a

  5. Efficient synthesis of tension modulation in strings and membranes based on energy estimation.

    Science.gov (United States)

    Avanzini, Federico; Marogna, Riccardo; Bank, Balázs

    2012-01-01

    String and membrane vibrations cannot be considered as linear above a certain amplitude due to the variation in string or membrane tension. A relevant special case is when the tension is spatially constant and varies in time only in dependence of the overall string length or membrane surface. The most apparent perceptual effect of this tension modulation phenomenon is the exponential decay of pitch in time. Pitch glides due to tension modulation are an important timbral characteristic of several musical instruments, including the electric guitar and tom-tom drum, and many ethnic instruments. This paper presents a unified formulation to the tension modulation problem for one-dimensional (1-D) (string) and two-dimensional (2-D) (membrane) cases. In addition, it shows that the short-time average of the tension variation, which is responsible for pitch glides, is approximately proportional to the system energy. This proportionality allows the efficient physics-based sound synthesis of pitch glides. The proposed models require only slightly more computational resources than linear models as opposed to earlier tension-modulated models of higher complexity. © 2012 Acoustical Society of America.

  6. Seedless synthesis and efficient recyclable catalytic activity of Ag@Fe nanocomposites towards methyl orange

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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).

  8. Enantioselective Synthesis of (-)-Vallesine: Late-Stage C17-Oxidation via Complex Indole Boronation.

    Science.gov (United States)

    Antropow, Alyssa H; Garcia, Nicholas R; White, Kolby L; Movassaghi, Mohammad

    2018-06-04

    The first enantioselective total synthesis of (-)-vallesine via a strategy that features a late-stage regioselective C17-oxidation followed by a highly stereoselective transannular cyclization is reported. The versatility of this approach is highlighted by the divergent synthesis of the archetypal alkaloid of this family, (+)-aspidospermidine, and an A-ring-oxygenated derivative, (+)-deacetylaspidospermine, the precursor to (-)-vallesine, from a common intermediate.

  9. Iridium-Catalyzed Dynamic Kinetic Isomerization: Expedient Synthesis of Carbohydrates from Achmatowicz Rearrangement Products.

    Science.gov (United States)

    Wang, Hao-Yuan; Yang, Ka; Bennett, Scott R; Guo, Sheng-rong; Tang, Weiping

    2015-07-20

    A highly stereoselective dynamic kinetic isomerization of Achmatowicz rearrangement products was discovered. This new internal redox isomerization provided ready access to key intermediates for the enantio- and diastereoselective synthesis of a series of naturally occurring sugars. The nature of the de novo synthesis also enables the preparation of both enantiomers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Synthesis of Α-azido-oximes from chiral cyclo-hexanones. Conformation monitoring by NMR

    International Nuclear Information System (INIS)

    Alves, R.J.; Fontes Prado, M.A.; Oliveira, A.B. de; Souza Filho, J.D. de; GArcia, J.I.; Olesker, A.; Lukacs, G.

    1993-01-01

    Carbon hydrates are the greatest source of chirality due to a large number of functional groups. Such compounds present preferential conformations, which result in reactions which high level of stereo-selectivity. This work is concerned to the preparation of intermediates to several other synthesis of biological interest and how the above mentioned properties influence these synthesis

  11. An Efficient Synthesis of Nitriles from Aldoximes Using Diethyl Phosphorocyanidate under Mild Conditions

    International Nuclear Information System (INIS)

    Lee, Kieseung; An, Hyeonseong; Hwang, Chanyeon

    2012-01-01

    Nitriles are valuable intermediates in organic synthesis not only because they serve as the appropriate precursors to various functional groups, but also because they are widely used as the key intermediates for pharmaceuticals, agrochemicals and various N-heterocyclic compounds. The cyano group itself is also frequently found in many biologically important molecules. Therefore, a variety of synthetic routes to nitriles from diverse chemical precursors have been developed. Among these routes, nitrile synthesis from aldoximes using an appropriate dehydrating agent has been a general and clean method. For this purpose, numerous reagents such as chlorosulfonyl isocyanate, di-2-pyridyl sulfite, Burgess reagent, [RuCl 2 (p-cymene)] 2 /MS, 4A, BOP, Pd(OAc) 2 /PPh 3 , Cu(OAc) 2 /ultrasound have been developed. These reagents, however, may have limitations in some respects such as harsh reaction conditions, use of expensive or less readily available reagents, low yields, and lack of generality. Therefore, there is still a need to develop mild and general method for this conversion. Diethyl phosphorocyanidate (DEPC) was initially introduced as an efficient peptide coupling reagent, and has been utilized for useful organic reactions. Previously, we reported that 2-chloro-1-methylpyridinium iodide is an efficient and mild reagent for the dehydration of aldoximes to nitriles under mild conditions. In continuation of our interest in developing mild method for the conversion of aldoximes to nitriles, we herein wish to report the first application of DEPC to the efficient synthesis of nitriles from aldoximes under mild conditions (Scheme 1). In order to obtain the information regarding the optimum reaction conditions, 4-pyridine aldoxime (1a) was reacted with DEPC without base, and in presence of various base in CH 2 Cl 2 at rt for a prolonged reaction time (20 h) (Table 1). CH 2 CI 2 was chosen as reaction medium in this reaction due to the good solubility for both 1 and 3 in CH

  12. An Efficient Synthesis of Nitriles from Aldoximes Using Diethyl Phosphorocyanidate under Mild Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kieseung; An, Hyeonseong; Hwang, Chanyeon [Woosuk Univ.,Wanju (Korea, Republic of)

    2012-10-15

    Nitriles are valuable intermediates in organic synthesis not only because they serve as the appropriate precursors to various functional groups, but also because they are widely used as the key intermediates for pharmaceuticals, agrochemicals and various N-heterocyclic compounds. The cyano group itself is also frequently found in many biologically important molecules. Therefore, a variety of synthetic routes to nitriles from diverse chemical precursors have been developed. Among these routes, nitrile synthesis from aldoximes using an appropriate dehydrating agent has been a general and clean method. For this purpose, numerous reagents such as chlorosulfonyl isocyanate, di-2-pyridyl sulfite, Burgess reagent, [RuCl{sub 2}(p-cymene)]{sub 2}/MS, 4A, BOP, Pd(OAc){sub 2}/PPh{sub 3}, Cu(OAc){sub 2}/ultrasound have been developed. These reagents, however, may have limitations in some respects such as harsh reaction conditions, use of expensive or less readily available reagents, low yields, and lack of generality. Therefore, there is still a need to develop mild and general method for this conversion. Diethyl phosphorocyanidate (DEPC) was initially introduced as an efficient peptide coupling reagent, and has been utilized for useful organic reactions. Previously, we reported that 2-chloro-1-methylpyridinium iodide is an efficient and mild reagent for the dehydration of aldoximes to nitriles under mild conditions. In continuation of our interest in developing mild method for the conversion of aldoximes to nitriles, we herein wish to report the first application of DEPC to the efficient synthesis of nitriles from aldoximes under mild conditions (Scheme 1). In order to obtain the information regarding the optimum reaction conditions, 4-pyridine aldoxime (1a) was reacted with DEPC without base, and in presence of various base in CH{sub 2}Cl{sub 2} at rt for a prolonged reaction time (20 h) (Table 1). CH{sub 2}CI{sub 2} was chosen as reaction medium in this reaction due to the

  13. Glucosamine derived DISAL donors for stereoselective glycosylations under neutral conditions

    DEFF Research Database (Denmark)

    Grathe, S.; Thygesen, M.B.; Larsen, K.

    2005-01-01

    DISAL (methyl 3,5-dinitrosa/icylate) D-glcosyl, D-galactosyl, D-mannosyl, and L-quinovosyl donors have previously provided the efficient glycosylation of a range of substrates under either strictly neutral, mildly basic, or very mildly Lewis acidic (LiClO4) conditions. Herein we report the synthe......DISAL (methyl 3,5-dinitrosa/icylate) D-glcosyl, D-galactosyl, D-mannosyl, and L-quinovosyl donors have previously provided the efficient glycosylation of a range of substrates under either strictly neutral, mildly basic, or very mildly Lewis acidic (LiClO4) conditions. Herein we report...... the synthesis of new glucosamine DISAL donors, carrying N-TCP, -Troc, or -TFAc protecting groups, and their use in beta-(1,2-trans) selective glycosylations, primarily in NMP in the absence of any added Lewis acids, or in CH3NO2 with LiClO4. Finally, precise microwave heating proved effective in promoting...

  14. New efficient catalyst for ammonia synthesis: barium-promoted cobalt on carbon

    DEFF Research Database (Denmark)

    Hagen, Stefan; Barfod, Rasmus; Fehrmann, Rasmus

    2002-01-01

    Barium-promoted cobalt catalysts supported on carbon exhibit higher ammonia activities at synthesis temperatures than the commercial, multipromoted iron catalyst and also a lower ammonia......Barium-promoted cobalt catalysts supported on carbon exhibit higher ammonia activities at synthesis temperatures than the commercial, multipromoted iron catalyst and also a lower ammonia...

  15. Synthesis of substituted 1,4-diazepines and 1,5-benzodiazepines using an efficient heteropolyacid-catalyzed procedure.

    Science.gov (United States)

    Kaoua, Rachedine; Bennamane, Norah; Bakhta, Saliha; Benadji, Sihame; Rabia, Cherifa; Nedjar-Kolli, Bellara

    2010-12-28

    An efficient and improved procedure for the synthesis of 1,4-diazepine and 1,5-benzodiazepine derivatives via the reaction of ketimine intermediates with aldehydes in the presence of Keggin-type heteropolyacids (HPAs) was developed. High yields and short reaction times were obtained for both electron-releasing and electron-withdrawing substituted 1,4-diazepine  and 1,5-benzodiazepines derivatives.

  16. Efficient sonochemical synthesis of alkyl 4-aryl-6-chloro-5-formyl-2-methyl-1,4-dihydropyridine-3-carboxylate derivatives.

    Science.gov (United States)

    Ruiz, Enrique; Rodríguez, Hortensia; Coro, Julieta; Niebla, Vladimir; Rodríguez, Alfredo; Martínez-Alvarez, Roberto; de Armas, Hector Novoa; Suárez, Margarita; Martín, Nazario

    2012-03-01

    A facile, efficient and environment-friendly protocol for the synthesis of 6-chloro-5-formyl-1,4-dihydropyridine derivatives has been developed by the convenient ultrasound-mediated reaction of 2(1H)pyridone derivatives with the Vilsmeier-Haack reagent. This method provides several advantages over current reaction methodologies including a simpler work-up procedure, shorter reaction times and higher yields. Copyright © 2011. Published by Elsevier B.V.

  17. Synthesis of Substituted 1,4-Diazepines and 1,5-Benzodiazepines Using an Efficient Heteropolyacid-Catalyzed Procedure

    Directory of Open Access Journals (Sweden)

    Sihame Benadji

    2010-12-01

    Full Text Available An efficient and improved procedure for the synthesis of 1,4-diazepine and 1,5-benzodiazepine derivatives via the reaction of ketimine intermediates with aldehydes in the presence of Keggin-type heteropolyacids (HPAs was developed. High yields and short reaction times were obtained for both electron-releasing and electron-withdrawing substituted 1,4-diazepine  and 1,5-benzodiazepines derivatives.

  18. Amberlyst-15: An Efficient and reusable heterogeneous catalyst for the synthesis of β-amino carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Pathakota Venkata Ramana

    2015-12-01

    Full Text Available A simple and efficient method has been developed for the synthesis of β-amino carbonyl compounds from aromatic ketones, aldehydes and amines by Mannich reaction in the presence of amberlyst-15 as a reusable heterogeneous catalyst at room temperature under solvent-free conditions. The noteworthy advantages of the present method are short reaction times, good product yields, simple procedures and use of non-toxic catalyst.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  1. Efficient synthesis of superparamagnetic magnetite nanoparticles under air for biomedical applications

    Energy Technology Data Exchange (ETDEWEB)

    Saxena, Namita, E-mail: saxenanamita@yahoo.com [School of Nano Sciences, Central University of Gujarat, Gandhinagar 382030 (India); Singh, Man, E-mail: mansingh50@hotmail.com [School of Chemical Sciences, Central University of Gujarat, Gandhinagar 382030 (India)

    2017-05-01

    The facile co-precipitation process of synthesising Superparamagnetic Iron Oxide Nanoparticles (SPIONs) especially magnetite was investigated and simplified, to develop a reproducible and scaled up synthesis process under air, for producing particles with enhanced percentage of magnetite, thus eliminating the crucial and complicated need of using the inert atmosphere. Presence of magnetite was confirmed by XRD, TEM, and Raman spectroscopy. Efficiency of synthesising magnetite was increased up to approx. ∼58 wt%, under air with no other phases but maghemite present. Alkali concentration was optimised, and particles with better magnetisation values were synthesised. The approximate weight percentage of magnetite was calculated using the simple and rapid XRD peak deconvolution method. Higher pH values from 13 to14 were investigated in the study while alkali concentration was varied from 0.5 to 4 M. 1Molar NaOH with a final pH of 13.4 was found to be optimum. Well crystallised particles with approx. 6–12 nm size, narrow size distribution and cubo-spheroidal shape were synthesised. Particles were Superparamagnetic with high values of saturation magnetisation of up to 68 emu/g and negligible values of remanence and coercivity. A reaction yield of up to 62% was obtained. Hydrophilic coated particles were produced in a single, one step facile process for biomedical applications, using optimised parameters of pH and alkali concentration obtained in the study. Single domain particles with good magnetisation formed stable aqueous dispersions. FTIR, UV-Visible and DLS were used to confirm the coating and dispersion stabilities of the particles. These particles have the requisite properties required for application in different biomedical fields.

  2. Alkenenitrile Transmissive Olefination: Synthesis of the Putative Lignan "Morinol I"

    Science.gov (United States)

    Fleming, Fraser F.; Liu, Wang; Yao, Lihua; Pitta, Bhaskar; Purzycki, Matthew; Ravikumar, P. C.

    2012-01-01

    Grignard reagents trigger an addition-elimination with α'-hydroxy acrylonitriles to selectively generate Z-alkenenitriles. The modular assembly of Z-alkenenitriles from a Grignard reagent, acrylonitrile, and an aldehyde is ideal for stereoselectively synthesizing alkenes as illustrated in the synthesis of the putative lignan "morinol I." PMID:22545004

  3. Stereoselectivity of Mucorales lipases toward triradylglycerols--a simple solution to a complex problem.

    Science.gov (United States)

    Scheib, H.; Pleiss, J.; Kovac, A.; Paltauf, F.; Schmid, R. D.

    1999-01-01

    The lipases from Rhizopus and Rhizomucor are members of the family of Mucorales lipases. Although they display high sequence homology, their stereoselectivity toward triradylglycerols (sn-2 substituted triacylglycerols) varies. Four different triradylglycerols were investigated, which were classified into two groups: flexible substrates with rotatable O'-C1' ether or ester bonds adjacent to C2 of glycerol and rigid substrates with a rigid N'-C1' amide bond or a phenyl ring in sn-2. Although Rhizopus lipase shows opposite stereopreference for flexible and rigid substrates (hydrolysis in sn-1 and sn-3, respectively), Rhizomucor lipase hydrolyzes both groups of triradylglycerols preferably in sn-1. To explain these experimental observations, computer-aided molecular modeling was applied to study the molecular basis of stereoselectivity. A generalized model for both lipases of the Mucorales family highlights the residues mediating stereoselectivity: (1) L258, the C-terminal neighbor of the catalytic histidine, and (2) G266, which is located in a loop contacting the glycerol backbone of a bound substrate. Interactions with triradylglycerol substrates are dominated by van der Waals contacts. Stereoselectivity can be predicted by analyzing the value of a single substrate torsion angle that discriminates between sn-1 and sn-3 stereopreference for all substrates and lipases investigated here. This simple model can be easily applied in enzyme and substrate engineering to predict Mucorales lipase variants and synthetic substrates with desired stereoselectivity. PMID:10210199

  4. Thermodynamic efficiency of synthesis, storage and breakdown of the high-energy metabolites by photosynthetic microalgae

    International Nuclear Information System (INIS)

    Sorgüven, Esra; Özilgen, Mustafa

    2013-01-01

    Lipids and carbohydrates are employed in the nature to store internal energy due to the large number of the high energy atomic bonds in their structure. Internal energy stored in the bonds is used to fuel work producing engines or metabolic activity of living organisms. This paper investigates the thermodynamic efficiency of the glucose and lipid synthesis and breakdown by photosynthetic microalgae. Photosynthetic microalgae are able to convert 3.8% of the solar exergy into the chemical exergy of algal lipid. As the microalgae convert the first product of the photosynthesis, i.e. glucose, into lipid, 47–49% of the chemical exergy is lost. If the microalgal cell consumes the photosynthetically produced glucose for its own energy demand, then about 30% of the glucose exergy can be converted into work potential in case of immediate and short-term energy demands. Organism can convert about 22% of the glucose exergy into work potential after a long-term storage. If the algal lipid is harvested for biodiesel production and the produced biodiesel is combusted in a Diesel engine, then about 17% of the exergy of the photosynthetically produced glucose can be converted into useful work. Biodiesel is among the most popular renewable fuels. The lipids are harvested from their storage in the cells to produce biodiesel before following the lipid breakdown path of the cellular metabolism. Our analysis indicates that, extracting the first product of photosynthesis, i.e. glucose or glucose polymers instead of lipids may be more efficient thermodynamically, if new motors capable to extract their bond energy is developed. - Highlights: • Photosynthetic microalgae convert 3.8% of the solar exergy into the chemical exergy of algal lipid. • Converting the first product of the photosynthesis (glucose) into lipid causes 47–49% of exergy loss. • Organism can convert 30% of the glucose exergy into work potential for its own immediate or short-term energy demand. • Organism can

  5. Stereo-selective hydrolytic reaction of toxic compounds by enzyme immobilized on porous ceramics; Takoshitsu ceramics kotaika koso ni yoru dokusei kagobutsu no rittai sentakuteki kasui bunkai hanno

    Energy Technology Data Exchange (ETDEWEB)

    Kato, K.; Saito, T. [National Industrial Research Institute of Nagoya, Nagoya (Japan)

    2000-08-25

    Experiment was made on stereo-selective hydrolytic reaction of trifluoroethyl ester of ketoprophene by various kinds of lipase. In addition, study was made on the stability of lipase simply immobilized on porous ceramics under the existence of organic solvent. In the experiment, the hydrolytic activity of 8 kinds of lipase was studied for ketoprophene monochloroethyl ester (1a) and trifluoroethyl ester (1b). The experiment result showed that lipase M originating in mold (Mucor Javanicus) shows a high reactivity and stereo-selectivity for the compound (1a). The lipase immobilized on porous ceramics was easily obtained by a very simple method composed of only throwing carriers into enzyme suspension, agitation and refrigerated drying. The lipase immobilized on porous ceramics 'Toyonite 200-A' synthesized from kaolinite retained the residual activity of nearly 50%, original selectivity and considerable stability after 5 times of repetitive uses. This study result is useful for bio- reactors and bio-sensors for synthesis or decomposition of compounds. (NEDO)

  6. An efficient and facile synthesis of divergent C-3/C-5 bis ...

    Indian Academy of Sciences (India)

    extensive attention in organic synthesis and also serve as potential synthons for the ... plays an important role in synthetic chemistry, because they also serve as ...... scope, rate acceleration and selective formation of bis-. MBH adduct with ...

  7. An efficient modification of ellipticine synthesis and preparation of 13-hydroxyellipticine

    Czech Academy of Sciences Publication Activity Database

    Dračínský, Martin; Sejbal, J.; Rygerová, B.; Stiborová, M.

    2007-01-01

    Roč. 48, č. 39 (2007), s. 6893-6895 ISSN 0040-4039 Institutional research plan: CEZ:AV0Z40550506 Keywords : 13-hydroxyellipticine * synthesis Subject RIV: CC - Organic Chemistry Impact factor: 2.615, year: 2007

  8. Fast and Efficient Synthesis of 4-Arylidene-3-phenylisoxazol-5-ones

    Directory of Open Access Journals (Sweden)

    Maryam Mirzazadeh

    2012-01-01

    Full Text Available A convenient and easy synthesis of 4-arylidene-3-phenylisoxazol-5-ones by the three-component reaction of hydroxylamine, ethyl benzoylacetate and aromatic aldehydes in the presence of DABCO in refluxing ethanol is reported.

  9. A Facile and Efficient Synthesis of (15R)-Latanoprost from Chiral ...

    Indian Academy of Sciences (India)

    aDepartment of Chemistry, JNTUH College of Engineering Jagtial, ... is not effective with these topically applied drugs, ... approaches for the synthesis of latanoprost.7 Recently, ... lected organic layer was washed with brine solution and.

  10. Diversity-Oriented Syntheses by Combining CuAAC and Stereoselective INCIC Reactions with Peptides

    DEFF Research Database (Denmark)

    Wang, Yuanyuan; Madsen, Anders; Diness, Frederik

    2017-01-01

    Cascade reactions proceeding through peptide-derived N-carbamoyl iminium ions are reported. Two new reactions of N-carbamoyl iminium ions are described, including a stereoselective double cyclization generating N,N′-aminals and an acid-promoted auto-oxidation. Mechanistic investigations revealed...... that the N,N′-aminal formation is reversible under strongly acidic conditions. Both of these new reactions proved to be completely orthogonal to subsequent CuAAC chemistry. The reactions were performed in solution and on solid support. The robustness and high stereoselectivity of the methodology holds great...

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  14. Enzymes as Green Catalysts for Precision Macromolecular Synthesis.

    Science.gov (United States)

    Shoda, Shin-ichiro; Uyama, Hiroshi; Kadokawa, Jun-ichi; Kimura, Shunsaku; Kobayashi, Shiro

    2016-02-24

    The present article comprehensively reviews the macromolecular synthesis using enzymes as catalysts. Among the six main classes of enzymes, the three classes, oxidoreductases, transferases, and hydrolases, have been employed as catalysts for the in vitro macromolecular synthesis and modification reactions. Appropriate design of reaction including monomer and enzyme catalyst produces macromolecules with precisely controlled structure, similarly as in vivo enzymatic reactions. The reaction controls the product structure with respect to substrate selectivity, chemo-selectivity, regio-selectivity, stereoselectivity, and choro-selectivity. Oxidoreductases catalyze various oxidation polymerizations of aromatic compounds as well as vinyl polymerizations. Transferases are effective catalysts for producing polysaccharide having a variety of structure and polyesters. Hydrolases catalyzing the bond-cleaving of macromolecules in vivo, catalyze the reverse reaction for bond forming in vitro to give various polysaccharides and functionalized polyesters. The enzymatic polymerizations allowed the first in vitro synthesis of natural polysaccharides having complicated structures like cellulose, amylose, xylan, chitin, hyaluronan, and chondroitin. These polymerizations are "green" with several respects; nontoxicity of enzyme, high catalyst efficiency, selective reactions under mild conditions using green solvents and renewable starting materials, and producing minimal byproducts. Thus, the enzymatic polymerization is desirable for the environment and contributes to "green polymer chemistry" for maintaining sustainable society.

  15. Sound Synthesis of the Harpsichord Using a Computationally Efficient Physical Model

    OpenAIRE

    Vesa Välimäki; Henri Penttinen; Mikael Laurson; Jonte Knif; Cumhur Erkut

    2004-01-01

    A sound synthesis algorithm for the harpsichord has been developed by applying the principles of digital waveguide modeling. A modification to the loss filter of the string model is introduced that allows more flexible control of decay rates of partials than is possible with a one-pole digital filter, which is a usual choice for the loss filter. A version of the commuted waveguide synthesis approach is used, where each tone is generated with a parallel combination of the string model and a s...

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

    Science.gov (United States)

    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.

  17. Photochemistry and stereoselectivity of cellular retinaldehyde-binding protein from bovine retina

    International Nuclear Information System (INIS)

    Saari, J.C.; Bredberg, D.L.

    1987-01-01

    11-cis-Retinaldehyde bound to cellular retinaldehyde-binding protein (CRALBP) is unaffected in bovine eyecup preparations by illumination that bleaches approximately 70% of the rhodopsin. Illumination of retinal homogenates to which CRALBP X [ 3 H]11-cis-retinaldehyde had been added did not result in a reduction of the specific activity of recovered 11-cis-retinaldehyde, ruling out a bleaching regeneration cycle. The quantum efficiency of photoisomerization for CRALBP X 11-cis-retinaldehyde was determined by comparing the rate of photoisomerization of 11-cis-retinaldehyde bound to purified CRALBP and opsin. The low value obtained (0.07), coupled with a low molar extinction coefficient (15,400 M-1 cm-1), results in a photosensitivity only about 4% that of rhodopsin. CRALBP binds 9-cis- and 11-cis-retinaldehyde, producing complexes with absorption maxima at 405 and 425 nm, respectively. No complexes were detected with 13-cis- and all-trans-retinaldehyde. Following incubation of CRALBP X 11-cis-retinol with an equimolar mixture of 9-, 11-, 13-cis-, and all-trans-retinaldehydes, only 11-cis-retinaldehyde and residual 11-cis-retinol are present on the protein following separation from excess retinoids. A similar result is obtained following incubation of CRALBP X 11-cis-retinol with mixtures of 9- and 11-cis-retinaldehyde ranging in composition from 9:1 to 1:9 (9-cis-:11-cis-,mol/mol). The results indicate that CRALBP X 11-cis-retinol is sufficiently stereoselective in its binding properties to warrant consideration as a component of the mechanism for the generation of 11-cis-retinaldehyde in the dark

  18. Efficient synthesis of sulfonamide derivatives on solid supports catalyzed using solvent-free and microwave-assisted methods

    Energy Technology Data Exchange (ETDEWEB)

    Camargo-Ordonez, Argelia; Moreno-Reyes, Christian; Olazaran-Santibanez, Fabian; Martinez-Hernandez, Sheila; Bocanegra-Garcia, Virgilio; Rivera, Gildardo [Universidad Autonoma de Tamaulipas, Reynosa (Mexico). Dep. de Farmacia y Quimica Medicinal

    2011-07-01

    In this work we report the synthesis of sulfonamide derivatives using a conventional procedure and with solid supports, such as silica gel, florisil, alumina, 4A molecular sieves, montmorillonite KSF, and montmorillonite K10 using solvent-free and microwave-assisted methods. Our results show that solid supports have a catalytic activity in the formation of sulfonamide derivatives. We found that florisil, montmorillonite KSF, and K10 could be used as inexpensive alternative catalysts that are easily separated from the reaction media. Additionally, solvent-free and microwave-assisted methods were more efficient in reducing reaction time and in increasing yield. (author)

  19. Efficient synthesis of sulfonamide derivatives on solid supports catalyzed using solvent-free and microwave-assisted methods

    International Nuclear Information System (INIS)

    Camargo-Ordonez, Argelia; Moreno-Reyes, Christian; Olazaran-Santibanez, Fabian; Martinez-Hernandez, Sheila; Bocanegra-Garcia, Virgilio; Rivera, Gildardo

    2011-01-01

    In this work we report the synthesis of sulfonamide derivatives using a conventional procedure and with solid supports, such as silica gel, florisil, alumina, 4A molecular sieves, montmorillonite KSF, and montmorillonite K10 using solvent-free and microwave-assisted methods. Our results show that solid supports have a catalytic activity in the formation of sulfonamide derivatives. We found that florisil, montmorillonite KSF, and K10 could be used as inexpensive alternative catalysts that are easily separated from the reaction media. Additionally, solvent-free and microwave-assisted methods were more efficient in reducing reaction time and in increasing yield. (author)

  20. An Efficient Solvent-Free Protocol for the Synthesis of 1-Amidoalkyl-2-naphthols using Silica-Supported Molybdatophosphoric Acid

    Directory of Open Access Journals (Sweden)

    Abdolkarim Zare

    2010-01-01

    Full Text Available A highly efficient, green and simple solvent-free method for the synthesis of 1-amidoalkyl-2-naphthols via one-pot multi-components condensation of 2-naphthol, aromatic aldehydes and amides in the presence of catalytic amount of silica-supported molybdatophosphoric acid (H3PMo12O40.xH2O/SiO2, 3.17 mol% is described. The reactions proceed rapidly and the title compounds are produced in high to excellent yields.

  1. A green and efficient method for the synthesis of homodimeric (β ...

    African Journals Online (AJOL)

    ... derivatives by intramolecular cyclization in various yields. Of particular interest is the use of the water as solvent of reaction and in absence of catalyst. Also these operating conditions protect the environment and economic points of view. Keywords: aqueous synthesis; bioactivity; dihydropyridine; dimedone; green method; ...

  2. ZnO nanoparticle as catalyst for efficient green one-pot synthesis of ...

    Indian Academy of Sciences (India)

    The zinc oxide (ZnO) nanoparticles functions as highly effective catalyst for the reactions of various o-hydroxy ... the synthesis of relatively large and complex molecules .... of ethylene diamine in hydrothermal ZnO nanorod syn- thesis. Di- and ...

  3. An efficient synthesis of isocoumarins via a CuI catalyzed cascade reaction process

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    3-Alkyl isocoumarins are provided by CuI/amino acid-catalyzed Sonogashira coupling reaction of o-bromo benzoic acids and terminal alkynes and the subsequent additive cyclization. This cascade process allows synthesis of diverse isocoumarins by varying both coupling partners bearing a wide range of functional groups.

  4. A Simple and Efficient Synthesis of 12-Aryl-8,9,10,12 ...

    African Journals Online (AJOL)

    Highly effective zinc oxide nanoparticles catalyzed solvent-free synthesis of some tetrahydrobenzo[a]xanthen-11-one derivatives via one-pot multi-component reaction of aldehydes, 2-naphthol and dimedone. The present approach creates a variety of biologically active heterocyclic compounds in excellent yields and short ...

  5. LaCl 3. 7H 2 O: An efficient catalyst for the synthesis of phosphinates ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 1 ... Abstract. An expeditious neat procedure was developed for the synthesis of a series of new methyl phenyl heterocyclic phosphinates (3a-l) through Michaelis-Arbuzov reaction by the reaction of various heterocyclic halides (Cl or Br) (1a-l) with dimethyl ...

  6. Efficient one-pot four-component synthesis of fused thiazolopyridin-2 ...

    Indian Academy of Sciences (India)

    . 30. 70. 8. [Net3][Ac]. 1:1:1:1. 3. 30. 80. 9. [bmim][Cl]. 1:1:1:1. 3. 30. 78. 10 .... Catalyst-free one-pot synthesis of thiazolopyridin-2-ones. 1479. Table 3. Optimization of the activity of ionic liquid after reuse. Sl. No. No. of cycle. Yield (%). 1. I. 94. 3.

  7. Efficient synthesis of large-scale thinned arrays using a density-taper initialised genetic algorithm

    CSIR Research Space (South Africa)

    Du Plessis, WP

    2011-09-01

    Full Text Available The use of the density-taper approach to initialise a genetic algorithm is shown to give excellent results in the synthesis of thinned arrays. This approach is shown to give better SLL values more consistently than using random values and difference...

  8. Copper-Catalyzed Asymmetric Allylic Alkylation of Halocrotonates : Efficient Synthesis of Versatile Chiral Multifunctional Building Blocks

    NARCIS (Netherlands)

    Hartog, Tim den; Maciá, Beatriz; Minnaard, Adriaan J.; Feringa, Bernard

    2010-01-01

    The highly enantioselective synthesis of α-methyl-substituted esters is reported in up to 90% yield and up to 99% ee using copper-TaniaPhos as chiral catalyst. The transformation proved scalable to at least 6.6 mmol (1.7 g scale). The products of this transformation have been further elaborated to

  9. Efficient and 'green' microwave-assisted synthesis of haloalkylphosphonates via the Michaelis-Arbuzov reaction

    Czech Academy of Sciences Publication Activity Database

    Jansa, Petr; Holý, Antonín; Dračínský, Martin; Baszczyňski, Ondřej; Česnek, Michal; Janeba, Zlatko

    2011-01-01

    Roč. 13, č. 4 (2011), s. 882-888 ISSN 1463-9262 R&D Projects: GA AV ČR KJB400550903; GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : microwave-assisted synthesis * haloalkylphosphonates * Michaelis-Arbuzov reaction Subject RIV: CC - Organic Chemistry Impact factor: 6.320, year: 2011

  10. One-pot efficient green synthesis of 1,4-dihydro-quinoxaline-2,3 ...

    Indian Academy of Sciences (India)

    Unknown

    Thermal and powder X-ray diffraction analysis was carried out for some hydrated crystals. Keywords. Green chemistry ... Elemental analyses were done using Carlo–Erba 1108 and Perkin–Elmer series II 2400 instruments. 2.3 General synthesis of quinoxaline derivatives ... with a pestle in a mortar at room temperature in an.

  11. Polyethylene glycol (PEG-400: An efficient medium for the synthesis of 1,2-disubstituted benzimidazoles

    Directory of Open Access Journals (Sweden)

    Raja Sekhar Mekala

    2015-12-01

    Full Text Available Polyethylene glycol (PEG-400 was found to be an inexpensive, non-toxic, and effective medium for the one-pot synthesis of 1,2-disubstituted benzimidazoles in excellent yields. Eco-friendliness, low cost, high yields, and recyclability of the PEG-400 are the important features of this protocol.

  12. A Concise Li/liq. NH{sub 3} Mediated Synthesis of (4E,10Z)-Tetradeca-4,10-dienyl Acetate: The Major Sex Pheromone of Apple Leafminer Moth, Phyllonorycter ringoniella

    Energy Technology Data Exchange (ETDEWEB)

    Prem Kumar, B.; Vijaykumar, B. V. D.; Harshavardhan, S. J.; Jung, Haedong; Xie, Yongsheng; Shin, Dongsoo; Jang, Kiwan [Changwon National Univ., Changwon (Korea, Republic of); Lee, Dong Ha [Hanbat National Univ., Daejeon (Korea, Republic of); Yoon, Yongjin [Gyeongsang National Univ., Jinju (Korea, Republic of)

    2014-01-15

    We have accomplished a protection free, concise, Li/liq. NH3 mediated and gram scale synthesis of (4E,10Z)-tetradeca-4,10-dienyl acetate (1), the major sex pheromone of apple leafminer moth, Phyllonorycter ringoniella starting from commercially available 1-pentyne, 1,4- dibromobutane and 4-petyne-1-ol in 24% overall yield. The Li/liq. NH3 based mono-alkynylation of dibromobutane has been introduced for the first time. The stereoselective formation of 10(Z) and 4(E) olefins are accomplished by partial hydrogenation (Lindlar's catalyst) and birch reduction respectively. The economy, efficiency, simplicity and high stereo chemical purity of this synthesis allow the potential use of pheromone 1 in integrated field studies to understand the behavioral responses of male apple leaf miner moth.

  13. Highly Regio- and Stereoselective Diels-Alder Cycloadditions via Two-Step and Multicomponent Reactions Promoted by Infrared Irradiation under Solvent-Free Conditions

    Science.gov (United States)

    Flores-Conde, Maria Ines; Reyes, Leonor; Herrera, Rafael; Rios, Hulme; Vazquez, Miguel A.; Miranda, Rene; Tamariz, Joaquin; Delgado, Francisco

    2012-01-01

    Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1–3 with the Knoevenagel adducts 4–6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13–17), under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13–16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO) calculations. PMID:22489113

  14. Highly Regio- and Stereoselective Diels-Alder Cycloadditions via Two-Step and Multicomponent Reactions Promoted by Infrared Irradiation under Solvent-Free Conditions

    Directory of Open Access Journals (Sweden)

    Francisco Delgado

    2012-02-01

    Full Text Available Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1–3 with the Knoevenagel adducts 4–6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13–17, under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13–16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO calculations.

  15. Visible-Light Photocatalytic Decarboxylation of α,β-Unsaturated Carboxylic Acids: Facile Access to Stereoselective Difluoromethylated Styrenes in Batch and Flow

    Science.gov (United States)

    2017-01-01

    The development of synthetic methodologies which provide access to both stereoisomers of α,β-disubstituted olefins is a challenging undertaking. Herein, we describe the development of an operationally simple and stereoselective synthesis of difluoromethylated styrenes via a visible-light photocatalytic decarboxylation strategy using fac-Ir(ppy)3 as the photocatalyst. Meta- and para-substituted cinnamic acids provide the expected E-isomer. In contrast, ortho-substituted cinnamic acids yield selectively the less stable Z-product, whereas the E-isomer can be obtained via continuous-flow processing through accurate control of the reaction time. Furthermore, our protocol is amenable to the decarboxylative difluoromethylation of aryl propiolic acids. PMID:29109904

  16. Rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes with substituted allenes: stereoselective construction of tri- and tetrasubstituted exocyclic olefins.

    Science.gov (United States)

    Evans, P Andrew; Negru, Daniela E; Shang, Deju

    2015-04-13

    The development of the stereoselective rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes (ACPs) with substituted allenes is described. This work demonstrates that activated and unactivated allenes preferentially undergo carbometalation at the distal terminus to generate tri- and tetrasubstituted exocyclic olefins with a neutral rhodium catalyst. In addition, this method provides a strategy for the total synthesis of the guaiane family of sesquiterpenes, which are not directly accessible using alkynes as exogenous π-components. Finally, the preparation of the bicyclo[5.4.0]undecane ring system using a homologated ACP tether serves to further illustrate the versatility of this approach. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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).

  18. Efficient Synthesis of Functionalized 1-oxo-1-phenyl-2-acetic Acids through Ru(II)-catalyzed Transfer Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaowei; Gong, Binwei; Meng, Yanqiu [Shenyang Univ. of Chemical Technology, Shenyang (Korea, Republic of); Yan, Yunnan [Gannan Medical Univ., Ganzhou (Korea, Republic of); Tang, Xiaobo; Eric Xu, H.; Yi, Wei [Chinese Academy of Sciences, Shanghai (China); Li, Qiu [Univ. of Science and Technology of China, Suzhou (China)

    2013-10-15

    A new and alternative method for the efficient synthesis of indanylacetic acid 2 has been developed. The methodology used RuCl(p-cymene)[(R,R)-TsDPEN] as the catalyst and formic acid-triethylamine as the hydrogen source at room temperature under solvent-free conditions, and the reactions have excellent chemoselectivity and good compatibility of substrates. Used our developed method as the starting step, gram scale synthesis of GR24 was achieved smoothly with an overall yield of 72%. All the results suggested that further development of such methodology may be of interest. Further work to establish the mechanistic reasons for selectivity and to further explore the synthetic scope of this mode of transfer hydrogenation is in progress. The synthetic SL analog, GR24 is a very potent germination stimulant, which is widely used in parasitic weed research to stimulate germination and as a standard for comparison of new germinating agents. Owing to the prevalence of GR24, its total synthesis constitutes a hot area of research. So far all known synthetic routes of GR24 used indanylacetic acid 2 as a key intermediate, for which very few methods of building compound 2 have been reported.

  19. Stereoselectivity in bioaccumulation and excretion of epoxiconazole by mealworm beetle (Tenebrio molitor) larvae.

    Science.gov (United States)

    Lv, Xiaotian; Liu, Chen; Li, Yaobin; Gao, Yongxin; Wang, Huili; Li, Jianzhong; Guo, Baoyuan

    2014-09-01

    Stereoselectivity in bioaccumulation and excretion of stereoisomers of epoxiconazole by mealworm beetle (Tenebrio molitor) larvae through dietary exposure was investigated. Liquid chromatography tandem mass spectrometry (HPLC-MS/MS) method that use a ChiralcelOD-3R[cellulosetris-Tris-(3, 5-dichlorophenyl-carbamate)] chromatography column was applied to carry out chiral separation of the stereoisomers. Wheat bran was spiked with racemic epoxiconazole at two dose levels of 20mg/kg and 2mg/kg (dry weight) to feed T. molitor larvae. The results showed that both the doses of epoxiconazole were taken up by Tenebrio molitor larvae rapidly at the initial stages. There was a significant trend of stereoselective bioaccumulation in the larvae with a preferential accumulation of (-)-epoxiconazole in the 20mg/kg dose. The stereoselectivity in bioaccumulation in the 2mg/kg dosage was not obvious compared to the 20mg/kg group. Results of excretion indicated an active excretion is an important pathway for the larvae to eliminate epoxiconazole which was a passive transport process with non stereoselectivity. The faster elimination might be the reason for the low accumulation of epoxiconazole, as measured by bioaccumulation factor (BAF). Copyright © 2014 Elsevier Inc. All rights reserved.

  20. Hexafluorobenzene: A powerful solvent for a noncovalent stereoselective organocatalytic Michael addition reaction

    KAUST Repository

    Lattanzi, Alessandra

    2012-01-01

    A dramatic enhancement of the diastereo- and enantioselectivity in the nitro-Michael addition reaction organocatalysed by a commercially available α,α-l-diaryl prolinol was disclosed when performing the reaction in unconventional hexafluorobenzene as a medium. DFT calculations were performed to clarify the origin of stereoselectivity and the role of C 6F 6. © The Royal Society of Chemistry 2012.

  1. DFT study of the mechanism and stereoselectivity of the 1,3-dipolar ...

    Indian Academy of Sciences (India)

    and methyl acrylate) using DFT method. An ana- lysis of ..... field (SCRF)30,46 model based on the polarizable con- tinuum model (PCM) of Tomasi's group47 have been applied. ... stereoselectivity relative to the gas-phase since the trends of ...

  2. Enantio- and Stereoselective Construction of Atisane Scaffold via Organocatalytic Intramolecular Michael Reaction and Diels-Alder Reaction.

    Science.gov (United States)

    Sekita, Hiroko; Adachi, Kyohei; Kobayashi, Ippei; Sato, Yusuke; Nakada, Masahisa

    2017-05-05

    An enantio- and stereoselective construction of the atisane scaffold via organocatalytic intramolecular Michael reaction and Diels-Alder reaction is described. The organocatalytic intramolecular Michael reaction has been found to stereoselectively generate a trans-stereodiad comprising an all-carbon quaternary and a tertiary stereogenic centers. Use of the chiral secondary amine bearing thiourea with benzoic acid as additive is the key to obtaining the desired product with excellent ee in synthetically acceptable yield. The prepared chiral building block has been successfully converted to the compound including the atisane scaffold via the highly stereoselective intramolecular Diels-Alder reaction.

  3. Stereoselective total syntheses of three Lycopodium alkaloids, (-)-magellanine, (+)-magellaninone, and (+)-paniculatine, based on two Pauson-Khand reactions.

    Science.gov (United States)

    Kozaka, Takashi; Miyakoshi, Naoki; Mukai, Chisato

    2007-12-21

    The total syntheses of (-)-magellanine, (+)-magellaninone, and (+)-paniculatine were completed from diethyl l-tartrate via the common intermediate in a stereoselective manner. The crucial steps in these syntheses involved two intramolecular Pauson-Khand reactions of enynes: the first Pauson-Khand reaction constructed the bicyclo[4.3.0] carbon framework, the corresponding A and B rings of these alkaloids in a highly stereoselective manner, whereas the second Pauson-Khand reaction stereoselectively produced the bicyclo[3.3.0]skeleton, which could be converted into the C and D rings of the target natural products.

  4. Stereoselective and regiospecific hydroxylation of ketamine and norketamine.

    Science.gov (United States)

    Desta, Zeruesenay; Moaddel, Ruin; Ogburn, Evan T; Xu, Cong; Ramamoorthy, Anuradha; Venkata, Swarajya Lakshmi Vattem; Sanghvi, Mitesh; Goldberg, Michael E; Torjman, Marc C; Wainer, Irving W

    2012-11-01

    The objective was to determine the cytochrome P450s (CYPs) responsible for the stereoselective and regiospecific hydroxylation of ketamine [(R,S)-Ket] to diastereomeric hydroxyketamines, (2S,6S;2R,6R)-HK (5a) and (2S,6R;2R,6S)-HK (5b) and norketamine [(R,S)-norKet] to hydroxynorketamines, (2S,6S;2R,6R)-HNK (4a), (2S,6R;2R,6S)-HNK (4b), (2S,5S;2R,5R)-HNK (4c), (2S,4S;2R,4R)-HNK (4d), (2S,4R;2R,4S)-HNK (4e), (2S,5R;2R,5S)-HNK (4f). The enantiomers of Ket and norKet were incubated with characterized human liver microsomes (HLMs) and expressed CYPs. Metabolites were identified and quantified using LC/MS/MS and apparent kinetic constants estimated using single-site Michaelis-Menten, Hill or substrate inhibition equation. 5a was predominantly formed from (S)-Ket by CYP2A6 and N-demethylated to 4a by CYP2B6. 5b was formed from (R)- and (S)-Ket by CYP3A4/3A5 and N-demethylated to 4b by multiple enzymes. norKet incubation produced 4a, 4c and 4f and minor amounts of 4d and 4e. CYP2A6 and CYP2B6 were the major enzymes responsible for the formation of 4a, 4d and 4f, and CYP3A4/3A5 for the formation of 4e. The 4b metabolite was not detected in the norKet incubates. 5a and 4b were detected in plasma samples from patients receiving (R,S)-Ket, indicating that 5a and 5b are significant Ket metabolites. Large variations in HNK concentrations were observed suggesting that pharmacogenetics and/or metabolic drug interactions may play a role in therapeutic response.

  5. Rapid and efficient synthesis of soluble graphene nanosheets using N-methyl-p-aminophenol sulfate as a reducing agent

    International Nuclear Information System (INIS)

    Wang Xialie; Wen Xiaohong; Liu Zhanpeng; Tan Yi; Yuan Ye; Zhang Ping

    2012-01-01

    Mass production of soluble graphene still remains a challenge, although several methodologies have been proposed. Here we report a rapid and efficient method for the synthesis of soluble graphene nanosheets (GNSs) with long-term dispersion stability in both aqueous and common organic solvents. Within only 12 min at 95 °C, exfoliated graphite oxide in ammonia solution (pH 10) was reduced to soluble GNSs using N-methyl-p-aminophenol sulfate (metol) as a reducing agent without external stabilizers. The prepared GNSs were characterized by different techniques and a comparison of metol and hydrazine hydrate as reducing agents was made. The results indicated that, with the advantages of being rapid, efficient, inexpensive and relatively environmentally friendly, the reduction of graphite oxide into soluble GNSs by metol is a promising substitute for hydrazine hydrate in the mass production of soluble GNSs. (paper)

  6. Efficient One-Pot Synthesis of Colloidal Zirconium Oxide Nanoparticles for High-Refractive-Index Nanocomposites.

    Science.gov (United States)

    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.

  7. New and Efficient Synthesis of Amides from Acid Chlorides Using Diisobutyl(amino)aluminum

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jae Kyo; Shin, Won Kyu; An, Duk Keun [Kangwon National Univ., Chuncheon (Korea, Republic of)

    2013-05-15

    In conclusion, we have developed a facile, alternative method for the formation of secondary and tertiary amides including morpholine amides from acid chlorides by using diisobutyl(amino)aluminum under mild reaction conditions. The advantages of the present method include the high product yields, simple experimental procedure, short reaction time (10 min), and the fact that an excess amount of amine is not required. This result suggests that our new method can provide an alternative method for the synthesis of useful amides from acid chlorides. Amides are valuable functional groups in biological, agrochemical, and pharmaceutical molecules. Several amides such as Weinreb amides, morpholine amides, and pyrrolidine amides are useful intermediates for the synthesis of aldehydes or ketones. Among them, morpholine amides are a cheap and good substitute for Weinreb amides.

  8. New and Efficient Synthesis of Amides from Acid Chlorides Using Diisobutyl(amino)aluminum

    International Nuclear Information System (INIS)

    Park, Jae Kyo; Shin, Won Kyu; An, Duk Keun

    2013-01-01

    In conclusion, we have developed a facile, alternative method for the formation of secondary and tertiary amides including morpholine amides from acid chlorides by using diisobutyl(amino)aluminum under mild reaction conditions. The advantages of the present method include the high product yields, simple experimental procedure, short reaction time (10 min), and the fact that an excess amount of amine is not required. This result suggests that our new method can provide an alternative method for the synthesis of useful amides from acid chlorides. Amides are valuable functional groups in biological, agrochemical, and pharmaceutical molecules. Several amides such as Weinreb amides, morpholine amides, and pyrrolidine amides are useful intermediates for the synthesis of aldehydes or ketones. Among them, morpholine amides are a cheap and good substitute for Weinreb amides

  9. An Efficient, Mild and Solvent-Free Synthesis of Benzene Ring Acylated Harmalines

    Directory of Open Access Journals (Sweden)

    Sabira Begum

    2009-12-01

    Full Text Available A facile synthesis of a series of benzene ring acylated analogues of harmaline has been achieved by Friedel-Crafts acylation under solvent-free conditions at room temperature using acyl halides/acid anhydrides and AlCl3. The reaction afforded 10- and 12-acyl analogues of harmaline in good yield, along with minor quantities of N-acyl-tryptamines and 8-acyl analogues of N-acyltryptamines.

  10. Efficient and reproducible synthesis of [1-{sup 11}C]acetyl chloride using the loop method

    Energy Technology Data Exchange (ETDEWEB)

    Arai, Takuya [Department of Molecular Probes, Molecular Imaging Center, National Institute of Radiological Sciences, 4-9-1 Anagawa, Inage-ku, Chiba 263-8555 (Japan); Zhang, Ming-Rong [Department of Molecular Probes, Molecular Imaging Center, National Institute of Radiological Sciences, 4-9-1 Anagawa, Inage-ku, Chiba 263-8555 (Japan)], E-mail: zhang@nirs.go.jp; Ogawa, Masanao [Department of Molecular Probes, Molecular Imaging Center, National Institute of Radiological Sciences, 4-9-1 Anagawa, Inage-ku, Chiba 263-8555 (Japan); SHI Accelerator Service Co. Ltd., 1-17-6 Osaki, Shinagawa-ku, Tokyo 141-8686 (Japan); Fukumura, Toshimitsu; Kato, Koichi; Suzuki, Kazutoshi [Department of Molecular Probes, Molecular Imaging Center, National Institute of Radiological Sciences, 4-9-1 Anagawa, Inage-ku, Chiba 263-8555 (Japan)

    2009-02-15

    [1-{sup 11}C]Acetyl chloride ([{sup 11}C]AcCl), an important [{sup 11}C]acylating agent, was synthesized by reacting [{sup 11}C]CO{sub 2} with methylmagnesium bromide coated on the inner surface of a polyethylene loop (loop method). By optimizing the reaction conditions and synthesis parameters, [1-{sup 11}C]phenylacetate and [1-{sup 11}C]benzylacetate were produced from [{sup 11}C]AcCl in high radiochemical yield and specific activity.

  11. Simple, mild, and highly efficient synthesis of 2-substituted benzimidazoles and bis-benzimidazoles

    OpenAIRE

    Eren,Bilge; Bekdemir,Yunus

    2014-01-01

    A new convenient method for preparation of 2-substituted benzimidazoles and bis-benzimidazoles is presented. In this method, o-phenylenediamines were condensed with bisulfite adducts of various aldehydes and di-aldehydes under neat conditions by microwave heating. The results were also compared with results of synthesis by conventional heating under reflux. Structures of the products were confirmed by infrared, ¹H- and 13C-NMR spectroscopy. Short reaction times, good yields, easy purification...

  12. Templated synthesis of nickel nanoparticles: Toward heterostructured nanocomposites for efficient hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, Nicholas Cole [Iowa State Univ., Ames, IA (United States)

    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 (Ni$\\subset$ SiO2) 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 Ni0 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$\\subset$SiO2 nanocapsules were used as seeds to induce heterogeneous nucleation and subsequent growth within the nanocapsule via electroless nickel plating. Nickel nanoparticle

  13. One-pot synthesis of well-defined polyether/polyester block copolymers and terpolymers by a highly efficient catalyst switch approach

    KAUST Repository

    Alamri, Haleema

    2016-04-20

    A highly efficient methodology, based on a novel catalyst switch approach with rapid crossover characteristics, was developed for the one-pot synthesis of block co/terpolymers of cyclic ethers and esters. This new approach, which takes advantage of one of the best catalysts for epoxide (t-BuP4) and cyclic ester (t-BuP2) polymerization, opens new horizons toward the synthesis of cyclic ether/ester complex macromolecular architectures. © The Royal Society of Chemistry 2016.

  14. One-pot synthesis of well-defined polyether/polyester block copolymers and terpolymers by a highly efficient catalyst switch approach

    KAUST Repository

    Alamri, Haleema; Hadjichristidis, Nikolaos

    2016-01-01

    A highly efficient methodology, based on a novel catalyst switch approach with rapid crossover characteristics, was developed for the one-pot synthesis of block co/terpolymers of cyclic ethers and esters. This new approach, which takes advantage of one of the best catalysts for epoxide (t-BuP4) and cyclic ester (t-BuP2) polymerization, opens new horizons toward the synthesis of cyclic ether/ester complex macromolecular architectures. © The Royal Society of Chemistry 2016.

  15. Simple, mild, and highly efficient synthesis of 2-substituted benzimidazoles and bis-benzimidazoles

    Energy Technology Data Exchange (ETDEWEB)

    Eren, Bilge, E-mail: bilge.eren@bilecik.edu.tr [Faculty of Science and Arts, Department of Chemistry, Bilecik Seyh Edebali University, (Turkey); Bekdemir, Yunus [Faculty of Science and Arts, Canik Basari University, Samsun (Turkey)

    2014-07-01

    A new convenient method for preparation of 2-substituted benzimidazoles and bis-benzimidazoles is presented. In this method, o-phenylenediamines were condensed with bisulfite adducts of various aldehydes and di-aldehydes under neat conditions by microwave heating. The results were also compared with results of synthesis by conventional heating under reflux. Structures of the products were confirmed by infrared, {sup 1}H- and {sup 13}C-NMR spectroscopy. Short reaction times, good yields, easy purification of products, and mild reaction conditions are the main advantages of this method. (author)

  16. Facile and efficient synthesis of [{sup 18}F]fluoromisonidazole using novel 2-nitroimidazole derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Young-Do; Lim, Seok Tae; Sohn, Myung-Hee; Kim, Hee-Kwon, E-mail: hkkim717@jbnu.ac.kr [Department of Nuclear Medicine, Chonbuk National University Medical School and Hospital, Jeonju (Korea, Republic of); Jung, Yongju [Department of Chemical Engineering, Korea University of Technology and Education, Cheonan (Korea, Republic of)

    2016-07-01

    [{sup 18}F]Fluoromisonidazole ([{sup 18}F]FMISO) is a hypoxia imaging marker utilized in positron emission tomography. Novel FMISO precursors were prepared from a commercially available material, and several reaction factors that affect synthesis of [{sup 18}F]FMISO were examined to achieve a higher fluorination yield. [{sup 18}F]FMISO was obtained from radiosynthesis, followed by the hydrolysis of protecting groups with HCl. New 2-nitroimidazole precursor showed a higher [{sup 18}F]fluorination and a higher synthetic yield. This result provided alternative guidelines for the preparation of hypoxia imaging marker. (author)

  17. 1,5-Anhydro-D-Fructose – Efficient Synthesis and Chemical Uses

    DEFF Research Database (Denmark)

    Lundt, Inge; Dekany, Gyula; Stütz, Arnold E.

    as well as for derivatives and analogues thereof. The potential of AF will be highlighted as will be the use of AF as a chiral building block for the preparation of other interesting compounds with biological activities such as, for example, Deoxymannojirimycin (DMJ). [1] S.M. Andersen, I. Lundt, J......1,5-Anhydro-D-fructose (AF) is a valuable chiral building block for organic synthesis.[1] However, the antioxidant and antimicrobial properties of AF are equally important.[1] Due to these interesting properties AF is heavily patented for the use in pharmaceuticals, foods and cosmetics. However...

  18. Highly Enantioselective Rhodium-Catalyzed Addition of Arylboroxines to Simple Aryl Ketones: Efficient Synthesis of Escitalopram.

    Science.gov (United States)

    Huang, Linwei; Zhu, Jinbin; Jiao, Guangjun; Wang, Zheng; Yu, Xingxin; Deng, Wei-Ping; Tang, Wenjun

    2016-03-24

    Highly enantioselective additions of arylboroxines to simple aryl ketones have been achieved for the first time with a Rh/(R,R,R,R)-WingPhos catalyst, thus providing a range of chiral diaryl alkyl carbinols with excellent ee values and yields. (R,R,R,R)-WingPhos has been proven to be crucial for the high reactivity and enantioselectivity. The method has enabled a new, concise, and enantioselective synthesis of the antidepressant drug escitalopram. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Simple, mild, and highly efficient synthesis of 2-substituted benzimidazoles and bis-benzimidazoles

    International Nuclear Information System (INIS)

    Eren, Bilge; Bekdemir, Yunus

    2014-01-01

    A new convenient method for preparation of 2-substituted benzimidazoles and bis-benzimidazoles is presented. In this method, o-phenylenediamines were condensed with bisulfite adducts of various aldehydes and di-aldehydes under neat conditions by microwave heating. The results were also compared with results of synthesis by conventional heating under reflux. Structures of the products were confirmed by infrared, 1 H- and 13 C-NMR spectroscopy. Short reaction times, good yields, easy purification of products, and mild reaction conditions are the main advantages of this method. (author)

  20. Simple, mild, and highly efficient synthesis of 2-substituted benzimidazoles and bis-benzimidazoles

    Directory of Open Access Journals (Sweden)

    Bilge Eren

    2014-01-01

    Full Text Available A new convenient method for preparation of 2-substituted benzimidazoles and bis-benzimidazoles is presented. In this method, o-phenylenediamines were condensed with bisulfite adducts of various aldehydes and di-aldehydes under neat conditions by microwave heating. The results were also compared with results of synthesis by conventional heating under reflux. Structures of the products were confirmed by infrared, ¹H- and 13C-NMR spectroscopy. Short reaction times, good yields, easy purification of products, and mild reaction conditions are the main advantages of this method.

  1. Financing of energy-efficient productive industrial projects. Situation and first ideas for the future. Synthesis

    International Nuclear Information System (INIS)

    Billard, Yannael; Julien, Emmanuel; Blaisonneau, Laurent; Streiff, Frederic; Padilla, Sylvie; Benazzi, Eric; Domergue, Bruno; Fraysse, Sebastien; Gaussens, Jean-Pierre; Packeu, Paris; Bodino, Didier; Randimbivololona, Prisca; Verbbrughe, Gregory; Bissonnier, Alain; Dantec, Caroline

    2016-11-01

    Based on in-depth interviews with decision makers and experts belonging to energy consuming industrial groups, or involved in technological offer or in financing, this study addressed the issue of energy efficiency in the industrial sector, and of its financing. Interviewed persons represented 11 large companies, 5 medium-sized companies, and 14 industrial sectors, and 3 main professional profiles (from technical to financial). The authors thus explored current financing models implemented to finance energy efficiency, by analysing existing decision-making processes, brakes on energy efficiency in industry, levers favourable to energy efficiency in industry, operational and functional organisations addressing issues related to energy efficiency, the risk management policy implemented for the assessment and follow-up of investments in energy efficiency, and existing and envisaged financial packages to make these investments possible. As far as financing is concerned, the authors analyse present practices, difficulties faced, good and repeatable practices, and discuss some lines of thought to mobilise actors in order to structure and promote energy efficiency in industrial projects, to reduce the risk for an easier financing of such projects, to structure financing tools, to promote incentive taxes and aids

  2. Efficient seed-mediated method for the large-scale synthesis of Au nanorods

    International Nuclear Information System (INIS)

    Ahmed, Waqqar; Bhatti, Arshad Saleem; Ruitenbeek, Jan M. van

    2017-01-01

    Seed-mediated methods are widely followed for the synthesis of Au nanorods (NRs). However, mostly dilute concentrations of the Au precursor (HAuCl_4) are used in the growth solution, which leads to a low final concentration of NRs. Attempts of increasing the concentration of NRs by simply increasing the concentration of HAuCl_4, other reagents in the growth solution and seeds lead to a faster growth kinetics which is not favourable for NR growth. Herein, we demonstrate that the increase in growth kinetics for high concentrations of reagents in growth solution can be neutralised by decreasing the pH of the solution. The synthesis of the NRs can be scaled up by using higher concentrations of reagents and adding an optimum concentration of HCl in the growth solution. The concentration of HAuCl_4 in the growth solution can be increased up to 5 mM, and 10–20 times more NRs can be synthesised for the same reaction volume compared to that of the conventional seed-mediated method. We have also noticed that a cetyltrimethylammonium bromide (CTAB)-to-HAuCl_4 molar ratio of 50 is sufficient for obtaining high yield of NRs.

  3. Sound Synthesis of the Harpsichord Using a Computationally Efficient Physical Model

    Directory of Open Access Journals (Sweden)

    Knif Jonte

    2004-01-01

    Full Text Available A sound synthesis algorithm for the harpsichord has been developed by applying the principles of digital waveguide modeling. A modification to the loss filter of the string model is introduced that allows more flexible control of decay rates of partials than is possible with a one-pole digital filter, which is a usual choice for the loss filter. A version of the commuted waveguide synthesis approach is used, where each tone is generated with a parallel combination of the string model and a second-order resonator that are excited with a common excitation signal. The second-order resonator, previously proposed for this purpose, approximately simulates the beating effect appearing in many harpsichord tones. The characteristic key-release thump terminating harpsichord tones is reproduced by triggering a sample that has been extracted from a recording. A digital filter model for the soundboard has been designed based on recorded bridge impulse responses of the harpsichord. The output of the string models is injected in the soundboard filter that imitates the reverberant nature of the soundbox and, particularly, the ringing of the short parts of the strings behind the bridge.

  4. Sound Synthesis of the Harpsichord Using a Computationally Efficient Physical Model

    Science.gov (United States)

    Välimäki, Vesa; Penttinen, Henri; Knif, Jonte; Laurson, Mikael; Erkut, Cumhur

    2004-12-01

    A sound synthesis algorithm for the harpsichord has been developed by applying the principles of digital waveguide modeling. A modification to the loss filter of the string model is introduced that allows more flexible control of decay rates of partials than is possible with a one-pole digital filter, which is a usual choice for the loss filter. A version of the commuted waveguide synthesis approach is used, where each tone is generated with a parallel combination of the string model and a second-order resonator that are excited with a common excitation signal. The second-order resonator, previously proposed for this purpose, approximately simulates the beating effect appearing in many harpsichord tones. The characteristic key-release thump terminating harpsichord tones is reproduced by triggering a sample that has been extracted from a recording. A digital filter model for the soundboard has been designed based on recorded bridge impulse responses of the harpsichord. The output of the string models is injected in the soundboard filter that imitates the reverberant nature of the soundbox and, particularly, the ringing of the short parts of the strings behind the bridge.

  5. Efficient seed-mediated method for the large-scale synthesis of Au nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, Waqqar; Bhatti, Arshad Saleem [COMSATS Institute of Information Technology, Department of Physics (Pakistan); Ruitenbeek, Jan M. van, E-mail: Ruitenbeek@physics.leidenuniv.nl [Leiden University, Huygens-Kamerlingh Onnes Laboratory (Netherlands)

    2017-03-15

    Seed-mediated methods are widely followed for the synthesis of Au nanorods (NRs). However, mostly dilute concentrations of the Au precursor (HAuCl{sub 4}) are used in the growth solution, which leads to a low final concentration of NRs. Attempts of increasing the concentration of NRs by simply increasing the concentration of HAuCl{sub 4}, other reagents in the growth solution and seeds lead to a faster growth kinetics which is not favourable for NR growth. Herein, we demonstrate that the increase in growth kinetics for high concentrations of reagents in growth solution can be neutralised by decreasing the pH of the solution. The synthesis of the NRs can be scaled up by using higher concentrations of reagents and adding an optimum concentration of HCl in the growth solution. The concentration of HAuCl{sub 4} in the growth solution can be increased up to 5 mM, and 10–20 times more NRs can be synthesised for the same reaction volume compared to that of the conventional seed-mediated method. We have also noticed that a cetyltrimethylammonium bromide (CTAB)-to-HAuCl{sub 4} molar ratio of 50 is sufficient for obtaining high yield of NRs.

  6. Spray-combustion synthesis: efficient solution route to high-performance oxide transistors.

    Science.gov (United States)

    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.

  7. Total synthesis and structural validation of cyclodepsipeptides solonamide A and B

    DEFF Research Database (Denmark)

    Kitir, Betül; Baldry, Mara; Ingmer, Hanne

    2014-01-01

    , autoinducing peptide I (AIP-I). To enable more comprehensive studies, we embarked on the chemical synthesis of solonamides A and B. The key synthetic steps were formation of the (R)-β-hydroxy-fatty-acids by stereo-selective aldol reactions and a cyclative macrolactamization, which proceeded under highly dilute...

  8. Modified Julia Olefination on Anhydrides: Extension and Limitations. Application to the Synthesis of Maculalactone B.

    Science.gov (United States)

    Dussart, Nicolas; Trinh, Huu Vinh; Gueyrard, David

    2016-10-07

    The preparation of exo-enol esters from cyclic anhydrides is reported using a modified Julia olefination. The reaction is highly stereoselective. The Smiles rearrangement can be performed in a one-pot process, giving a straightforward access to exo-enol lactones. Furthermore, the reaction was extended to semistabilized sulfones, and this methodology was applied to the synthesis of maculalactone B.

  9. A Green, Enantioselective Synthesis of Warfarin for the Undergraduate Organic Laboratory

    Science.gov (United States)

    Wong, Terence C.; Sultana, Camille M.; Vosburg, David A.

    2010-01-01

    The enantioselective synthesis of drugs is of fundamental importance in the pharmaceutical industry. In this experiment, students synthesize either enantiomer of warfarin, a widely used anticoagulant, in a single step from inexpensive starting materials. Stereoselectivity is induced by a commercial organocatalyst, ("R","R")- or…

  10. A concise, efficient synthesis of sugar-based benzothiazoles through chemoselective intramolecular C-S coupling

    KAUST Repository

    Shen, Chao; Xia, Haijun; Yan, Hua; Chen, Xinzhi; Ranjit, Sadananda; Xie, Xiaoji; Tan, Davin; Lee, Richmond; Yang, Yanmei; Xing, Bengang; Huang, Kuo-Wei; Zhang, Pengfei; Liu, Xiaogang

    2012-01-01

    in the efficiency and chemoselectivity of reaction. These fluorescent glycoconjugates can be observed to readily enter mammalian tumor cells and exhibit potential in vitro antitumor activity. This journal is © The Royal Society of Chemistry 2012.

  11. Atom-Economical Dimerization Strategy by the Rhodium-Catalyzed Addition of Carboxylic Acids to Allenes: Protecting-Group-Free Synthesis of Clavosolide A and Late-Stage Modification.

    Science.gov (United States)

    Haydl, Alexander M; Breit, Bernhard

    2015-12-14

    Natural products of polyketide origin with a high level of symmetry, in particular C2 -symmetric diolides as a special macrolactone-based product class, often possess a broad spectrum of biological activity. An efficient route to this important structural motif was developed as part of a concise and highly convergent synthesis of clavosolide A. This strategy features an atom-economic "head-to-tail" dimerization by the stereoselective rhodium-catalyzed addition of carboxylic acids to terminal allenes with the simultaneous construction of two new stereocenters. The excellent efficiency and selectivity with which the C2 -symmetric core structures were obtained are remarkable considering the outcome under classical dimerization conditions. Furthermore, this approach facilitates late-stage modification and provides ready access to potential new lead structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Synthesis and Biological Investigation of Antioxidant Pyrrolomorpholine Spiroketal Natural Products

    Science.gov (United States)

    Verano, Alyssa Leigh

    The pyrrolomorpholine spiroketal natural product family is comprised of epimeric furanose and pyranose isomers. These compounds were isolated from diverse plant species, all of which are used as traditional Chinese medicines for the treatment of a variety of diseases. Notably, the spiroketal natural products acortatarins A and B exhibit antioxidant activity in a diabetic renal cell model, significantly attenuating hyperglycemia-induced production of reactive oxygen species (ROS), a hallmark of diabetic nephropathy. The xylapyrrosides, additional members of the family, also inhibit t-butyl hydroperoxide-induced cytotoxicity in rat vascular smooth muscle cells. Accordingly, these natural products have therapeutic potential for the treatment of oxidative stress-related pathologies, and synthetic access would provide an exciting opportunity to investigate bioactivity and mechanism of action. Herein, we report the stereoselective synthesis of acortatarins A and B, furanose members of the pyrrolomorpholine spiroketal family. Our synthetic route was expanded to synthesize the pyranose congeners, thus completing entire D-enantiomeric family of natural products. Efficient access towards these scaffolds enabled systematic analogue synthesis, investigation of mechanism-of-action, and the discovery of novel antioxidants.

  13. An efficient method based on the uniformity principle for synthesis of large-scale heat exchanger networks

    International Nuclear Information System (INIS)

    Zhang, Chunwei; Cui, Guomin; Chen, Shang

    2016-01-01

    Highlights: • Two dimensionless uniformity factors are presented to heat exchange network. • The grouping of process streams reduces the computational complexity of large-scale HENS problems. • The optimal sub-network can be obtained by Powell particle swarm optimization algorithm. • The method is illustrated by a case study involving 39 process streams, with a better solution. - Abstract: The optimal design of large-scale heat exchanger networks is a difficult task due to the inherent non-linear characteristics and the combinatorial nature of heat exchangers. To solve large-scale heat exchanger network synthesis (HENS) problems, two dimensionless uniformity factors to describe the heat exchanger network (HEN) uniformity in terms of the temperature difference and the accuracy of process stream grouping are deduced. Additionally, a novel algorithm that combines deterministic and stochastic optimizations to obtain an optimal sub-network with a suitable heat load for a given group of streams is proposed, and is named the Powell particle swarm optimization (PPSO). As a result, the synthesis of large-scale heat exchanger networks is divided into two corresponding sub-parts, namely, the grouping of process streams and the optimization of sub-networks. This approach reduces the computational complexity and increases the efficiency of the proposed method. The robustness and effectiveness of the proposed method are demonstrated by solving a large-scale HENS problem involving 39 process streams, and the results obtained are better than those previously published in the literature.

  14. A straightforward and efficient synthesis of 3-(pyrimidinyl)propanoates from levulinic acid

    International Nuclear Information System (INIS)

    Flores, Alex F.C.; Malavolta, Juliana L.; Souto, Alynne A.; Goularte, Rayane B.; Flores, Darlene C.

    2013-01-01

    The cyclocondensation of methyl 7,7,7-trifluoro-4-methoxy-6-oxo-4-heptenoate and methyl 7,7,7-trichloro-4-methoxy-6-oxo-4-heptenoate, derived from levulinic acid with amidines [NH 2 CONH 2 , NH 2 CR(NH) (R = H, Me, Ph, NH 2 , SMe and 1H-pyrazol-1-yl), 5-amino-3-methyl-1H-pyrazol and 2-aminothiazole] into pyrimidine and pyrimidine-like derivatives as a new type of glutamate-like 3-(trihalomethylatedpyrimidinyl)propanoate is reported. Preparation of 3-(trihalomethylatedpyrimidinyl) propanohydrazides is also described. The synthetic potential of this straightforward protocol was established by the synthesis of fourteen new 3-(pyrimidinyl) propanoates in regular to good yields (38-92%). The structural assignments were based on the analysis of their 1 H and 13 C nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry (GC-MS) data. (author)

  15. Synthesis of taurine–fluorescein conjugate and evaluation of its retina-targeted efficiency in vitro

    Directory of Open Access Journals (Sweden)

    Meihong Huang

    2014-12-01

    Full Text Available In this work, retinal penetration of fluorescein was achieved in vitro by covalent attachment of taurine to fluorescein, yielding the F–Tau conjugate. Nuclear magnetic resonance (NMR and high resolution mass spectrometry (HRMS were used to confirm the successful synthesis of F–Tau. The cellular uptake of F–Tau in adult retinal pigment epithelial cells (ARPE-19 and human retinal microvascular endothelial cells (hRMECs was visualized via confocal scanning microscopy. The results indicated an improvement of solubility and a reduction of logP of F–Tau compared with fluorescein. As compared with fluorescein, F–Tau showed little toxicity, and was retained longer by cells in uptake experiments. F–Tau also displayed higher transepithelial permeabilities than fluorescein in ARPE-19 and hRMECs monolayer cells (P<0.05. These results showed that taurine may be a useful ligand for targeting small-molecule hydrophobic pharmaceuticals into the retina.

  16. A straightforward and efficient synthesis of 3-(pyrimidinyl)propanoates from levulinic acid

    Energy Technology Data Exchange (ETDEWEB)

    Flores, Alex F.C.; Malavolta, Juliana L.; Souto, Alynne A.; Goularte, Rayane B.; Flores, Darlene C., E-mail: alex.fcf@ufsm.br [Universidade Federal de Santa Maria (UFSM/NUQUIMHE), RS (Brazil). Departamento de Quimica. Nucleo de Quimica de Heterociclos

    2013-04-15

    The cyclocondensation of methyl 7,7,7-trifluoro-4-methoxy-6-oxo-4-heptenoate and methyl 7,7,7-trichloro-4-methoxy-6-oxo-4-heptenoate, derived from levulinic acid with amidines [NH{sub 2}CONH{sub 2}, NH{sub 2}CR(NH) (R = H, Me, Ph, NH{sub 2}, SMe and 1H-pyrazol-1-yl), 5-amino-3-methyl-1H-pyrazol and 2-aminothiazole] into pyrimidine and pyrimidine-like derivatives as a new type of glutamate-like 3-(trihalomethylatedpyrimidinyl)propanoate is reported. Preparation of 3-(trihalomethylatedpyrimidinyl) propanohydrazides is also described. The synthetic potential of this straightforward protocol was established by the synthesis of fourteen new 3-(pyrimidinyl) propanoates in regular to good yields (38-92%). The structural assignments were based on the analysis of their {sup 1}H and {sup 13}C nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry (GC-MS) data. (author)

  17. An Efficient Amide-Aldehyde-Alkene Condensation: Synthesis for the N-Allyl Amides.

    Science.gov (United States)

    Quan, Zheng-Jun; Wang, Xi-Cun

    2016-02-01

    The allylamine skeleton represents a significant class of biologically active nitrogen compounds that are found in various natural products and drugs with well-recognized pharmacological properties. In this personal account, we will briefly discuss the synthesis of allylamine skeletons. We will focus on showing a general protocol for Lewis acid-catalyzed N-allylation of electron-poor N-heterocyclic amides and sulfonamide via an amide-aldehyde-alkene condensation reaction. The substrate scope with respect to N-heterocyclic amides, aldehydes, and alkenes will be discussed. This method is also capable of preparing the Naftifine motif from N-methyl-1-naphthamide or methyl (naphthalene-1-ylmethyl)carbamate, with paraformaldehyde and styrene in a one-pot manner. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Selective and efficient synthesis of ethanol from dimethyl ether and syngas

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn

    well-established processes. Syngas can be produced from biomass, making the entire process sustainable and environmentally friendly. The main benefit of this method is its unprecedented selectivity towards EtOH, while MeOH, the primary by-product, and the unreacted syngas are easily recycled...... but it is not sufficiently active or stable to be applied industrially. In this PhD project, the formation of MA over Mordenite has been studied experimentally and by density functional theory (DFT) calculations. The DFT study of the reaction path has shown that ketene is a reaction intermediate, a result with has been...... in the feed, the deactivation rate decreases with increasing MA concentration. However, the precise connection is still unknown. The results of this PhD project contribute significantly to the understanding of the reactions taking place on Mordenite during MA synthesis and form a firm foundation...

  19. Efficient method of enzymatic synthesis of nucleosides labelled with 14C and 3H

    International Nuclear Information System (INIS)

    Nejedly, Z.; Filip, J.

    1988-01-01

    The method is presented of enzymatic synthesis of nucleosides labelled with 14 C or 3 H either uniformly or specifically in the base or the deoxyribosyl or ribosyl moiety. The method is based on the ribosylation or deoxyribosylation of the nucleic acid bases (non-labelled or labelled with 14 C or 3 H) by the catalytic effect of enzymes occurring in the supernatant fractions of non-purified homogenates of Escherichia coli B. bacteria. The non-labelled and labelled nucleosides are used as donors of ribosyl or deoxyribosyl groups. The HPLC method is used for separating labelled nucleosides. The radiochemical purity of the labelled nucleosides is higher than 98%, molar activity ranges from 9.2 to 18.5 GBq.mmol -1 ( 14 C-labelled compounds) and from 0.6 to 1.9 TBq.mmol -1 (3H-labelled compounds). (author). 4 figs., 8 refs

  20. Synthesis of NiO:V2O5 nanocomposite and its photocatalytic efficiency for methyl orange degradation

    Directory of Open Access Journals (Sweden)

    Salam A. Mohammed

    2018-03-01

    Full Text Available Vanadium oxide has been largely exploited as a catalyst in many industrial applications. In this article, we show the synthesis of vanadium oxide (V2O5: Nickel Oxide (NiO composite using sol-gel method at optimum conditions. The composite nanomaterials were used to remove methyl orange from waste water via harnessing the photocatalytic activity of it which showed an excellent efficiency of removal at 88%, and 93% after the exposure to the light, and light with heating respectively. This will pave the way into further implementation of these nanomaterials in the removal of some other dyes and contaminants from wastewater. Keywords: Materials chemistry, Physical chemistry, Chemical engineering, Inorganic chemistry

  1. Synthesis of dye-sensitized solar cells. Efficiency cells as a thickness of titanium dioxide

    Directory of Open Access Journals (Sweden)

    Szura Dominika

    2017-01-01

    Full Text Available Defying the influence of the thickness of TiO2 efficiency of dye-sensitized solar cell. It was confirmed that the compatibility of printed layers with the parameters closely related with the DSSC. It was found that the increase in thickness of the titanium dioxide layer, increases the distance between the electrodes, determined by the thickness of the Surlyn foil. With the rise of thickness of dyed layer of TiO2 established decrease in the value of its transmittance. Greatest transparency and aesthetic value obtained for photovoltaic modules with a single layer of titanium dioxide. The improved performance efficiency and preferred yields maximum power were noticed and exhibited by the cells covered with three layers of TiO2. It was established that the behaviour of economic efficiency in the production process, provides a range of cells with two layers of oxide, showing a similar performance and greater transparency.

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

    Science.gov (United States)

    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.

  3. Climate and energy efficiency policies: synthesis of France commitments and results

    International Nuclear Information System (INIS)

    2011-01-01

    After a brief recall of the definitions of energy efficiency, of direct and indirect emissions, of total emissions, and of the main French commitments (first climate plan, energy policy orientations in the POPE law, Grenelle de l'Environnement, national action plan for energy efficiency, Grenelle laws), this document briefly presents the current situation and predictions in terms of energy consumption and greenhouse gas emissions. For different sectors, it presents key measures and evokes actual or expected results. These sectors are: energy production, housing and office building, transports, industry, State and local communities, agriculture and forest, information and education, wastes

  4. Exploiting Synergistic Effects in Organozinc Chemistry for Direct Stereoselective C-Glycosylation Reactions at Room Temperature.

    Science.gov (United States)

    Hernan-Gomez, Alberto; Orr, Samantha; Uzelac, Marina; Kennedy, Alan; Barroso, Santiago; Jusseau, Xavier; Lemaire, Sebastien; Farina, Vittorio; Hevia, Eva

    2018-06-01

    Pairing a range of bis(aryl) zinc reagents ZnAr2 with the stronger Lewis acidic [(ZnArF2)] (ArF = C6F5), enables highly stereoselective cross-coupling between glycosyl bromides and ZnAr2 without the use of a transition metal. Reactions occur at room temperature with excellent levels of stereoselectivity, where ZnArF2 acts as a non-coupling partner although its presence is crucial for the execution of the C(sp2)-C(sp3) bond formation process. Mechanistic studies have uncovered a unique synergistic partnership between the two zinc reagents, which circumvents the need for transition-metal catalysis or forcing reaction conditions. Key to the success of the coupling is the avoidance of solvents that act as Lewis bases vs. diarylzinc compounds (e.g. THF. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Efficient utilization of crude glycerol as fermentation substrate in the synthesis of poly(3-hydroxybutyrate) biopolymers

    Science.gov (United States)

    One refined and 2 crude glycerol samples were utilized to produce poly(3-hydroxybutyrate) (PHB) by Pseudomonas oleovorans NRRL B-14682. Fermentation conditions were determined to efficiently utilize glycerol while maintaining PHB yields. A batch culture protocol including 1% glycerol and an aerati...

  6. A Simple, Rapid and Efficient One-pot Protocol for the Synthesis of 2 ...

    African Journals Online (AJOL)

    NJD

    A rapid and efficient condensation reaction of 2-aminothiophenol with various fatty acids in solvent-free conditions with or without microwave irradiation was ... heterocyclic compounds that have widespread applications in pharmaceutical and ... catalyzed reaction of aryl halides with o-aminothiophenol in presence of carbon ...

  7. Stereoselective Phytotoxicity of HCH Mediated by Photosynthetic and Antioxidant Defense Systems in Arabidopsis thaliana

    OpenAIRE

    Zhang, Qiong; Zhou, Cong; Zhang, Quan; Qian, Haifeng; Liu, Weiping; Zhao, Meirong

    2013-01-01

    BACKGROUND: Hexachlorocyclohexane (HCH) has been used for plant protection and sanitation world-widely, and its isomers have been detected in water, soil, and air as well as in vegetation. As a sink for lipophilic pollutants, vegetation is very important for the degradation and fate of organic contamination; however, little was known about their phytotoxicity and mechanisms of toxic effect. In this study, the stereoselective phototoxicity of four isomers (α, β, γ, and δ) of HCHs mediated by i...

  8. Stereoselective hydrogenation of H-alkynes on boron-nickel catalysts

    International Nuclear Information System (INIS)

    Petrova, S.S.; Sijmer, Eh.Kh.; Amitan, I.I.

    1992-01-01

    It is ascertained that in the course of stereoselective hydrogenation of H-alkynes on boron-nickel catalysts the contact modified by 2-phenyl-1,5 dimethylpyrasol-2-anom in the ratio Ni(2+):BH 4 -=1:5 is the most active and selective one. Moreover, cis-alkane was prepared with the yield of 94.5% and selective of 79%

  9. Biological stereoselective reduction of 3,3,5-trimethylcyclohexanone by Glomerella cingulata.

    Science.gov (United States)

    Okamura, S; Kameoka, H; Miyazawa, M

    2001-01-01

    The microbial transformation of 3,3,5-trimethylcyclohexanone was investigated using the plant pathogenic fungus, Glomerella cingulata. With this organism 3,3,5-trimethylcyclohexanone gave the corresponding cis- and trans-3,3,5-trimethylcyclohexanols with the ratio of 20:1 forming the cis-isomer highly stereoselectively, upon 5 days incubation together with 3,3,5-trimethyl-2-cyclohexen-1-one (isophrone) as a minor product.

  10. Stereoselective sulfate conjugation of racemic 4-hydroxypropranolol by human and rat liver cytosol

    Energy Technology Data Exchange (ETDEWEB)

    Walle, T.; Walle, U.K. (Department of Cell and Molecular Pharmacology and Experimental Therapeutics, Medical University of South Carolina, Charleston (USA))

    1991-03-01

    The objective of this study was to determine the stereochemistry of sulfoconjugation of a chiral phenolic amine drug, 4-hydroxypropranolol (HOP), by the human liver. The reaction was catalyzed by the 100,000 g cytosol as the phenolsulfotransferase (PST) enzyme source with PAP35S as the co-substrate. The enantiomers of the intact sulfate conjugate formed, (+)-HOP35S and (-)-HOP35S, were separated by HPLC and measured by liquid scintillation spectrometry. Complex velocity vs. substrate concentration curves were obtained with two peaks of activity, one at 3 microM (high affinity) and one at 500 microM (low affinity). The high-affinity reaction demonstrated a high degree of stereoselectivity. Whereas the affinity of the enantiomers for this reaction was identical, with a very low apparent KM value of 0.59 microM, the apparent Vmax value for (+)-HOPS formation was 4.6-fold higher than for (-)-HOPS. In sharp contrast, the low-affinity reaction, with an apparent KM of 65 microM, was not stereoselective. Inhibition of the high-affinity reaction by elevated temperature, but not by dichloronitrophenol, indicated that this activity was due to a monoamine form of PST. Inhibition of the low-affinity reaction by dichloronitrophenol, but not by elevated temperature, indicated that this activity was due to a phenol form of PST. As a comparison, experiments with the rat liver cytosol demonstrated only one activity, with apparent KM values of 50 microM for both enantiomers and opposite stereoselectivity in maximum velocity compared to humans, {plus minus}-HOPS ratio 0.72. The results of this study demonstrate stereoselectivity in human hepatic sulfation of a chiral phenolic amine, with clear differences between PST isoenzymes.

  11. Stereoselective handling of perhexiline: implications regarding accumulation within the human myocardium.

    Science.gov (United States)

    Chong, Cher-Rin; Drury, Nigel E; Licari, Giovanni; Frenneaux, Michael P; Horowitz, John D; Pagano, Domenico; Sallustio, Benedetta C

    2015-12-01

    Perhexiline is a prophylactic anti-ischaemic agent with weak calcium antagonist effect which has been increasingly utilised in the management of refractory angina. The metabolic clearance of perhexiline is modulated by CYP2D6 metaboliser status and stereoselectivity. The current study sought to (1) determine whether the acute accumulation of perhexiline in the myocardium is stereoselective and (2) investigate the relationship between duration of short-term therapy and the potential stereoselective effects of perhexiline within myocardium. Patients (n = 129) from the active arm of a randomised controlled trial of preoperative perhexiline in cardiac surgery were treated with oral perhexiline for a median of 9 days. Correlates of atrial and ventricular concentrations of enantiomers were sought via univariate followed by multivariate analyses. Myocardial uptake of both (+) and (-) perhexiline was greater in ventricles than in atria, and there was more rapid clearance of (-) than (+) perhexiline. The main determinants of atrial uptake of both (+) and (-) perhexiline were the plasma concentrations [(+) perhexiline: β = -0.256, p = 0.015; (-) perhexiline: β = -0.347, p = 0.001] and patients' age [(+) perhexiline: β = 0.300, p = 0.004; (-) perhexiline: β = 0.288, p = 0.005]. Atrial uptake of (+) enantiomer also varied directly with duration of therapy (β = 0.228, p = 0.025), while atrial uptake of (-) perhexiline varied inversely with simultaneous heart rate (β = -0.240, p = 0.015). (1) Uptake of both perhexiline enantiomers into atrium is greater with advanced age and displays evidence of both saturability and minor stereoselectivity. (2) Atrial uptake of (-) perhexiline may selectively modulate heart rate reduction.

  12. Stereoselective separation of β-adrenergic blocking agents containing two chiral centers by countercurrent chromatography.

    Science.gov (United States)

    Lv, Liqiong; Bu, Zhisi; Lu, Mengxia; Wang, Xiaoping; Yan, Jizhong; Tong, Shengqiang

    2017-09-01

    Four β-adrenergic blocking agents, including 1-[(1-methylethyl)amino]-3-phenoxy-2-propanol (1), 1-[(1-methylethyl)amino]-3-(3-methylphenoxy)-2-propanol (2), 1,1'-[1,4-phenylenebis(oxy)]bis[3-[(1-methylethyl)amino]-2-propanol (3) and 1,1'-[(4-methyl-1,2-phenylene)bis(oxy)]bis[3-[(1-methylethyl)amino]-2-propanol (4), were stereoselectively separated by countercurrent chromatography using di-n-hexyl l-tartrate and boric acid as chiral selector. The compounds (3) and (4) have four optical isomers since they contained two chiral centers. A two-phase solvent system composed of chloroform-0.05molL -1 of acetate buffer containing 0.10molL -1 of boric acid (1:1, v/v) was selected, in which 0.10molL -1 of di-n-hexyl l-tartrate was added in the organic phase as chiral selector. 20-42mg of each racemate was stereoselectively separated by countercurrent chromatography in a single run with high purity of 96-98%, and the recovery of each separated compound reached around 87-93%. This is the first time report on successful stereoselective separation of optical isomeric compounds containing two chiral centers by countercurrent chromatography. At the same time, a chiral stationary phase was screened for analytical stereoselective separation of compounds (3) and (4) by high performance liquid chromatography. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Stereoselective and nonstereoselective effects of ibuprofen enantiomers on mitochondrial beta-oxidation of fatty acids

    Energy Technology Data Exchange (ETDEWEB)

    Freneaux, E.; Fromenty, B.; Berson, A.; Labbe, G.; Degott, C.; Letteron, P.; Larrey, D.; Pessayre, D. (Unite de Recherches de Physiolopathologie Hepatique (INSERM U-24), Hopital Beaujon, Clichy (France))

    1990-11-01

    The effects of the R-(-) and S-(+)ibuprofen enantiomers were first studied in vitro with mouse liver mitochondria incubated in the presence of various concentrations of exogenous coenzyme A. In the presence of a low concentration of coenzyme A (2.5 microM), the R-(-)enantiomer (which forms an acylcoenzyme A) inhibited stereoselectively the beta oxidation of (1-{sup 14}C)palmitic acid but not that of (1-{sup 14}C)palmitoyl-L-carnitine (which can directly enter the mitochondria). In the presence, however, of a concentration of coenzyme A (50 microM) reproducing that present in liver cell cytosol, both enantiomers (2 mM) slightly inhibited the beta oxidation of (1-{sup 14}C)palmitic acid and markedly inhibited the beta oxidation of (1-{sup 14}C)octanoic acid and (1-{sup 14}C)butyric acid. In vivo, both enantiomers (1 mmol.kg-1) similarly inhibited the formation of ({sup 14}C)CO{sub 2} from (1-{sup 14}C)fatty acids. Both enantiomers similarly decreased plasma ketone bodies. Both similarly increased hepatic triglycerides, and both produced mild microvesicular steatosis of the liver. We conclude that both ibuprofen enantiomers inhibit beta oxidation of fatty acids in vitro and in vivo. In addition, the R-(-)enantiomer may stereoselectively sequester coenzyme A; at low concentrations of coenzyme A in vitro, this may stereoselectively inhibit the mitochondrial uptake and beta oxidation of long chain fatty acids.

  14. Electronic forces as descriptors of nucleophilic and electrophilic regioselectivity and stereoselectivity.

    Science.gov (United States)

    Liu, Shubin; Rong, Chunying; Lu, Tian

    2017-01-04

    One of the main tasks of theoretical chemistry is to rationalize computational results with chemical insights. Key concepts of such nature include nucleophilicity, electrophilicity, regioselectivity, and stereoselectivity. While computational tools are available to predict barrier heights and other reactivity properties with acceptable accuracy, a conceptual framework to appreciate above quantities is still lacking. In this work, we introduce the electronic force as the fundamental driving force of chemical processes to understand and predict molecular reactivity. It has three components but only two are independent. These forces, electrostatic and steric, can be employed as reliable descriptors for nucleophilic and electrophilic regioselectivity and stereoselectivity. The advantages of using these forces to evaluate molecular reactivity are that electrophilic and nucleophilic attacks are featured by distinct characteristics in the electrostatic force and no knowledge of quantum effects included in the kinetic and exchange-correlation energies is required. Examples are provided to highlight the validity and general applicability of these reactivity descriptors. Possible applications in ambident reactivity, σ and π holes, frustrated Lewis pairs, and stereoselective reactions are also included in this work.

  15. Stereoselective and nonstereoselective effects of ibuprofen enantiomers on mitochondrial beta-oxidation of fatty acids

    International Nuclear Information System (INIS)

    Freneaux, E.; Fromenty, B.; Berson, A.; Labbe, G.; Degott, C.; Letteron, P.; Larrey, D.; Pessayre, D.

    1990-01-01

    The effects of the R-(-) and S-(+)ibuprofen enantiomers were first studied in vitro with mouse liver mitochondria incubated in the presence of various concentrations of exogenous coenzyme A. In the presence of a low concentration of coenzyme A (2.5 microM), the R-(-)enantiomer (which forms an acylcoenzyme A) inhibited stereoselectively the beta oxidation of [1- 14 C]palmitic acid but not that of [1- 14 C]palmitoyl-L-carnitine (which can directly enter the mitochondria). In the presence, however, of a concentration of coenzyme A (50 microM) reproducing that present in liver cell cytosol, both enantiomers (2 mM) slightly inhibited the beta oxidation of [1- 14 C]palmitic acid and markedly inhibited the beta oxidation of [1- 14 C]octanoic acid and [1- 14 C]butyric acid. In vivo, both enantiomers (1 mmol.kg-1) similarly inhibited the formation of [ 14 C]CO 2 from [1- 14 C]fatty acids. Both enantiomers similarly decreased plasma ketone bodies. Both similarly increased hepatic triglycerides, and both produced mild microvesicular steatosis of the liver. We conclude that both ibuprofen enantiomers inhibit beta oxidation of fatty acids in vitro and in vivo. In addition, the R-(-)enantiomer may stereoselectively sequester coenzyme A; at low concentrations of coenzyme A in vitro, this may stereoselectively inhibit the mitochondrial uptake and beta oxidation of long chain fatty acids

  16. Surfactant-free synthesis of hierarchical niobic acid microflowers assembled from ultrathin nanosheets with efficient photoactivities

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Wenhao [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 (Singapore); Singapore-Peking University Research Centre, Centre for Research Excellence & Technological Enterprise (CREATE), Singapore, 138602 (Singapore); Pan, Feng, E-mail: phypf2012@163.com [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 (Singapore); Singapore-Peking University Research Centre, Centre for Research Excellence & Technological Enterprise (CREATE), Singapore, 138602 (Singapore); Wang, Yanyan [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 (Singapore); Singapore-Peking University Research Centre, Centre for Research Excellence & Technological Enterprise (CREATE), Singapore, 138602 (Singapore); Xiao, Shuning [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 (Singapore); International Joint Lab on Resource Chemistry SHNU-NUS-PU, Department of Chemistry, Shanghai Normal University, Shanghai 200234 (China); Wu, Kai [Singapore-Peking University Research Centre, Centre for Research Excellence & Technological Enterprise (CREATE), Singapore, 138602 (Singapore); BNLMS, SKLSCUSS, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871 (China); Xu, Guo Qin [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 (Singapore); Singapore-Peking University Research Centre, Centre for Research Excellence & Technological Enterprise (CREATE), Singapore, 138602 (Singapore); National University of Singapore (Suzhou) Research Institute, 377 Lin Quan Street, Suzhou Industrial Park, Jiangsu Prov., 215123 (China); and others

    2017-01-15

    Highlights: • 3D hierarchical niobic acid microflower was synthesized by a surfactant-free method. • The microflower was composed of ultrathin nanosheets with ∼5 nm thickness. • The microflower showed high photoactivity owing to the 3D structural features. • This microflower was converted to Nb{sub 2}O{sub 5} without significant structural alteration. • Nb{sub 2}O{sub 5} nanoneedles can also be obtained by adjusting the pH value during synthesis. - Abstract: Hierarchical niobic acid (Nb{sub 2}O{sub 5}·nH{sub 2}O) microflowers are synthesized by a surfactant-free hydrothermal approach. The three-dimensional microflowers are assembled from two-dimensional ultrathin nanosheets with thickness of ∼5 nm. Using rhodamine B as a probe, the Nb{sub 2}O{sub 5}·nH{sub 2}O microflowers exhibit high photocatalytic activity under UV light irradiation. Furthermore, the Nb{sub 2}O{sub 5}·nH{sub 2}O microflowers are easily converted to niobium pentoxide without significant structural alteration.

  17. An Efficient and Versatile Synthesis of Isoflavones from 2-Methoxybenzoic Acids

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jae In [Duksung Women' s University, Seoul (Korea, Republic of)

    2016-07-15

    Isoflavones (3-aryl-4H-1-benzopyran-4-ones) are found naturally in soybeans and many plants of the Leguminosae family. They have attracted much attention due to their biological activities, such as their anti-cancer, anti-inflammatory, and antifungal properties. Isoflavones intake through foods is important to human health, because they potentially regulate fatty acid metabolism and methoxy-substituted isoflavones in particular increase cell permeability. Isoflavones have also been synthesized by the coupling of 3-iodochromones with arylboronic acids. The condensation of 2'-hydroxyacetophenones with DMF dimethyl acetal formed 3-(dimethylamino)-2'-hydroxyphenylpropenones, which were cyclized using iodine to form 3-iodochromones. This process was followed by Suzuki coupling with arylboronic acids or aryl boronates to obtain isoflavones. The synthesis of isoflavones (6) from 5 was based on the formylation of the methylene group of 5 using DMF-POCl{sub 3}. Previously, the reaction of the DMF-POCl{sub 3} complex on benzyl 2-hydroxyphenyl ketones led to isoflavones, for which DMF was used as the reagent and solvent for 18 h at gentle reflux.

  18. One-Pot Synthesis of 2-Acylindole-3-acetylketones via Domino Aza-alkylation/Michael Reaction Using o-Aminophenyl α,β-Unsaturated Ketones Followed by Desulfonative Dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Kim, A Reum; Yu, Mi Rim; Sim, Jong Tack; Kim, Sung Gon [Kyonggi Univ., Suwon (Korea, Republic of)

    2016-09-15

    The development of novel and practical synthetic methods with a minimum number of operations for the construction of bioactive structurally complex compounds is a major challenge in synthetic organic chemistry. Recently, we reported an efficient method for the stereoselective synthesis of 2,3-disubstituted indoline derivatives; cis-2,3-disubstituted indolines were obtained by the aza-alkylation/Michael cascade reaction of 2-(tosylamino)phenyl α,β-unsaturated ketones with α-bromoacetophenones in good yields and with excellent diastereoselectivities (Scheme 2, Eq. (1)). Among the available synthetic strategies, domino or cascade reactions have received wide acceptance as highly efficient and powerful methods for the synthesis of molecules with a high structural complexity. An efficient synthesis of 2,3-disubstituted indoles was developed by the domino aza-alkylation/intramolecular Michael reaction of 2-(tosylamino)phenyl α,β-unsaturated ketones with α-bromoacetophenones, followed by desulfonative dehydrogenation with DBU. The reaction afforded structurally diverse and highly functionalized 2,3-disubstituted indoles in moderate to excellent yields (up to 99%). The synthesis of 2,3-disubstituted indoles without desulfonation through DDQ-induced oxidative dehydrogenation was also achieved.

  19. Synthesis of ZnO/CdSe hierarchical heterostructure with improved visible photocatalytic efficiency

    International Nuclear Information System (INIS)

    Wu, Yao; Xu, Fang; Guo, Defu; Gao, Zhiyong; Wu, Dapeng; Jiang, Kai

    2013-01-01

    ZnO/CdSe hierarchical heterostructure was prepared using pompon-like ZnO as substrate materials, and hexagonal CdSe nanoparticles were dispersed on the ZnO plates. The hybrid ZnO/CdSe samples were intensively investigated by XRD, SEM, TEM, HRTEM, PL and UV–vis absorption spectrum. The photocatalytic experiments confirm that ZnO/CdSe heterostructure exhibits improved photocatalytic efficiency compared to pure ZnO under visible light irradiation. CdSe nanoparticles are believed to serve as photosensitizers to extend the absorption spectrum to visible light region. In addition, the incorporation of CdSe can suppress the recombination of photogenerated electron-hole pairs, which contributes to the enhancement of photocatalytic efficiency.

  20. Synthesis of nitrogen-doped porous carbon nanofibers as an efficient electrode material for supercapacitors.

    Science.gov (United States)

    Chen, Li-Feng; Zhang, Xu-Dong; Liang, Hai-Wei; Kong, Mingguang; Guan, Qing-Fang; Chen, Ping; Wu, Zhen-Yu; Yu, Shu-Hong

    2012-08-28

    Supercapacitors (also known as ultracapacitors) are considered to be the most promising approach to meet the pressing requirements of energy storage. Supercapacitive electrode materials, which are closely related to the high-efficiency storage of energy, have provoked more interest. Herein, we present a high-capacity supercapacitor material based on the nitrogen-doped porous carbon nanofibers synthesized by carbonization of macroscopic-scale carbonaceous nanofibers (CNFs) coated with polypyrrole (CNFs@polypyrrole) at an appropriate temperature. The composite nanofibers exhibit a reversible specific capacitance of 202.0 F g(-1) at the current density of 1.0 A g(-1) in 6.0 mol L(-1) aqueous KOH electrolyte, meanwhile maintaining a high-class capacitance retention capability and a maximum power density of 89.57 kW kg(-1). This kind of nitrogen-doped carbon nanofiber represents an alternative promising candidate for an efficient electrode material for supercapacitors.

  1. Nano-Ticl 4 .SiO 2 : a Versatile and Efficient Catalyst for Synthesis of ...

    African Journals Online (AJOL)

    Nano-TiCl4.SiO2 has been found to be an extremely efficient catalyst for the preparation of 3,4-dihydropyrimidinones/thiones via three-component reactions of an aldehyde, β-ketoester or β-diketone and urea or thiourea under mild conditions. Nano-TiCl4.SiO2 as a solid Lewis acid has been synthesized by reaction of ...

  2. Effects of chemical structure on the thermodynamic efficiency of radical chain carriers for organic synthesis.

    Science.gov (United States)

    Lin, Ching Yeh; Peh, Jessie; Coote, Michelle L

    2011-03-18

    The chain carrier index (CCI), defined as the ratio of the bond dissociation free energies (BDFE) of corresponding chain carrier halides and hydrides, is proposed as a measure of the thermodynamic efficiency of chain carriers for radical dehalogenation. The larger this value is relative to the corresponding value of the organic substrate, the more thermodynamically efficient the process. The chloride and bromide CCIs were evaluated at the G3(MP2)-RAD(+) level of theory for 120 different R-groups, covering a broad range of carbon-centered and noncarbon-centered species; the effects of solvent and temperature have also been studied. The broad finding from this work is that successful chain carriers generally maximize the strength of their halide (versus hydride bonds) through charge-shift bonding. As a result, the thermodynamic efficiency of a chain carrier tends to increase down the periodic table, and also with the inclusion of stronger electron donating substituents. The CCIs of carbon-centered species fall into a relatively narrow range so that, even when the CCI is maximized through inclusion of lone pair donor OMe or NMe(2) groups, the thermodynamic driving force for dehalogenation of other organic substrates is modest at best, and the process is likely to be kinetically hampered. Among the noncarbon-centered species studied, bismuth- and borane-centered compounds have some of the highest CCI values and, although their kinetics requires further optimization, these classes of compounds would be worth further investigation as tin-free radical reducing agents.

  3. An efficient method for synthesis of bis(indolylmethane and di-bis(indolylmethane derivatives in environmentally benign conditions using TBAHS

    Directory of Open Access Journals (Sweden)

    Seyed Hossein Siyadatifard

    2016-05-01

    Full Text Available An efficient procedure for the synthesis of bisindolylmethanes (BIMs from condensation of indole and aromatic aldehydes or ketones is described. The aromatic electrophilic substitution reactions of indole with aromatic aldehydes and ketones are achieved in the presence of tetrabutylammonium hydrogen sulfate (TBAHS as a mild and efficient solid acid catalyst. This methodology offers several advantages such as good yields, simple procedure, mild and environmentally benign conditions.

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

    Science.gov (United States)

    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.

  5. Efficient Lewis Acid Ionic Liquid-Catalyzed Synthesis of the Key Intermediate of Coenzyme Q10 under Microwave Irradiation

    Directory of Open Access Journals (Sweden)

    Thomas Efferth

    2010-12-01

    Full Text Available An efficient synthesis of a valuable intermediate of coenzyme Q10 by microwave-assisted Lewis acidic ionic liquid (IL-catalyzed Friedel-Crafts alkylation is reported. The acidity of six [Etpy]BF4-based ionic liquids was characterized by means of the FT-IR technique using acetonitrile as a molecular probe. The catalytic activities of these ionic liquids were correlated with their Lewis acidity. With increasing Lewis acid strength of the ionic liquids, their catalytic activity in the Friedel-Crafts reaction increased, except for [Etpy]BF4-AlCl3. The effects of the reaction system, the molar fraction of Lewis acid in the Lewis acid ILs and heating techniques were also investigated. Among the six Lewis acid ionic liquids tested [Etpy]BF4-ZnCl2 showed the best catalytic activity, with a yield of 89% after a very short reaction time (150 seconds. This procedure has the advantages of higher efficiency, better reusability of ILs, energy conservation and eco-friendliness. The method has practical value for preparation of CoQ10 on an industrial scale.

  6. Graphite oxide-mediated synthesis of porous CeO2 quadrangular prisms and their high-efficiency adsorptive performance

    International Nuclear Information System (INIS)

    Chang, Ling; Wang, Fengxian; Xie, Dong; Zhang, Jun; Du, Gaohui

    2013-01-01

    Graphical abstract: - Highlights: • Porous CeO 2 quadrangular prisms have been prepared via graphite oxide-mediated synthesis. • Dual-pore hierarchical systems are formed with the pore distributions around 4 nm and 30 nm. • Porous CeO 2 exhibits a rapid adsorption to Rhodamine B with a removal efficiency of ∼99%. • Porous CeO 2 retains the same performances in different pH solutions. - Abstract: We report a graphite oxide-mediated approach for synthesizing porous CeO 2 through a facile hydrothermal process followed by thermal annealing in air. The phase structure, morphology, microstructure and porosity of the products have been revealed by a combination of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and N 2 adsorption. The as-prepared CeO 2 products show well-defined quadrangular prism morphology, and they are composed of interconnected nanoparticles with diameters around 30–100 nm. In particular, the dual-pore hierarchical systems are created in the CeO 2 quadrangular prisms with the pore distributions around 4 nm and 30 nm. The dye sorption capacity of the porous CeO 2 is investigated, which exhibits a rapid adsorption to rhodamine B with a high removal efficiency of ∼99%. Moreover, the CeO 2 absorbent retains the same performances in different pH solutions

  7. Zr(HSO44: An Efficient Catalyst for the Synthesis of 3-(2'- Benzothiazolyl-2,3-dihydroquinazolin- 4(1H-ones

    Directory of Open Access Journals (Sweden)

    Liqiang Wu

    2012-01-01

    Full Text Available A simple and efficient synthesis of 3-(2'-benzothiazolyl-2,3-dihydro quinazolin-4(1H- ones has been accomplished by the one-pot condensation of isatoic anhydride, aldehyde and 2-aminobenzothiazole under solvent-free conditions in the presence of Zr(HSO44.

  8. An Efficient Synthesis of Substituted Furans by Cupric Halide-Mediated Intramolecular Halocyclization of 2-(1-Alkynyl)-2-alken-1-ones

    International Nuclear Information System (INIS)

    Fu, Weijun; Guo, Wenbo; Zhu, Mei; Xu, Chen; Xu, Fengjuan

    2013-01-01

    An efficient synthesis of 3-halofurans by the intramolecular cyclization of 2-(1-alkynyl)-2-alken-1-ones with cupric halide has been developed. A broad range of 3-chloro- and 3-bromofuran derivatives could be obtained in the present method in moderate to good yields. The 3-halofuran derivatives are potential synthetic intermediates for amplification of molecular complexity

  9. Update: An efficient synthesis of poly(ethylene glycol)-supported iron(II) porphyrin using a click reaction and its application for the catalytic olefination of aldehydes

    KAUST Repository

    Chinnusamy, Tamilselvi R.; Rodionov, Valentin; Kü hn, Fritz; Reiser, Oliver

    2012-01-01

    The facile synthesis of polyethylene glycol (PEG)-immobilized iron(II) porphyrin using a copper-catalyzed azide-alkyne [3+2] cycloaddition "click" reaction is reported. The prepared complex 5 (PEG-C 51H 39FeN 7O) was found to be an efficient

  10. An efficient protocol for the synthesis of highly sensitive indole imines utilizing green chemistry: optimization of reaction conditions.

    Science.gov (United States)

    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.

  11. An Efficient and Short Route for the Synthesis of Reverse Pyrrole Ribonucleosides

    Directory of Open Access Journals (Sweden)

    Pereira Letícia O. R.

    2002-01-01

    Full Text Available The synthesis of reverse pyrrole ribonucleosides methyl 5-C-(4-acetyl-5-methyl-pyrrol-1-yl-2,3-O-isopropylidene-5-deoxy- beta-D-ribofuranoside (10, methyl 5-C-(4-ethoxycarbonyl-5-methyl-pyrrol-1-yl-2,3-O-isopropylidene-5-deoxy- beta-D-ribofuranoside (11, methyl 5-C-(4-acetyl-5-methyl-pyrrol-1-yl-5-deoxy-beta-D-ribofuranoside (12, methyl 5-C-(4-ethoxycarbonyl-5-methyl-pyrrol-1-yl-5-deoxy- beta-D-ribofuranoside (13, methyl 5-deoxy-5-C-(3'-formyl-4'-hydroxypropyl-pyrrol-1'-yl-2,3-O-isopropylidene- beta-D-ribofuranoside (16 and methyl 5-deoxy-5-C-(3'-formyl-pyrrol-1'-yl-2,3-O-isopropylidene- beta-D-ribofuranoside (18 are described starting from readily available methyl 5-amino-5-deoxy-2,3-O-isopropylidene-beta-D-ribofuranoside (9. The synthetic strategy for the construction of the heterocyclic ring was based on the nucleophilic attack of (9 to 4-acetyl-2-n-butoxy-5-methyl-4,5-dihydrofuran (4, 4-carbetoxy-2-n-butoxy-5-methyl-4,5-dihydrofuran (5, 4-formyl-2-n-butoxy-4,5-dihydrofuran (6 and 4-formyl-1-methyl dioxabyciclo[3.3.0]oct-3-en (8, in situ. The later compounds were obtained from reaction between 3-diazo-2,4-pentadione (1, ethyl 2-diazoacetoacetate (2 or diazomalonaldehyde (3 and enol ethers using dirhodium tetraacetate as a catalyst.

  12. Efficient synthesis of graphene oxide and the mechanisms of oxidation and exfoliation

    Science.gov (United States)

    Yuan, Rui; Yuan, Jing; Wu, Yanping; Chen, Lei; Zhou, Huidi; Chen, Jianmin

    2017-09-01

    An efficient method for the preparation of graphene oxide (GO) was descried through inducing the ultrasonic in the rate-determining step of oxidation processes. Both the transformation procedures and the detailed molecular behavior of parent graphene (PG), partially oxidized graphene (PGO) and GO in H2SO4 and aqueous solution were investigated by molecular dynamic simulation (MD) combining with experiments. The results obtained from MD simulation show that the addition of KMnO4 truly marked the beginning of the reaction which carried out from the border of PG flakes to the centre. This oxidation procedure was the rate-determining step and mainly contained three steps: the boundary carbon atoms oxidized, the distance of the corresponding interlayer enlarged and the oxidizing agent diffused into the unoxidized region, the processes was repeated until oxidized completely. So, the introducing ultrasonic in this section can accelerate not only the exfoliation of layers but also the diffusion of oxidizer and finally raises the oxidation efficiency dramatically. To further clarify these simulation results, the GO was prepared by the method mentioned above. The analyses results for the X-ray diffraction (XRD), Raman spectra and X-ray photoelectron spectroscopy (XPS) of the resulting GO show that the ultrasonic method could perfectly shortens the oxidation time from 12 h to 3 h and forms the higher degree of oxidation products with more carboxylic acid groups on its edges. Thus, this study provides a better understanding of the transformation procedures of graphite and proposes an efficient way to produce GOs suitable for various chemical modifications.

  13. Plasma-Assisted Synthesis of NiCoP for Efficient Overall Water Splitting

    KAUST Repository

    Liang, Hanfeng

    2016-11-09

    Efficient water splitting requires highly active, earth-abundant, and robust catalysts. Monometallic phosphides such as NiP have been shown to be active toward water splitting. Our theoretical analysis has suggested that their performance can be further enhanced by substitution with extrinsic metals, though very little work has been conducted in this area. Here we present for the first time a novel PH plasma-assisted approach to convert NiCo hydroxides into ternary NiCoP. The obtained NiCoP nanostructure supported on Ni foam shows superior catalytic activity toward the hydrogen evolution reaction (HER) with a low overpotential of 32 mV at 10 mA cm in alkaline media. Moreover, it is also capable of catalyzing the oxygen evolution reaction (OER) with high efficiency though the real active sites are surface oxides in situ formed during the catalysis. Specifically, a current density of 10 mA cm is achieved at overpotential of 280 mV. These overpotentials are among the best reported values for non-noble metal catalysts. Most importantly, when used as both the cathode and anode for overall water splitting, a current density of 10 mA cm is achieved at a cell voltage as low as 1.58 V, making NiCoP among the most efficient earth-abundant catalysts for water splitting. Moreover, our new synthetic approach can serve as a versatile route to synthesize various bimetallic or even more complex phosphides for various applications.

  14. Comparison of the energy efficiency to produce agroethanol between various industries and processes: Synthesis

    International Nuclear Information System (INIS)

    Chavanne, Xavier; Frangi, Jean-Pierre

    2011-01-01

    The article assesses the energy R required by a system to transform a cereal or sugar plant into ethanol. From the specific consumption r j of each process j and its weight w j in the system, process consumption share R j is deduced and hence R, sum of R j . Depending on w j definition, R j and R are relative to either 100 J of ethanol produced or 100 J of plant harvested. Depending on the nature of r j , R j and R represent either only primary external energies, or all fuel and electricity consumed directly, or external and internal energies. From one definition to another R for average sugar cane based industries is the best or the worst relative to other plants. This results also from the use of cane residues as fuels while operating outdated processes. Through r j the process based analysis allows to examine for each system the impact of modern processes or different use of residues. All systems benefit except sugar beet based industry close to its best efficiency. This flexibility permits even to build a self-sufficient system where existing processes produce from system resources substitutes to external energies. R becomes an unambiguous definition of a system efficiency. It shows that all agroethanol systems are more consuming than petroleum industry. The system can be expanded to the vehicle stage to compare with alternatives to ethanol such as electricity and biogas. Wheat straw burnt to produce electricity used in an electrical vehicle will present R close to that of petroleum industry. -- Highlights: → Study of the energy consumptions of agroethanol industries with a process based analysis. → Different definitions of energy efficiency with potential opposite conclusions. → Previous highlight is overcome using self sufficient systems with existing processes. → Consumptions of average and improved agroethanol industries larger than for petroleum industries. → Electricity from wheat straw combustion can compete with gasoline from crude oil.

  15. A concise, efficient synthesis of sugar-based benzothiazoles through chemoselective intramolecular C-S coupling

    KAUST Repository

    Shen, Chao

    2012-01-01

    Sugar-based benzothiazoles are a new class of molecules promising for many biological applications. Here, we have synthesized a wide range of sugar-based benzothiazoles from readily accessible glycosyl thioureas by chemoselective, palladium-catalyzed C-S coupling reactions. Corroborated by theoretical calculations, a mechanistic investigation indicates that the coordination to the palladium by a pivaloyl carbonyl group and the presence of intramolecular hydrogen bonding play important roles in the efficiency and chemoselectivity of reaction. These fluorescent glycoconjugates can be observed to readily enter mammalian tumor cells and exhibit potential in vitro antitumor activity. This journal is © The Royal Society of Chemistry 2012.

  16. Synthesis and photoactivity of the highly efficient Ag species/TiO2 nanoflakes photocatalysts

    International Nuclear Information System (INIS)

    Liu Yong; Hu Juncheng; Li Jinlin

    2011-01-01

    Research highlights: → Highly efficient Ag species-TiO 2 nanoflakes catalyst was prepared. → The variety and relative amount of Ag species in TiO 2 can be well tuned. → The enhanced photocatalytic activity can be attributed to the Ag species. - Abstract: Ag species/TiO 2 nanoflakes photocatalysts with different relative contents (Ag + , Ag 2+ , Ag 0 ) have been successfully synthesized by a simple template-free synthetic strategy. X-ray photoelectron spectroscopy, X-ray diffraction, and UV-vis diffuse reflectance spectra indicated that the dopant ions (Ag + or Ag 2+ ) were partly incorporated into the titanium dioxide nanoflakes. Meanwhile, part of the silver ions migrated to the surface after the subsequent calcination and aggregated into ultra-small metallic Ag nanoclusters (NCs) (1-2 nm), which are well dispersed on the surface of TiO 2 nanoflakes. The photocatalytic activities of the Ag species/TiO 2 materials obtained were evaluated by testing the photodegradation of the azo dye reactive brilliant X-3B (X-3B) under near UV irradiation. Interestingly, it was found that the maximum photocatalytic efficiency was observed when Ag species coexisted in three valence states (Ag + , Ag 2+ , Ag 0 NCs), which was higher than that of Degussa P25. The high photocatalytic activity of the Ag species/TiO 2 can be attributed to the synergy effect of the three Ag species.

  17. Synthesis, characterization and corrosion inhibition efficiency of N-(4-(Morpholinomethyl Carbamoyl Phenyl Furan-2-Carboxamide

    Directory of Open Access Journals (Sweden)

    N. Zulfareen

    2016-01-01

    Full Text Available A mannich base namely N-(4-(Morpholinomethyl Carbamoyl Phenyl Furan-2-Carboxamide (MFC was synthesized and characterized by FT-IR, 1H NMR, and 13C NMR. The molecular weight of MFC was confirmed by LC-MS. The inhibition effect of MFC on brass in 1 M HCl medium has been investigated by weight loss measurement, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS and cyclic voltametry (CV. Thermodynamic parameters such as free energy, entropy and enthalpy were calculated to describe the mechanism of corrosion inhibitor. The inhibition efficiency of MFC increases with increase in concentration and temperature ranges from 30 °C to 60 °C. Polarization measurements indicated that MFC acts as a mixed type corrosion inhibitor. AC impedance indicates that Rct value increases with increase in the concentration of inhibitor. CV reveals that the oxidation of the copper is controlled by the addition of inhibitor on the brass metal. Surface analysis using scanning electron microscope (SEM shows a significant morphological improvement on the brass surface with the addition of the inhibitor. The adsorption of MFC on brass obeys Langmuir adsorption isotherm. The molecular structure of MFC was distorted to quantum chemical indices using density functional theory (DFT which indicates that the inhibition efficiency of MFC is closely related to quantum parameters.

  18. Efficient utilization of waste date pits for the synthesis of green diesel and jet fuel fractions

    International Nuclear Information System (INIS)

    Al-Muhtaseb, Ala’a H.; Jamil, Farrukh; Al-Haj, Lamya; Al-Hinai, Mohab A.; Baawain, Mahad; Myint, Myo Tay Zar; Rooney, David

    2016-01-01

    Highlights: • Active catalysts Pt/C and Pd/C were developed from waste date pits. • Catalysts showed good activity in hydrodeoxygenation of date pit oil to alkane fuels. • The liquid product fractions lay within the range of the jet fuel and green diesel. • Green diesel fraction obtained by Pd/C was 72.03% and jet fuel was 30.39%. • Date pits can be a promising platform for the production of catalysts and biofuels. - Abstract: Date pits are considered one of the major agricultural wastes in Oman. The present work involves the synthesis of active catalysts from waste date pits carbon produced by carbonization and impregnation with Pt and Pd metals. Synthesized catalysts Pt/C and Pd/C were characterized by XRD, SEM, TEM, EDX, BET and XPS. The activity of the catalysts’ performance was evaluated by the hydrodeoxygenation of date pits oil for the production of second-generation biofuels, which includes jet fuel and green diesel fractions. Results indicate that the synthesized catalysts were highly active for the hydrodeoxygenation of date pits oil. Based on the elemental analysis, the degree of deoxygenation (DOD) of product oil was 97.5% and 89.4% for the Pd/C and Pt/C catalysts respectively. The high DOD was also confirmed by product analyses that mainly consist of paraffinic hydrocarbons. Results also showed that between the two catalysts, Pd/C showed a higher activity towards hydrodeoxygenation, a conclusion that was based on the high DOD of the product oil due to hydrocarbons formation. Based on the type of components in the product oil, the maximum fraction of hydrocarbons formed lay within the range of 72.03% and 72.78% green diesel, and 30.39% and 28.25% jet fuel using Pd/C and Pt/C catalysts respectively. It can be concluded that waste date pits can be a promising platform for the production of catalysts and biofuels.

  19. Asymmetric noncovalent synthesis of self-assembled one-dimensional stacks by a chiral supramolecular auxiliary approach

    NARCIS (Netherlands)

    George, S.J.; Tomovic, Z.; Averbeke, Van B.; Beljonne, D.; Lazzaroni, R.; Schenning, A.P.H.J.; Meijer, E.W.

    2012-01-01

    Stereoselective noncovalent synthesis of one-dimensional helical self-assembled stacks of achiral oligo(p-phenylenevinylene) ureidotriazine (AOPV3) monomers is obtained by a chiral supramolecular auxiliary approach. The racemic mixture of helical stacks of achiral AOPV3 molecules is converted into

  20. A selective C-H insertion/olefination protocol for the synthesis of α-methylene-γ-butyrolactone natural products.

    Science.gov (United States)

    Lloyd, Matthew G; D'Acunto, Mariantonietta; Taylor, Richard J K; Unsworth, William P

    2016-02-07

    A regio- and stereoselective one-pot C-H insertion/olefination protocol has been developed for the late stage installation of α-methylene-γ-butyrolactones into conformationally restricted cyclohexanol-derivatives. The method has been successfully applied in the total synthesis of eudesmanolide natural product frameworks, including α-cyclocostunolide.

  1. Rational Design and Synthesis of Efficient Sunscreens To Boost the Solar Protection Factor.

    Science.gov (United States)

    Losantos, Raúl; Funes-Ardoiz, Ignacio; Aguilera, José; Herrera-Ceballos, Enrique; García-Iriepa, Cristina; Campos, Pedro J; Sampedro, Diego

    2017-03-01

    Skin cancer incidence has been increasing in the last decades, but most of the commercial formulations used as sunscreens are designed to protect only against solar erythema. Many of the active components present in sunscreens show critical weaknesses, such as low stability and toxicity. Thus, the development of more efficient components is an urgent health necessity and an attractive industrial target. We have rationally designed core moieties with increased photoprotective capacities and a new energy dissipation mechanism. Using these scaffolds, we have synthesized a series of compounds with tunable properties suitable for their use in sunscreens, and enhanced properties in terms of stability, light energy dissipation, and toxicity. Moreover, some representative compounds were included in final sunscreen formulations and a relevant solar protection factor boost was measured. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Electrodeposited synthesis of self-supported Ni-P cathode for efficient electrocatalytic hydrogen generation

    Directory of Open Access Journals (Sweden)

    Ruixian Wu

    2016-06-01

    Full Text Available One of the key challenges for electrochemical water splitting is the development of low-cost and efficient hydrogen evolution cathode. In this work, a self-supported Ni-P cathode was synthesized by a facile electrodeposition method. The composition and morphology were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. The Ni-P cathode performed low onset over-potential, good catalytic activity and long-term stability under neutral and alkaline conditions. The mechanism of Ni-P electrode for hydrogen production was discussed by electrochemical impedance spectroscopy. The excellent performance of Ni-P cathode was mainly attributed to the synergistic effect of phosphate anions and the self-supported feature.

  3. Efficient Synthesis of β-Aryl-γ-lactams and Their Resolution with (S-Naproxen: Preparation of (R- and (S-Baclofen

    Directory of Open Access Journals (Sweden)

    Iris J. Montoya-Balbás

    2015-12-01

    Full Text Available An efficient synthesis of enantiomerically-pure β-aryl-γ-lactams is described. The principal feature of this synthesis is the practical resolution of β-aryl-γ-lactams with (S-Naproxen. The procedure is based on the Michael addition of nitromethane to benzylidenemalonates, which was easily obtained, followed by the reduction of the γ-nitroester in the presence of Raney nickel and the subsequent saponification/decarboxylation reaction. The utility of this methodology was highlighted by the preparation of enantiomerically-pure (R- and (S-Baclofen hydrochloride.

  4. Influence of a pulse duration of high-voltage supply on the efficiency of ozone synthesis in the 'needle-plane' electrode system

    International Nuclear Information System (INIS)

    Golota, V.I.; Zavada, L.M.; Karas, V.I.; Kotjukov, O.V.; Poliakov, O.V.; Pugach, S.G.

    2007-01-01

    We present the results of studies of the electrodynamic characteristics of a barrier less discharge with electrodes of the 'needle-plane' type and a high-voltage pulse of positive polarity, being applied to the edge electrode. The efficiency of ozone synthesis is determined as a function of the pulse duration and repetition rate. It is shown that the electrodynamic characteristics of the discharge and the effectiveness of ozone synthesis in oxygen-containing gas mixtures essentially depend on the parameters of the pulse supply

  5. An efficient one-pot three-component synthesis of α-amino nitriles via Strecker reaction catalysed by bismuth(III nitrate

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor

    2016-09-01

    Full Text Available A convenient and efficient one-pot method for the synthesis of a variety of α-amino nitriles from aldehydes, amines and trimethylsilyl cyanide (TMSCN in the presence of a catalytic amount of Bi(NO33 at room temperature in acetonitrile (MeCN is described. The significant features of this method are simple work-up procedure, inexpensive and non-toxic catalyst, shorter reaction times and excellent product yields. The catalyst Bi(NO33 can be reused. The reusability of the catalyst has been studied for the synthesis of various amino nitriles.

  6. Rapid and Efficient Synthesis of Silver Nanofluid Using Electrical Discharge Machining

    Directory of Open Access Journals (Sweden)

    Kuo-Hsiung Tseng

    2013-01-01

    Full Text Available The electrical discharge machining (EDM system has been proven feasible as a rapid and efficient method for silver nanofluid preparation. This study prepared the silver nano-fluid via EDM and investigated the relationship between its process parameters and product characteristics. The prior study had found that the silver nano-fluid prepared by EDM contained both silver nanoparticles and silver ions. Silver ions had revealed the cause of the high suspension of the silver nanoparticles. To examine the relationship between the stability of silver nanofluid and the process parameters, this study quantified the relationship of process parameters to the material removal rate (MRR of silver electrode and silver ion output rate (IOR in the fluid, in order to achieve the most effective process parameter condition. Furthermore, the stability of silver nano-fluid was analyzed by various devices, including UV-Vis spectroscopy, size-distribution, and Zeta-potential analyzer. The effects of MRR, IOR, particle size, Zeta-potential, and optical properties of silver nanofluid under different process parameters are also discussed.

  7. Synthesis of Zirconium-Containing Polyhedral Oligometallasilsesquioxane as an Efficient Thermal Stabilizer for Silicone Rubber

    Directory of Open Access Journals (Sweden)

    Jiedong Qiu

    2018-05-01

    Full Text Available Free radicals play a negative role during the thermal degradation of silicone rubber (SR. Quenching free radicals is proposed to be an efficient way to improve the thermal-oxidative stability of SR. In this work, a novel zirconium-containing polyhedral oligometallasilsesquioxane (Zr-POSS with free-radical quenching capability was synthesized and characterized. The incorporation of Zr-POSS effectively improved the thermal-oxidative stability of SR. The T5 (temperature at 5% weight loss of SR/Zr-POSS significantly increased by 31.7 °C when compared to the unmodified SR. Notably, after aging 12 h at 280 °C, SR/Zr-POSS was still retaining about 65%, 60%, 75%, and 100% of the tensile strength, tear strength, elongation at break, and hardness before aging, respectively, while the mechanical properties of the unmodified SR were significantly decreased. The possible mechanism of Zr-POSS for improving the thermal-oxidative stability of SR was intensively studied and it was revealed that the POSS structure could act as a limiting point to suppress the random scission reaction of backbone. Furthermore, Zr could quench the free radicals by its empty orbital and transformation of valence states. Therefore, it effectively suppressed the thermal-oxidative degradation and crosslinking reaction of the side chains.

  8. Efficient production of isotopically labeled proteins by cell-free synthesis: A practical protocol

    Energy Technology Data Exchange (ETDEWEB)

    Torizawa, Takuya; Shimizu, Masato [Crest, Jst (Japan); Taoka, Masato [Tokyo Metropolitan University, Graduate School of Science (Japan); Miyano, Hiroshi [Ajinomoto Co., Inc. Institute of Life Sciences (Japan); Kainosho, Masatsune [Crest, Jst (Japan)], E-mail: kainosho@nmr.chem.metro-u.ac.jp

    2004-11-15

    We provide detailed descriptions of our refined protocols for the cell-free production of labeled protein samples for NMR spectroscopy. These methods are efficient and overcome two critical problems associated with the use of conventional Escherichia coli extract systems. Endogenous amino acids normally present in E. coli S30 extracts dilute the added labeled amino acids and degrade the quality of NMR spectra of the target protein. This problem was solved by altering the protocol used in preparing the S30 extract so as to minimize the content of endogenous amino acids. The second problem encountered in conventional E. coli cell-free protein production is non-uniformity in the N-terminus of the target protein, which can complicate the NMR spectra. This problem was solved by adding a DNA sequence to the construct that codes for a cleavable N-terminal peptide tag. Addition of the tag serves to increase the yield of the protein as well as to ensure a homogeneous protein product following tag cleavage. We illustrate the method by describing its stepwise application to the production of calmodulin samples with different stable isotope labeling patterns for NMR analysis.

  9. Synthesis of Highly Uniform and Compact Lithium Zinc Ferrite Ceramics via an Efficient Low Temperature Approach.

    Science.gov (United States)

    Xu, Fang; Liao, Yulong; Zhang, Dainan; Zhou, Tingchuan; Li, Jie; Gan, Gongwen; Zhang, Huaiwu

    2017-04-17

    LiZn ferrite ceramics with high saturation magnetization (4πM s ) and low ferromagnetic resonance line widths (ΔH) represent a very critical class of material for microwave ferrite devices. Many existing approaches emphasize promotion of the grain growth (average size is 10-50 μm) of ferrite ceramics to improve the gyromagnetic properties at relatively low sintering temperatures. This paper describes a new strategy for obtaining uniform and compact LiZn ferrite ceramics (average grains size is ∼2 μm) with enhanced magnetic performance by suppressing grain growth in great detail. The LiZn ferrites with a formula of Li 0.415 Zn 0.27 Mn 0.06 Ti 0.1 Fe 2.155 O 4 were prepared by solid reaction routes with two new sintering strategies. Interestingly, results show that uniform, compact, and pure spinel ferrite ceramics were synthesized at a low temperature (∼850 °C) without obvious grain growth. We also find that a fast second sintering treatment (FSST) can further improve their gyromagnetic properties, such as higher 4πM s and lower ΔH. The two new strategies are facile and efficient for densification of LiZn ferrite ceramics via suppressing grain growth at low temperatures. The sintering strategy reported in this study also provides a referential experience for other ceramics, such as soft magnetism ferrite ceramics or dielectric ceramics.

  10. Efficient One-Pot Synthesis of 5-Chloromethylfurfural (CMF from Carbohydrates in Mild Biphasic Systems

    Directory of Open Access Journals (Sweden)

    Dimitris S. Argyropoulos

    2013-07-01

    Full Text Available 5-Halomethylfurfurals can be considered as platform chemicals of high reactivity making them useful for the preparation of a variety of important compounds. In this study, a one-pot route for the conversion of carbohydrates into 5-chloromethylfurfural (CMF in a simple and efficient (HCl-H3PO4/CHCl3 biphasic system has been investigated. Monosaccharides such as D-fructose, D-glucose and sorbose, disaccharides such as sucrose and cellobiose and polysaccharides such as cellulose were successfully converted into CMF in satisfactory yields under mild conditions. Our data shows that when using D-fructose the optimum yield of CMF was about 47%. This understanding allowed us to extent our work to biomaterials, such as wood powder and wood pulps with yields of CMF obtained being comparable to those seen with some of the enumerated mono and disaccharides. Overall, the proposed (HCl-H3PO4/CHCl3 optimized biphasic system provides a simple, mild, and cost-effective means to prepare CMF from renewable resources.

  11. SYNTHESIS OF MAGNETITE NANOPARTICLES AND EVALUATION OF ITS EFFICIENCY FOR ARSENIC REMOVAL FROM SIMULATED INDUSTRIAL WASTEWATER

    Directory of Open Access Journals (Sweden)

    A. Khodabakhshi

    2011-09-01

    Full Text Available In this study the efficiency of magnetic nanoparticles for removal of trivalent arsenic from synthetic industrial wastewater was evaluated. The nanoparticles was prepared by sol-gel method and characterized by X-ray methods including XRD, XRF, and SEM, and vibrating sample magnetometer (VSM. The results showed that synthesized nanoparticles were in the size range of 40-300 nm, purity of about 90%, and magnetization of nanoparticles was 36.5emu/g. In initial conditions including: pH=7, As(III concentration of 10 mg/L, nanomagnetite concentration of 1g/L, shaking speed of 250 rpm and 20 minute retention time, 82% of As (III was removed. Competition from common coexisting ions such as Na+, Ni2+, Cu2+, SO42-, and Cl- was ignorable but for NO3- was significant. The adsorption data of magnetite nanoparticles fit well with Freundlich isotherm equations. The adsorption capacity of the Fe3O4 for As (III at pH=7 was obtained as 23.8 mg/g. It was concluded that magnetite nanoparticles have considerable potential in removal of As(III from synthetic industrial wastewaters.

  12. Efficient production of isotopically labeled proteins by cell-free synthesis: A practical protocol

    International Nuclear Information System (INIS)

    Torizawa, Takuya; Shimizu, Masato; Taoka, Masato; Miyano, Hiroshi; Kainosho, Masatsune

    2004-01-01

    We provide detailed descriptions of our refined protocols for the cell-free production of labeled protein samples for NMR spectroscopy. These methods are efficient and overcome two critical problems associated with the use of conventional Escherichia coli extract systems. Endogenous amino acids normally present in E. coli S30 extracts dilute the added labeled amino acids and degrade the quality of NMR spectra of the target protein. This problem was solved by altering the protocol used in preparing the S30 extract so as to minimize the content of endogenous amino acids. The second problem encountered in conventional E. coli cell-free protein production is non-uniformity in the N-terminus of the target protein, which can complicate the NMR spectra. This problem was solved by adding a DNA sequence to the construct that codes for a cleavable N-terminal peptide tag. Addition of the tag serves to increase the yield of the protein as well as to ensure a homogeneous protein product following tag cleavage. We illustrate the method by describing its stepwise application to the production of calmodulin samples with different stable isotope labeling patterns for NMR analysis

  13. L-allo-threonine aldolase with an H128Y/S292R mutation from Aeromonas jandaei DK-39 reveals the structural basis of changes in substrate stereoselectivity.

    Science.gov (United States)

    Qin, Hui-Min; Imai, Fabiana Lica; Miyakawa, Takuya; Kataoka, Michihiko; Kitamura, Nahoko; Urano, Nobuyuki; Mori, Koji; Kawabata, Hiroshi; Okai, Masahiko; Ohtsuka, Jun; Hou, Feng; Nagata, Koji; Shimizu, Sakayu; Tanokura, Masaru

    2014-06-01

    L-allo-Threonine aldolase (LATA), a pyridoxal-5'-phosphate-dependent enzyme from Aeromonas jandaei DK-39, stereospecifically catalyzes the reversible interconversion of L-allo-threonine to glycine and acetaldehyde. Here, the crystal structures of LATA and its mutant LATA_H128Y/S292R were determined at 2.59 and 2.50 Å resolution, respectively. Their structures implied that conformational changes in the loop consisting of residues Ala123-Pro131, where His128 moved 4.2 Å outwards from the active site on mutation to a tyrosine residue, regulate the substrate specificity for L-allo-threonine versus L-threonine. Saturation mutagenesis of His128 led to diverse stereoselectivity towards L-allo-threonine and L-threonine. Moreover, the H128Y mutant showed the highest activity towards the two substrates, with an 8.4-fold increase towards L-threonine and a 2.0-fold increase towards L-allo-threonine compared with the wild-type enzyme. The crystal structures of LATA and its mutant LATA_H128Y/S292R reported here will provide further insights into the regulation of the stereoselectivity of threonine aldolases targeted for the catalysis of L-allo-threonine/L-threonine synthesis.

  14. Emiliania huxleyi endures N-limitation with an efficient metabolic budgeting and effective ATP synthesis.

    Science.gov (United States)

    Rokitta, Sebastian D; Von Dassow, Peter; Rost, Björn; John, Uwe

    2014-12-02

    Global change will affect patterns of nutrient upwelling in marine environments, potentially becoming even stricter regulators of phytoplankton primary productivity. To better understand phytoplankton nutrient utilization on the subcellular basis, we assessed the transcriptomic responses of the life-cycle stages of the biogeochemically important microalgae Emiliania huxleyi to nitrogen-limitation. Cells grown in batch cultures were harvested at 'early' and 'full' nitrogen-limitation and were compared with non-limited cells. We applied microarray-based transcriptome profilings, covering ~10.000 known E. huxleyi gene models, and screened for expression patterns that indicate the subcellular responses. The diploid life-cycle stage scavenges nitrogen from external organic sources and -like diatoms- uses the ornithine-urea cycle to rapidly turn over cellular nitrogen. The haploid stage reacts similarly, although nitrogen scavenging is less pronounced and lipid oxidation is more prominent. Generally, polyamines and proline appear to constitute major organic pools that back up cellular nitrogen. Both stages induce a malate:quinone-oxidoreductase that efficiently feeds electrons into the respiratory chain and drives ATP generation with reduced respiratory carbon throughput. The use of the ornithine-urea cycle to budget the cellular nitrogen in situations of limitation resembles the responses observed earlier in diatoms. This suggests that underlying biochemical mechanisms are conserved among distant clades of marine phototrophic protists. The ornithine-urea cycle and proline oxidation appear to constitute a sensory-regulatory system that monitors and controls cellular nitrogen budgets under limitation. The similarity between the responses of the life-cycle stages, despite the usage of different genes, also indicates a strong functional consistency in the responses to nitrogen-limitation that appears to be owed to biochemical requirements. The malate

  15. Synthesis of 32P labelled phosphate sources with different solubility and their efficient s as fertilizers

    International Nuclear Information System (INIS)

    De Luca, Edgar Fernando; Boaretto, Antonio Enedi; Muraoka, Takashi

    1999-01-01

    The study was carried out at the Centro de Energia Nuclear na Agricultura, Universidade de Sao Paulo (CENA/USP), Brazil. With the objective to determine, by the isotopic tracer, the P recovery by rice (Oriza sativa) plants and eucalypt (Eucalyptus grandis) seedlings from the P sources with different solubilities, an experiment was carried out in greenhouse, using Quartzpsamment soil samples, which is very poor in P content. Monocalcium, bicalcium, and tricalcium phosphate, Ca(H2 32 PO4).H2O, CaH 32 PO4.2H2O and Ca3(32 PO4)2, respectively were obtained in laboratory. Their solubilities and the X-ray difratometry and differential thermal analysis comproved that the laboratory procedures were adequate for obtaining the desired compounds. These products were applied in the soil as fertilizers. Plants were harvested 60 days after growth period, digested and analysed for total P and 32 P counting through Cerenkov effect. The P recovery from the sources varied from 14.1% [Ca(H2 32 PO4).H2O] to 17.0% [CaH 32 PO4.2H2O] for eucalypt, and from 15.0% [Ca3(32 PO4)2] to 22.2% [CaH 32 PO4.2H2O] for rice. The rice plants showed better ability to absorb P from the laboratory prepared sources, but the eucalypt presented higher P nutritional efficiency index. The difference method, used for determining the P recovery, underestimated the eucalypt and rice plant ability to absorb this nutrient compared to the isotopic method

  16. Facile synthesis of cobalt-doped zinc oxide thin films for highly efficient visible light photocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Altintas Yildirim, Ozlem, E-mail: ozlemaltintas@gmail.com [Department of Metallurgical and Materials Engineering, Selcuk University, Konya (Turkey); Arslan, Hanife; Sönmezoğlu, Savaş [Department of Metallurgical and Materials Engineering, Karamanoglu Mehmetbey University, Karaman (Turkey); Nanotechnology R& D Laboratory, Karamanoglu Mehmetbey University, Karaman (Turkey)

    2016-12-30

    Highlights: • Photocatalytically active Co-ZnO thin film was obtained by sol-gel method. • Co{sup 2+} doping narrowed the band gap of pure ZnO to an extent of 3.18 eV. • Co-ZnO was effective in MB degradation under visible light. • Optimum dopant content to show high performance was 3 at.%. - Abstract: Cobalt-doped zinc oxide (Co:ZnO) thin films with dopant contents ranging from 0 to 5 at.% were prepared using the sol–gel method, and their structural, morphological, optical, and photocatalytic properties were characterized. The effect of the dopant content on the photocatalytic properties of the films was investigated by examining the degradation behavior of methylene blue (MB) under visible light irradiation, and a detailed investigation of their photocatalytic activities was performed by determining the apparent quantum yields (AQYs). Co{sup 2+} ions were observed to be substitutionally incorporated into Zn{sup 2+} sites in the ZnO crystal, leading to lattice parameter constriction and band gap narrowing due to the photoinduced carriers produced under the visible light irradiation. Thus, the light absorption range of the Co:ZnO films was improved compared with that of the undoped ZnO film, and the Co:ZnO films exhibited highly efficient photocatalytic activity (∼92% decomposition of MB after 60-min visible light irradiation for the 3 at.% Co:ZnO film). The AQYs of the Co:ZnO films were greatly enhanced under visible light irradiation compared with that of the undoped ZnO thin film, demonstrating the effect of the Co doping level on the photocatalytic activity of the films.

  17. Convergent Synthesis of Piperidines by the Union of Conjugated Alkynes with Imines: A Unique Regioselective Bond Construction for Heterocycle Synthesis

    Science.gov (United States)

    Chen, Ming Z.; Micalizio, Glenn C.

    2009-01-01

    A two-step process is described for the union of aromatic imines, conjugated alkynes and aldehydes that results in a stereoselective synthesis of highly substituted piperidines. This synthetic process has been made possible by defining a unique regioselective functionalization of conjugated alkynes that establishes a suitably functionalized substrate for subsequent heterocycle-forming cationic annulation. Given the flexibility of the coupling process, heterocycles can be accessed through a process that establishes up to four stereogenic centers and four fused rings. PMID:19817447

  18. Rational engineering of p-hydroxybenzoate hydroxylase to enable efficient gallic acid synthesis via a novel artificial biosynthetic pathway.

    Science.gov (United States)

    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.

  19. Protein Engineering and Homologous Expression of Serratia marcescens Lipase for Efficient Synthesis of a Pharmaceutically Relevant Chiral Epoxyester.

    Science.gov (United States)

    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.

  20. Structure elucidation and stereoselective total synthesis of pavettamine, the causal agent of gousiekte

    CSIR Research Space (South Africa)

    Bode, ML

    2010-03-01

    Full Text Available resolution fast atom bombardment (FAB) mass spectra were recorded by Dr. L. Fourie, University of Potchefstroom, on a VG 7070-E spectrometer (Xe beam, m-nitrobenzyl alcohol matrix, detection of positive ions with m/z>99). Electrospray-mass spectrometry (ES...), 45.46T (C-1), 31.46T and 31.16T (C-3), 30.00Q ((CH3)2C), 28.44Q (C(CH3)3), 19.87Q and 19.71Q ((CH3)2C). HRMS (FAB): m/z 631.4042 (M+); calcd for C31H57N3O10: 631.4044. 3.5 Diethyl (2S)-malate (4) (2S)-Malic acid (100 g, 0.746 mol) was suspended...

  1. Stereoselective Synthesis of Tetrahydroindolizines through the Catalytic Formation of Pyridinium Ylides from Diazo Compounds.

    Science.gov (United States)

    Day, Jonathan; McKeever-Abbas, Ben; Dowden, James

    2016-05-04

    Commercially available iron(III) and copper(I) complexes catalyzed multicomponent cycloaddition reactions between diazo compounds, pyridines, and electrophilic alkenes to give alkaloid-inspired tetrahydroindolizidines in high yield with high diastereoselectivity. Hitherto, the catalytic formation of versatile pyridinium ylides from metal carbenes has been poorly developed; the broad utility demonstrated herein sets the stage for the invention of further multicomponent reactions in future. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis of novel cyano-cyclitols and their stereoselective biotransformation catalyzed by Rhodococcus erythropolis A4

    Czech Academy of Sciences Publication Activity Database

    D’Antona, N.; Nicolosi, G.; Morrone, R.; Kubáč, David; Kaplan, Ondřej; Martínková, Ludmila

    2010-01-01

    Roč. 21, č. 6 (2010), s. 695-702 ISSN 0957-4166 R&D Projects: GA MŠk OC09046 Institutional research plan: CEZ:AV0Z50200510 Keywords : ALICYCLIC NITRILES * ASYMMETRIZATION * HYDROLYSIS Subject RIV: CC - Organic Chemistry Impact factor: 2.484, year: 2010

  3. Stereoselective cathodic synthesis of 8-substituted (1R,3R,4S-menthylamines

    Directory of Open Access Journals (Sweden)

    Carolin Edinger

    2015-02-01

    Full Text Available The electrochemical generation of menthylamines from the corresponding menthone oximes equipped with an additional substituent in position 8 is described. Due to 1,3-diaxial interactions a pronounced diastereoselectivity for the menthylamines is found.

  4. Photoprompted Hot Electrons from Bulk Cross-Linked Graphene Materials and Their Efficient Catalysis for Atmospheric Ammonia Synthesis.

    Science.gov (United States)

    Lu, Yanhong; Yang, Yang; Zhang, Tengfei; Ge, Zhen; Chang, Huicong; Xiao, Peishuang; Xie, Yuanyuan; Hua, Lei; Li, Qingyun; Li, Haiyang; Ma, Bo; Guan, Naijia; Ma, Yanfeng; Chen, Yongsheng

    2016-11-22

    Ammonia synthesis is the single most important chemical process in industry and has used the successful heterogeneous Haber-Bosch catalyst for over 100 years and requires processing under both high temperature (300-500 °C) and pressure (200-300 atm); thus, it has huge energy costs accounting for about 1-3% of human's energy consumption. Therefore, there has been a long and vigorous exploration to find a milder alternative process. Here, we demonstrate that by using an iron- and graphene-based catalyst, Fe@3DGraphene, hot (ejected) electrons from this composite catalyst induced by visible light in a wide range of wavelength up to red could efficiently facilitate the activation of N 2 and generate ammonia with H 2 directly at ambient pressure using light (including simulated sun light) illumination directly. No external voltage or electrochemical or any other agent is needed. The production rate increases with increasing light frequency under the same power and with increasing power under the same frequency. The mechanism is confirmed by the detection of the intermediate N 2 H 4 and also with a measured apparent activation energy only ∼1/4 of the iron based Haber-Bosch catalyst. Combined with the morphology control using alumina as the structural promoter, the catalyst retains its activity in a 50 h test.

  5. Amine-Free Synthesis of Cesium Lead Halide Perovskite Quantum Dots for Efficient Light-Emitting Diodes

    KAUST Repository

    Yassitepe, Emre; Yang, Zhenyu; Voznyy, Oleksandr; Kim, Younghoon; Walters, Grant; Castañ eda, Juan Andres; Kanjanaboos, Pongsakorn; Yuan, Mingjian; Gong, Xiwen; Fan, Fengjia; Pan, Jun; Hoogland, Sjoerd; Comin, Riccardo; Bakr, Osman; Padilha, Lazaro A.; Nogueira, Ana F.; Sargent, Edward H.

    2016-01-01

    Cesium lead halide perovskite quantum dots (PQDs) have attracted significant interest for optoelectronic applications in view of their high brightness and narrow emission linewidth at visible wavelengths. A remaining challenge is the degradation of PQDs during purification from the synthesis solution. This is attributed to proton transfer between oleic acid and oleylamine surface capping agents that leads to facile ligand loss. Here, a new synthetic method is reported that enhances the colloidal stability of PQDs by capping them solely using oleic acid (OA). Quaternary alkylammonium halides are used as precursors, eliminating the need for oleylamine. This strategy enhances the colloidal stability of OA capped PQDs during purification, allowing us to remove excess organic content in thin films. Inverted red, green, and blue PQD light-emitting diodes (LED) are fabricated for the first time with solution-processed polymer-based hole transport layers due to higher robustness of OA capped PQDs to solution processing. The blue and green LEDs exhibit threefold and tenfold improved external quantum efficiency (EQE), respectively, compared to prior related reports for amine/ammonium capped cross-linked PQDs. The brightest blue LED based on all inorganic CsPb(Br1- xClx)3 PQDs is also reported. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Highly efficient one-step synthesis of carbon encapsulated nanocrystals by the oxidation of metal π-complexes

    Science.gov (United States)

    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.

  7. Multifunctional Fe3O4/Au core/satellite nanocubes: an efficient chemical synthesis, characterization and functionalization of streptavidin protein.

    Science.gov (United States)

    Abbas, Mohamed; RamuluTorati, Sri; Kim, CheolGi

    2017-02-14

    A novel and efficient chemical approach for the synthesis of Fe 3 O 4 /Au core/satellite nanocubes is reported. In a one-pot reaction, metallic Au nanodots were successfully deposited on the polyvinylpyrrolidone (PVP) functionalized Fe 3 O 4 nanocube surface for the fabrication of a core/satellite structure (Fe 3 O 4 /Au) by the reduction of HAuCl 4 using ammonia. Transmission electron microscopy and energy dispersive spectroscopy mapping revealed that small Au nanodots of about 2 nm average size decorated the surface of Fe 3 O 4 nanocubes. X-ray diffraction data was used to confirm the formation of both the phases of a cubic inverse spinel structure for Fe 3 O 4 and a bcc structure for Au in the core/satellite structure of Fe 3 O 4 /Au nanocubes. The magnetic properties of the seed Fe 3 O 4 nanocubes and Fe 3 O 4 /Au core/satellite nanocubes were measured by using a superconducting quantum interference device at 300 K. For biological application purposes, the as-synthesized Fe 3 O 4 /Au core/satellite nanocubes were functionalized by cysteamine followed by successful immobilization of streptavidin protein as confirmed through the fluorescence confocal microscopy images.

  8. Amine-Free Synthesis of Cesium Lead Halide Perovskite Quantum Dots for Efficient Light-Emitting Diodes

    KAUST Repository

    Yassitepe, Emre

    2016-10-31

    Cesium lead halide perovskite quantum dots (PQDs) have attracted significant interest for optoelectronic applications in view of their high brightness and narrow emission linewidth at visible wavelengths. A remaining challenge is the degradation of PQDs during purification from the synthesis solution. This is attributed to proton transfer between oleic acid and oleylamine surface capping agents that leads to facile ligand loss. Here, a new synthetic method is reported that enhances the colloidal stability of PQDs by capping them solely using oleic acid (OA). Quaternary alkylammonium halides are used as precursors, eliminating the need for oleylamine. This strategy enhances the colloidal stability of OA capped PQDs during purification, allowing us to remove excess organic content in thin films. Inverted red, green, and blue PQD light-emitting diodes (LED) are fabricated for the first time with solution-processed polymer-based hole transport layers due to higher robustness of OA capped PQDs to solution processing. The blue and green LEDs exhibit threefold and tenfold improved external quantum efficiency (EQE), respectively, compared to prior related reports for amine/ammonium capped cross-linked PQDs. The brightest blue LED based on all inorganic CsPb(Br1- xClx)3 PQDs is also reported. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Controllable Electrochemical Synthesis of Reduced Graphene Oxide Thin-Film Constructed as Efficient Photoanode in Dye-Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Soon Weng Chong

    2016-01-01

    Full Text Available A controllable electrochemical synthesis to convert reduced graphene oxide (rGO from graphite flakes was introduced and investigated in detail. Electrochemical reduction was used to prepare rGO because of its cost effectiveness, environmental friendliness, and ability to produce rGO thin films in industrial scale. This study aimed to determine the optimum applied potential for the electrochemical reduction. An applied voltage of 15 V successfully formed a uniformly coated rGO thin film, which significantly promoted effective electron transfer within dye-sensitized solar cells (DSSCs. Thus, DSSC performance improved. However, rGO thin films formed in voltages below or exceeding 15 V resulted in poor DSSC performance. This behavior was due to poor electron transfer within the rGO thin films caused by poor uniformity. These results revealed that DSSC constructed using 15 V rGO thin film exhibited high efficiency (η = 1.5211% attributed to its higher surface uniformity than other samples. The addition of natural lemon juice (pH ~ 2.3 to the electrolyte accelerated the deposition and strengthened the adhesion of rGO thin film onto fluorine-doped tin oxide (FTO glasses.

  10. 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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Nad, Shreya [Department of Electrical and Computer Engineering, Michigan State University, East Lansing, Michigan 48824 (United States); Department of Physics and Astronomy, Michigan State University, East Lansing, Michigan 48824 (United States); Gu, Yajun; Asmussen, Jes [Department of Electrical and Computer Engineering, Michigan State University, East Lansing, Michigan 48824 (United States)

    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 efficiencies (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.

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

    Science.gov (United States)

    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.

  13. Single and double stereoselective fluorination of (E-allylsilanes

    Directory of Open Access Journals (Sweden)

    Tredwell Matthew

    2007-10-01

    Full Text Available Abstract Acyclic allylic monofluorides were prepared by electrophilic fluorination of branched (E-allylsilanes with Selectfluor. These reactions proceeded with efficient transfer of chirality from the silylated to the fluorinated stereocentre. Upon double fluorination, an unsymmetrical ethyl syn-2,5-difluoroalk-3-enoic ester was prepared, the silyl group acting as an anti stereodirecting group for the two C-F bond forming events.

  14. Autographa californica multiple nucleopolyhedrovirus ac66 is required for the efficient egress of nucleocapsids from the nucleus, general synthesis of preoccluded virions and occlusion body formation

    International Nuclear Information System (INIS)

    Ke Jianhao; Wang Jinwen; Deng Riqiang; Wang Xunzhang

    2008-01-01

    Although orf66 (ac66) of Autographa californica multiple nucleopolyhedrovirus (AcMNPV) is conserved in all sequenced lepidopteran baculovirus genomes, its function is not known. This paper describes generation of an ac66 knockout AcMNPV bacmid mutant and analyses of the influence of ac66 deletion on the virus replication in Sf-9 cells so as to determine the role of ac66 in the viral life cycle. Results indicated that budded virus (BV) yields were reduced over 99% in ac66-null mutant infected cells in comparison to that in wild-type virus infected cells. Optical microscopy revealed that occlusion body synthesis was significantly reduced in the ac66 knockout bacmid-transfected cells. In addition, ac66 deletion interrupted preoccluded virion synthesis. The mutant phenotype was rescued by an ac66 repair bacmid. On the other hand, real-time PCR analysis indicated that ac66 deletion did not affect the levels of viral DNA replication. Electron microscopy revealed that ac66 is not essential for nucleocapsid assembly, but for the efficient transport of nucleocapsids from the nucleus to the cytoplasm. These results suggested that ac66 plays an important role for the efficient exit of nucleocapsids from the nucleus to the cytoplasm for BV synthesis as well as for preoccluded virion and occlusion synthesis

  15. Stereoselective 1,3-Insertions of Rhodium(II) Azavinyl Carbenes

    Science.gov (United States)

    Chuprakov, Stepan; Worrell, Brady T.; Selander, Nicklas; Sit, Rakesh K.; Fokin, Valery V.

    2014-01-01

    Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild and convergent formal 1,3-insertion into N–H and O–H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bis-functionalized Z-olefins with perfect regio- and stereoselectively. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles. PMID:24295389

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  19. Zinc (II) [tetra(4-methylphenyl)] Porphyrin: a Novel and Reusable Catalyst for Efficient Synthesis of 2,4,5-trisubstituted Imidazoles Under Ultrasound Irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Safari, Javad; Khalili, Shiva Dehghan; Banitaba, Sayed Hossein; Dehghani, Hossein [Univ. of Kashan, Kashan (Iran, Islamic Republic of)

    2011-10-15

    An efficient three-component one-step synthesis of 2,4,5-trisubstituted imidazoles by condensation reaction of 1,2-diketones or α-hydroxyketones with aromatic aldehydes and ammonium acetate using Zinc (II) [tetra (4-methylphenyl)] porphyrin as a novel and reusable catalyst under ultrasound irradiation at ambient temperature is described. In this method, α-hydroxyketones as well as 1,2-diketones were converted to their corresponding 2,4,5-trisubstituted imidazoles in excellent yields.

  20. Polyethylene Glycol (PEG-400: An Efficient and Recyclable Reaction Medium for the Synthesis of Pyrazolo[3,4-b]pyridin-6(7H-one Derivatives

    Directory of Open Access Journals (Sweden)

    Deming Wang

    2013-10-01

    Full Text Available A mild and efficient synthesis of pyrazolo[3,4-b]pyridine-6(7H-one derivatives via a three-component reaction of an aldehyde, Meldrum’s acid and 3-methyl-1H-pyrazol-5-amine using recyclable polyethylene glycol (PEG-400 as a reaction medium is described. This method has the advantages of accessible starting materials, good yields, mild reaction conditions and begin environmentally friendly.

  1. Biocatalysts for the pharmaceutical industry created by structure-guided directed evolution of stereoselective enzymes.

    Science.gov (United States)

    Li, Guangyue; Wang, Jian-Bo; Reetz, Manfred T

    2018-04-01

    Enzymes have been used for a long time as catalysts in the asymmetric synthesis of chiral intermediates needed in the production of therapeutic drugs. However, this alternative to man-made catalysts has suffered traditionally from distinct limitations, namely the often observed wrong or insufficient enantio- and/or regioselectivity, low activity, narrow substrate range, and insufficient thermostability. With the advent of directed evolution, these problems can be generally solved. The challenge is to develop and apply the most efficient mutagenesis methods which lead to highest-quality mutant libraries requiring minimal screening. Structure-guided saturation mutagenesis and its iterative form have emerged as the method of choice for evolving stereo- and regioselective mutant enzymes needed in the asymmetric synthesis of chiral intermediates. The number of (industrial) applications in the preparation of chiral pharmaceuticals is rapidly increasing. This review features and analyzes typical case studies. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Tin-free visible light photoredox catalysed cyclisation of enamides as a mild procedure for the synthesis of γ-lactams

    KAUST Repository

    Fava, Eleonora

    2016-07-13

    The first visible light mediated tin-free cyclisation of α-chloroenamides leading to the synthesis of substituted γ-lactams with excellent stereoselectivity is reported. The protocol employs the single-electron reduction of activated C–Cl bonds, which are typically inert towards reduction.

  3. Tin-free visible light photoredox catalysed cyclisation of enamides as a mild procedure for the synthesis of γ-lactams

    KAUST Repository

    Fava, Eleonora; Nakajima, Masaki; Tabak, Martin B.; Rueping, Magnus

    2016-01-01

    The first visible light mediated tin-free cyclisation of α-chloroenamides leading to the synthesis of substituted γ-lactams with excellent stereoselectivity is reported. The protocol employs the single-electron reduction of activated C–Cl bonds, which are typically inert towards reduction.

  4. Diastereoselective Synthesis of Novel Heterocyclic Scaffolds through Tandem Petasis 3-Component/Intramolecular Diels-Alder and ROM-RCM Reactions

    DEFF Research Database (Denmark)

    Ishøy, Mette; Petersen, Rico; Petersen, Michael Åxman

    2017-01-01

    A high-yielding, stereoselective and extraordinarily complexity generatingPetasis 3-component/intramolecular Diels-Alderreaction has been developed. In combination with ROM-RCM, rapid access to complex sp3-rich heterocyclic scaffolds amenableto subsequent functionalization and library synthesis...

  5. Efficient synthesis of tungsten oxide hydrate-based nanocomposites for applications in bifunctional electrochromic-energy storage devices

    Science.gov (United States)

    Chang, Xueting; Hu, Ruirui; Sun, Shibin; Lu, Tong; Liu, Tao; Lei, Yanhua; Dong, Lihua; Yin, Yansheng; Zhu, Yanqiu

    2018-05-01

    In this work, we realized the large-scale synthesis of WO3 · H2O nanoflakes (NFs), g-C3N4/WO3 · H2O nanocomposite (NC) and graphene (G)/WO3 · H2O NC via a sonochemical process with tungsten salt as the precursor, g-C3N4 or G sheets as the supports, and distilled water as the solvent. Both the g-C3N4/WO3 · H2O NC and G/WO3 · H2O NC exhibited much better electrochromic (EC) performance (higher coloration efficiencies and faster response times) than that of the WO3 · H2O NFs. Using the WO3 · H2O-based materials as electrode materials, EC batteries that integrate the energy storage and EC functions in one device have been assembled. The energy status of the EC batteries could be visually indicated by the reversible color variations. Compared with the plain WO3 · H2O-based EC batteries, the NC-based EC batteries possessed a lower color contrast between the charged and discharged conditions but much longer discharge durations. The EC batteries could be quickly charged in a few seconds by adding H2O2, and the charged batteries exhibited significantly-enhanced discharging durations in comparison with the initial ones. The g-C3N4/WO3 · H2O NC-EC batteries charged by a small amount of H2O2 could produce a long discharging duration up to 760 min.

  6. Synthesis of highly phosphonic acid functionalized benzene-bridged periodic mesoporous organosilicas for use as efficient dye adsorbents

    International Nuclear Information System (INIS)

    Deka, Juti Rani; Liu, Chia-Ling; Wang, Tzu-Hua; Chang, Wei-Chieh; Kao, Hsien-Ming

    2014-01-01

    Highlights: • Synthesis of highly phosphonic acid functionalized benzene-bridged PMOs. • Phosphonic acid loaded PMOs as adsorbent for cationic and anionic dyes. • Due to electrostatic interaction the adsorbent has high dye adsorption capacity. • π–π stacking interaction between benzene and dye enhances adsorption capacity. • Intraparticle diffusion played a dominant role in the adsorption process. - Abstract: Periodic mesoporous organosilicas (PMOs) with benzene bridging groups in the silica wall were functionalized with a tunable content of phosphonic acid groups. These bifunctional materials were synthesized by co-condensation of two different organosilane precursors, that is, 1,4-bis(triethoxysilyl)benzene (BTEB) and sodium 3-(trihydroxysilyl)propyl methyl phosphate (SPMP), under acidic conditions using nonionic surfactant Brij-S10 as template. The materials exhibited well-ordered mesostructures and were characterized by X-ray diffraction, nitrogen sorption, TEM, TGA, FTIR, and solid-state NMR measurements. The materials thus obtained were employed as adsorbents to remove different types of dyes, for example, cationic dyes methylene blue and phenosafranine, anionic orange II, and amphoteric rhodamine B, from aqueous solutions. The materials exhibited a remarkably high adsorption capacity than activated carbon due to their ordered mesostructures, a large number of phosphonic acid groups, and high surface areas. The adsorption was mainly governed by electrostatic interaction, but also involved π–π stacking interaction as well as hydrogen bonding. The adsorption kinetics can be better fitted by the pseudo-second order model. The adsorption process was controlled by the mechanisms of external mass transfer and intraparticle diffusion. The materials retained more than 97% dye removal efficiency after use for five consecutive cycles

  7. Tannic Acid an Efficient Catalyst for the Synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one Derivatives

    Directory of Open Access Journals (Sweden)

    Deepak S. Kawade

    2015-06-01

    Full Text Available Tannic acid explore a highly efficient catalytic activity for the synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one derivatives in excellent yields via cyclocondensation of aromatic aldehyde, β-naphthol and dimedone. Catalyst having advantages such as it is cheap and biodegradable and the protocol avoids the use of expensive catalyst and toxic solvent. We believe that this methodology is an efficient, simple, highly yielding, time saving and environmentally friendly. DOI: http://dx.doi.org/10.17807/orbital.v7i2.683

  8. Potassium phthalimide as efficient basic organocatalyst for the synthesis of 3,4-disubstituted isoxazol-5(4H-ones in aqueous medium

    Directory of Open Access Journals (Sweden)

    Hamzeh Kiyani

    2017-01-01

    Full Text Available Potassium phthalimide (PPI is employed as an efficient and effective basic organocatalyst for the one-pot three-component reaction of β-oxoesters with hydroxylamine hydrochloride and various aromatic aldehydes. This cyclocondensation reaction was performed in water as an environmentally benign solvent at room temperature giving 3,4-disubstituted isoxazol-5(4H-ones in good to excellent yields. PPI was found to be an effective organocatalyst for the synthesis of isoxazol-5(4H-one system. The advantages of this method are efficiency, clean, easy work-up, high yields, shorter reaction times, inexpensive, and readily available catalyst.

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

    Science.gov (United States)

    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.

  10. A Novel and Efficient Five-Component Synthesis of Pyrazole Based Pyrido[2,3-d]pyrimidine-diones in Water: A Triply Green Synthesis

    Directory of Open Access Journals (Sweden)

    Majid M. Heravi

    2016-04-01

    Full Text Available A novel one pot synthesis of pyrazolo[4′,3′:5,6]pyrido[2,3-d]pyrimidine-diones, via a five-component reaction, involving, hydrazine hydrate, ethyl acetoacetate, and 1,3-dimethyl barbituric acid, an appropriate aryl aldehydes and ammonium acetate catalyzed via both of heterogeneous and homogeneous catalysis in water, is reported.

  11. Synthesis of modified proanthocyanidins: easy and general introduction of a hydroxy group at C-6 of catechin; efficient synthesis of elephantorrhizol.

    Science.gov (United States)

    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.

  12. Probing the stereoselective interaction of ofloxacin enantiomers with corresponding monoclonal antibodies by multiple spectrometry

    Science.gov (United States)

    Mu, Hongtao; Xu, Zhenlin; Liu, Yingju; Sun, Yuanming; Wang, Baoling; Sun, Xiulan; Wang, Zhanhui; Eremin, Sergei; Zherdev, Anatoly V.; Dzantiev, Boris B.; Lei, Hongtao

    2018-04-01

    Although stereoselective antibody has immense potential in chiral compounds detection and separation, the interaction traits between stereoselective antibody and the corresponding antigenic enantiomers are not yet fully exploited. In this study, the stereospecific interactions between ofloxacin isomers and corresponding monoclonal antibodies (McAb-WR1 and McAb-MS1) were investigated using time-resolved fluorescence, steady-state fluorescence, and circular dichroism (CD) spectroscopic methods. The chiral recognition discrepancies of antibodies with ofloxacin isomers were reflected through binding constant, number of binding sites, driving forces and conformational changes. The major interacting forces of McAb-WR1 and McAb-MS1 chiral interaction systems were hydrophobic force and van der Waals forces joined up with hydrogen bonds, respectively. Synchronous fluorescence spectra and CD spectra results showed that the disturbing of tyrosine and tryptophan micro-environments were so slightly that no obvious secondary structure changes were found during the chiral hapten binding. Clarification of stereospecific interaction of antibody will facilitate the application of immunoassay to analyze chiral contaminants in food and other areas.

  13. Microbial Stereoselective One-Step Conversion of Diols to Chiral Lactones in Yeast Cultures

    Directory of Open Access Journals (Sweden)

    Filip Boratyński

    2015-12-01

    Full Text Available It has been shown that whole cells of different strains of yeast catalyze stereoselective oxidation of meso diols to the corresponding chiral lactones. Among screening-scale experiments, Candida pelliculosa ZP22 was selected as the most effective biocatalyst for the oxidation of monocyclic diols 3a–b with respect to the ratio of high conversion to stereoselectivity. This strain was used in the preparative oxidation, affording enantiomerically-enriched isomers of lactones: (+-(3aR,7aS-cis-hexahydro-1(3H -isobenzofuranone (2a and (+-(3aS,4,7,7aR-cis-tetrahydro-1(3H-isobenzofuranone (2b. Scaling up the culture growth, as well as biotransformation conditions has been successfully accomplished. Among more bulky substrates, bicyclic diol 3d was totally converted into enantiomerically-pure exo-bridged (+-(3aR,4S,7R,7aS-cis-tetrahydro-4,7-methanoisobenzofuran -1(3H-one (2d by Yarrovia lipolytica AR71. Microbial oxidation of diol 3f by Candida sake AM908 and Rhodotorula rubra AM4 afforded optically-pure cis-3-butylhexahydro-1(3H -isobenzofuranone (2f, however with low conversion.

  14. Stereoselective bioaccumulation of chiral PCB 91 in earthworm and its metabolomic and lipidomic responses.

    Science.gov (United States)

    He, Zeying; Wang, Yuehua; Zhang, Yanwei; Cheng, Haiyan; Liu, Xiaowei

    2018-07-01

    Stereoselective bioaccumulation, elimination, metabolomic and lipidomic responses of earthworm Eisenia fetida exposed to chiral polychlorinated biphenyl (PCB) 91 in an earthworm-soil system were investigated. Preferential bioaccumulation of (-)-PCB 91 and elimination of (+)-PCB 91 were observed following 50 and 500 μg/kg dwt exposures. Enantiomer fraction (EF) values decreased over time during the uptake and elimination periods. Metabolomics and lipidomics techniques based on ultra-performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS) revealed significant changes in 108 metabolites after earthworms exposure to (+)-, (-)-, and (±)-PCB 91, compared to control groups. Forty two of these metabolites were identified as amino acids, nucleosides, fatty acids, dicarboxylic acids, vitamins or others. Lysophospholipids including six lysophosphatidylcholines (LPC), six lysophosphatidylethanolamine (LPE), eight lysophosphatidylinositol (LPI) and five lysophosphatidylserine (LPS) were also differentially expressed between exposure and control groups. Alterations in the levels of metabolites and lipids indicated stereoselective effects of chiral PCB 91 on earthworm amino acid, energy, and nucleotide metabolism, neurodevelopment and gene expression. Overall, the effects of (+)-PCB 91 were more pronounced than that of (-)- and (±)-PCB 91. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Stereoselective formation of a cholesterol ester conjugate from fenvalerate by mouse microsomal carboxyesterase(s).

    Science.gov (United States)

    Miyamoto, J; Kaneko, H; Takamatsu, Y

    1986-06-01

    In accordance with in vivo findings, of the four chiral isomers of fenvalerate (S-5602 Sumicidin, Pydrin, [RS]-alpha-cyano-3-phenoxybenzyl [RS]-2-(4-chlorophenyl)isovalerate), only the [2R, alpha S]-isomer (B-isomer) yielded cholesteryl [2R]-2-(4-chlorophenyl)isovalerate (CPIA-cholesterol ester) in the in vitro study using several tissue homogenates of mice, rats, dogs, and monkeys. There were species differences in the extent of CPIA-cholesterol-ester formation, with mouse tissues showing relatively higher activity than those of other animals. The kidney, brain, and spleen of mice showed relatively higher capacities to form this ester compared to other tissues, and the enzyme activity was mainly localized in microsomal fractions. The CPIA-cholesterol ester did not seem to be produced by three known biosynthetic pathways of endogenous cholesterol esters--acyl-CoA:cholesterol O-acyltransferase (ACAT), lecithin:cholesterol O-acyltransferase (LCAT), and cholesterol esterase. Carboxyesterase(s) of mouse kidney microsomes solubilized by digitonin hydrolyzed only the B alpha-isomer of fenvalerate, yielding CPIA, whereas they yielded the corresponding cholesterol ester in the presence of artificial liposomes containing cholesterol. Thus, it appears that the stereoselective formation of the CPIA-cholesterol ester results from the stereoselective formation of the CPIA-carboxyesterase complex only from the B alpha-isomer, which subsequently undergoes cleavage by cholesterol to yield the CPIA-cholesterol ester.

  16. Stereo-controlled synthesis of polyheterocycles via the diene-transmissive hetero-Diels-Alder reaction of β,γ-unsaturated α-keto esters.

    Science.gov (United States)

    Otani, Takashi; Tamai, Yumiko; Seki, Kazunori; Kikuchi, Tomohiro; Miyazawa, Taiichiro; Saito, Takao

    2015-06-07

    We describe the stereoselective synthesis of polyring-fused heterocyclic compounds based on diene-transmissive hetero-Diels-Alder reactions utilizing β,γ-unsaturated α-keto esters. This protocol involves the initial endo- or exo-selective Diels-Alder (DA) reactions with electron-rich dienophiles, methylenation of the ester carbonyl groups with the Tebbe reagent, and a stereoselective second DA reaction with electron-deficient dienophiles. The use of enantioselective DA reactions in the initial reaction enables access to chiral polyring-fused heterocyclic compounds with multiple chiral centres.

  17. Metabolic stereoselectivity of cytochrome P450 3A4 towards deoxypodophyllotoxin : In silico predictions and experimental validation

    NARCIS (Netherlands)

    Julsing, Mattijs K.; Vasilev, Nikolay P.; Schneidman-Duhovny, Dina; Muntendarn, Remco; Woerdenbag, Herman J.; Quax, Wim J.; Wolfson, Haim J.; Ionkova, Iliana; Kayser, Oliver

    Deoxypodophyllotoxin is stereoselectively converted into epipodophyllotoxin by recombinant human cytochrome P450 3A4 (CY-P3A4). Further kinetic analysis revealed that the Michaelis-Menten K(m) and V(max) for hydroxylation of deoxypodophyllotoxin by CYP3A4 at C7 position were 1.93 mu M and 1.48

  18. Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

    KAUST Repository

    Vidal, Fernando

    2016-07-07

    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

  19. Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

    KAUST Repository

    Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y.-X.

    2016-01-01

    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

  20. First total synthesis of (-)-AL-2.

    Science.gov (United States)

    Miyakoshi, Naoki; Mukai, Chisato

    2003-06-26

    Treatment of the 3,4-dioxygenated-9-hydroxy-1-nonyn-5-one derivative, derived from diethyl l-tartrate, with a palladium catalyst in methanol under a CO atmosphere effected an intramolecular acetalization and a stereoselective construction of the (E)-methoxycarbonylmethylidene functionality resulting in formation of the core framework of the diacetylenic spiroacetal enol ether natural products. Chemical transformations of the 1,6-dioxaspiro[4.5]decane derivative thus formed led to the first total synthesis of (-)-AL-2. [reaction: see text

  1. First total synthesis of (-)-ichthyothereol and its acetate.

    Science.gov (United States)

    Mukai, C; Miyakoshi, N; Hanaoka, M

    2001-08-24

    The first and stereoselective total syntheses of (-)-ichthyothereol (1) and its acetate ((+)-2) were achieved by incorporation of the two chiral centers of diethyl L-tartrate. The starting diethyl L-tartrate was converted into trans-2-ethynyl-3-hydroxytetrahydropyran 14 in a stereoselective manner via the endo mode cyclization of the epoxy-alkyne derivative 12. The alcohol 12 was then transformed into (E)-iodoolefin derivative 15, which was exposed to a coupling reaction with 1-tributylstannyl-1,3,5-heptyne (19), derived from the corresponding 1-trimethylsilyl-1,3,5-heptyne (18), under Stille conditions to produce the all-carbon framework of the target natural products. Chemical modification of the coupled product 20 under conventional conditions completed the first total synthesis of (-)-ichthyothereol (1) and its acetate ((+)-2).

  2. A General Catalytic Method for Highly Cost- and Atom-Efficient Nucleophilic Substitutions.

    Science.gov (United States)

    Huy, Peter H; Filbrich, Isabel

    2018-05-23

    A general formamide-catalyzed protocol for the efficient transformation of alcohols into alkyl chlorides, which is promoted by substoichiometric amounts (down to 34 mol %) of inexpensive trichlorotriazine (TCT), is introduced. This is the first example of a TCT-mediated dihydroxychlorination of an OH-containing substrate (e.g., alcohols and carboxylic acids) in which all three chlorine atoms of TCT are transferred to the starting material. The consequently enhanced atom economy facilitates a significantly improved waste balance (E-factors down to 4), cost efficiency, and scalability (>50 g). Furthermore, the current procedure is distinguished by high levels of functional-group compatibility and stereoselectivity, as only weakly acidic cyanuric acid is released as exclusive byproduct. Finally, a one-pot protocol for the preparation of amines, azides, ethers, and sulfides enabled the synthesis of the drug rivastigmine with twofold S N 2 inversion, which demonstrates the high practical value of the presented method. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Integration of Fermentation and Organic Synthesis: Studies of Roquefortine C and Biosynthetic Derivatives

    Science.gov (United States)

    Gober, Claire Marie

    Roquefortine C is one of the most ubiquitous indoline alkaloids of fungal origin. It has been isolated from over 30 different species of Penicillium fungi and has garnered attention in recent years for its role as a biosynthetic precursor to the triazaspirocyclic natural products glandicoline B, meleagrin, and oxaline. The triazaspirocyclic motif, which encompasses three nitrogen atoms attached to one quaternary carbon forming a spirocyclic scaffold, is a unique chemical moiety that has been shown to impart a wide array of biological activity, from anti-bacterial activity and antiproliferative activity against cancer cell lines to anti-biofouling against marine organisms. Despite the promise of these compounds in the pharmaceutical and materials industries, few syntheses of triazaspirocycles exist in the literature. The biosynthesis of roquefortine C-derived triazaspirocycles, however, provides inspiration for the synthesis of these compounds, namely through a nitrone-promoted transannular rearrangement. This type of internal rearrangement has never been carried out synthetically and would provide an efficient stereoselective synthesis of triazaspirocycles. This work encompasses efforts towards elucidating the biosynthetic pathway of roquefortine C-derived triazaspirocycles as well as synthetic efforts towards the construction of triazaspirocycles. Chapter 1 will discuss a large-scale fermentation procedure for the production of roquefortine C from Penicillium crustosum. Chapters 2 and 3 explore (through enzymatic and synthetic means, respectively) the formation of the key indoline nitrone moiety required for the proposed transannular rearrangement. Finally, chapter 4 will discuss synthetic efforts towards the synthesis of triazaspirocycles. This work has considerably enhanced our understanding of the roquefortine C biosynthetic pathway and the unique chemistry of this natural product, and our efforts towards the synthesis of triazaspirocycles will facilitate the

  4. Controllable synthesis of mesoporous carbon nanospheres and Fe-N/carbon nanospheres as efficient oxygen reduction electrocatalysts

    Science.gov (United States)

    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

  5. An unprecedented chemospecific and stereoselective tandem nucleophilic addition/cycloaddition reaction of nucleophilic carbenes with ketenimines.

    Science.gov (United States)

    Cheng, Ying; Ma, Yang-Guang; Wang, Xiao-Rong; Mo, Jun-Ming

    2009-01-16

    The first study of the reaction between nucleophilic carbenes and ketenimines is reported. The interaction of thiazole and benzothiazole carbenes with ketenimines proceeded in a chemospecific and stereoselective manner to produce thiazole- and benzothiazole-spiro-pyrrole derivatives generally in good yields. The reaction was proposed to proceed via a tandem nucleophilic addition of carbene to the C=N bond of ketenimine followed by a stepwise [3+2] cycloaddition of the 1,3-dipolar intermediate with the C=C bond of ketenimine. This reaction provides a powerful protocol for the construction of novel polyfunctional thiazole-spiro-pyrrole or benzothiazole-spiro-pyrrole compounds that are not readily accessible by other methods.

  6. Stereoselective toxicity of etoxazole to MCF-7 cells and its dissipation behavior in citrus and soil.

    Science.gov (United States)

    Sun, Dali; Pang, Junxiao; Fang, Qi; Zhou, Zhiqin; Jiao, Bining

    2016-12-01

    The stereoselective cytotoxicity of new chiral acaricide etoxazole and its dissipation in citrus and soil were investigated for the first time. Enantioselective toxicity and oxidative stress of etoxazole toward MCF-7 cells was conducted. The phenomenon of dose- and form-dependent cytotoxicity was demonstrated by MTT and LDH assays, ROS generation, and SOD and CAT activity alternation. Cytotoxicity ranks were found to be consistent with oxidative damage as (R)- > Rac- > (S)-etoxazole. Moreover, the results of enantioselective degradation showed that (S)-etoxazole degraded faster than its antipode (R)-etoxazole. The gradual raise of EF values indicated the achievement of enantioselective degradation in citrus and soil, leaving the enrichment of (R)-etoxazole isomer. Significant differences of environmental behavior and cytotoxicity of etoxazole enantiomers were found in this study which provided valuable insight into the mechanism of potential toxicity and warranted more careful assessment of this pesticide before its agricultural application.

  7. Update: An efficient synthesis of poly(ethylene glycol)-supported iron(II) porphyrin using a click reaction and its application for the catalytic olefination of aldehydes

    KAUST Repository

    Chinnusamy, Tamilselvi R.

    2012-05-09

    The facile synthesis of polyethylene glycol (PEG)-immobilized iron(II) porphyrin using a copper-catalyzed azide-alkyne [3+2] cycloaddition "click" reaction is reported. The prepared complex 5 (PEG-C 51H 39FeN 7O) was found to be an efficient catalyst for the selective olefination of aldehydes with ethyl diazoacetate in the presence of triphenylphosphine, and afforded excellent olefin yields with high (E) selectivities. The PEG-supported catalyst 5 was readily recovered by precipitation and filtration, and was recycled through ten runs without significant activity loss. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. A new Ni(II complex as a novel and efficient recyclable catalyst for the synthesis of pyrano[2,3-d]pyrimidines

    Directory of Open Access Journals (Sweden)

    M. Habibi Kheirabadi

    2016-12-01

    Full Text Available A simple and highly efficient one-pot three-component synthesis of a series of pyrido[2,3-d]pyrimidines from the condensation of barbituric acid, malononitrile and aromatic aldehydes using catalytic amount of a new Ni(II complex based on 5-nitro-N1-((pyridin-2-ylmethylene benzene-1,2-diamine (NiL is reported. This new heterogeneous catalyst has the advantages of being environmentally friendly, simple work-up and high yields character.

  9. Palladium-catalyzed domino C,N-coupling/carbonylation/Suzuki coupling reaction: an efficient synthesis of 2-aroyl-/heteroaroylindoles.

    Science.gov (United States)

    Arthuis, Martin; Pontikis, Renée; Florent, Jean-Claude

    2009-10-15

    A convenient one-pot synthesis of 2-aroylindoles using a domino palladium-catalyzed C,N-coupling/carbonylation/C,C-coupling sequence is described. The reaction involved easily prepared 2-gem-dibromovinylanilines and boronic acids under carbon monoxide. Optimized reaction conditions allowed the construction of a wide variety of highly functionalized 2-aroyl-/heteroaroylindoles in satisfactory yields.

  10. The versatile enzyme Araf51 allowed efficient synthesis of rare pathogen-related beta-D-galactofuranosyl-pyranoside disaccharides

    Czech Academy of Sciences Publication Activity Database

    Chlubnová, I.; Králová, B.; Dvořáková, H.; Hošek, P.; Spiwok, V.; Filipp, Dominik; Nugier-Chauvin, C.; Daniellou, R.; Ferrieres, V.

    2014-01-01

    Roč. 12, č. 19 (2014), s. 3080-3089 ISSN 1477-0520 Grant - others:GA MŠk(CZ) LM2010005 Institutional support: RVO:68378050 Keywords : Galactofuranosyl-pyranoside dipeptides * Araf51 enzymatic synthesis * computer modelling Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 3.562, year: 2014

  11. An efficient synthesis of linear β-(1→6)-galactan oligosaccharides related to plant cell wall glycans

    DEFF Research Database (Denmark)

    Andersen, Mathias Christian Franch; Arentoft, Camilla Anna Søholt; Boos, Irene

    2017-01-01

    Galactans are linear structures mainly found in arabinogalactan glycans and RG-I side chains. As a follow-up to our work on both β-(1→3)-linked and β-(1→4)-linked galactans, we herein report a convergent synthesis of β-(1→6)-galactan using our previously synthesized 4,6-benzylidene protected disa...

  12. Nano-particulate Aluminium Nitride/Al: An Efficient and Versatile Heterogeneous Catalyst for the Synthesis of Biginelli Scaffolds

    Science.gov (United States)

    Tekale, S. U.; Tekale, A. B.; Kanhe, N. S.; Bhoraskar, S. V.; Pawar, R. P.

    2011-12-01

    Nano-particulate aluminium nitride/Al (7:1) is reported as a new heterogeneous solid acid catalyst for the synthesis of 3, 4-dihydroxypyrimidi-2-(1H)-ones and their sulphur analogues using the Biginelli reaction. This method involves short reaction time, easy separation, high yields and purity of products.

  13. Arx: a toolset for the efficient simulation and direct synthesis of high-performance signal processing algorithms

    NARCIS (Netherlands)

    Hofstra, K.L.; Gerez, Sabih H.

    2007-01-01

    This paper addresses the efficient implementation of highperformance signal-processing algorithms. In early stages of such designs many computation-intensive simulations may be necessary. This calls for hardware description formalisms targeted for efficient simulation (such as the programming

  14. Green synthesis of 3,4-dihydropyrimidinones using nano Fe3O4@meglumine sulfonic acid as a new efficient solid acid catalyst under microwave irradiation

    Directory of Open Access Journals (Sweden)

    Leila Moradi

    2018-01-01

    Full Text Available Design, synthesis and characterization of nano Fe3O4@meglumine sulfonic acid as a new solid acid catalyst for the simple and green one pot multicomponent synthesis of 3,4-dihydropyrimidin-2(1H-ones/thiones was studied. New solid acid catalyst was prepared through a clean and simple protocol and characterized using FTIR, VSM, TGA, SEM, elemental analysis (CHN and XRD techniques. Heterogenization of homogeneous catalyst as a green approach is a useful method for enhancing the efficiency of catalyst. Presented study was a new method for attachment of homogeneous highly soluble catalyst (meglumine sulfate to the magnetite nanoparticle surfaces for preparing a heterogeneous and effective catalyst. Obtained heterogeneous and reusable solid acid catalyst has high performance in the synthesis of Biginelli compounds. The reaction was performed under microwave irradiation as a rapid and green condition. Easy work up as well as excellent yield (90–98% of products in short reaction times (40–200 s and reusable catalyst are the main advantages of presented procedure. Reaction products were characterized in details using physical and chemical techniques such as melting point, 1H NMR, 13C NMR and FTIR.

  15. Cyclopropenes in Metallacycle-Mediated Cross-Coupling with Alkynes: Convergent Synthesis of Highly Substituted Vinylcyclopropanes.

    Science.gov (United States)

    O'Rourke, Natasha F; Micalizio, Glenn C

    2016-03-18

    Stereodivergent metallacycle-mediated cross-coupling reactions are described for the synthesis of densely functionalized vinylcyclopropanes from the union of alkynes with cyclopropenes. Strategies explored include hydroxyl-directed and nondirected processes, with the latter of these delivering vinylcyclopropanes with exquisite levels of regio- and stereoselectivity. Challenges inherent to these coupling reactions include diastereoselectivity (with respect to the cyclopropene) and regioselectivity (with respect to both coupling partners).

  16. DNA repair genes RAD52 and SRS2, a cell wall synthesis regulator gene SMI1, and the membrane sterol synthesis scaffold gene ERG28 are important in efficient Agrobacterium-mediated yeast transformation with chromosomal T-DNA.

    Science.gov (United States)

    Ohmine, Yuta; Satoh, Yukari; Kiyokawa, Kazuya; Yamamoto, Shinji; Moriguchi, Kazuki; Suzuki, Katsunori

    2016-04-02

    Plant pathogenic Agrobacterium strains can transfer T-DNA regions of their Ti plasmids to a broad range of eukaryotic hosts, including fungi, in vitro. In the recent decade, the yeast Saccharomyces cerevisiae is used as a model host to reveal important host proteins for the Agrobacterium-mediated transformation (AMT). Further investigation is required to understand the fundamental mechanism of AMT, including interaction at the cell surface, to expand the host range, and to develop new tools. In this study, we screened a yeast mutant library for low AMT mutant strains by advantage of a chromosome type T-DNA, which transfer is efficient and independent on integration into host chromosome. By the mutant screening, we identified four mutant strains (srs2Δ, rad52Δ, smi1Δ and erg28Δ), which showed considerably low AMT efficiency. Structural analysis of T-DNA product replicons in AMT colonies of mutants lacking each of the two DNA repair genes, SRS2 and RAD52, suggested that the genes act soon after T-DNA entry for modification of the chromosomal T-DNA to stably maintain them as linear replicons and to circularize certain T-DNA simultaneously. The cell wall synthesis regulator SMI1 might have a role in the cell surface interaction between the donor and recipient cells, but the smi1Δ mutant exhibited pleiotropic effect, i.e. low effector protein transport as well as low AMT for the chromosomal T-DNA, but relatively high AMT for integrative T-DNAs. The ergosterol synthesis regulator/enzyme-scaffold gene ERG28 probably contributes by sensing a congested environment, because growth of erg28Δ strain was unaffected by the presence of donor bacterial cells, while the growth of the wild-type and other mutant yeast strains was suppressed by their presence. RAD52 and the DNA helicase/anti-recombinase gene SRS2 are necessary to form and maintain artificial chromosomes through the AMT of chromosomal T-DNA. A sterol synthesis scaffold gene ERG28 is important in the high-efficiency

  17. A simple and efficient approach for synthesis of 1,4-dihydro-pyridines using nano-crystalline solid acid catalyst

    Directory of Open Access Journals (Sweden)

    A. Moatari

    2013-09-01

    Full Text Available A simple highly versatile and efficient synthesis of various 1,4-dihydropyridines in the condensation of aromatic aldehydes with β-dicarbonyl compounds and ammonium acetate in the presence of nano-sulfated zirconia, nano-structured ZnO, nano-γ-alumina and nano-ZSM-5 zeolites, as catalyst in the ethanol at moderate temperature is presented. The advantages of method are short reaction times and milder conditions and easy work-up. The catalysts can be recovered for the subsequent reactions and reused without any appreciable loss of efficiency.DOI: http://dx.doi.org/10.4314/bcse.v27i3.12

  18. Synthesis of Won-WX2 (n=2.7, 2.9; X=S, Se) Heterostructures for Highly Efficient Green Quantum Dot Light-Emitting Diodes

    KAUST Repository

    Han, Shikui

    2017-07-04

    Preparation of two-dimensional (2D) heterostructures is important not only fundamentally, but also technologically for applications in electronics and optoelectronics. Herein, we report a facile colloidal method for the synthesis of WOn -WX2 (n=2.7, 2.9; X=S, Se) heterostructures by sulfurization or selenization of WOn nanomaterials. The WOn -WX2 heterostructures are composed of WO2.9 nanoparticles (NPs) or WO2.7 nanowires (NWs) grown together with single- or few-layer WX2 nanosheets (NSs). As a proof-of-concept application, the WOn -WX2 heterostructures are used as the anode interfacial buffer layer for green quantum dot light-emitting diodes (QLEDs). The QLED prepared with WO2.9 NP-WSe2 NS heterostructures achieves external quantum efficiency (EQE) of 8.53 %. To our knowledge, this is the highest efficiency in the reported green QLEDs using inorganic materials as the hole injection layer.

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

    Science.gov (United States)

    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.

  20. Synthesis and simulation of efficient divided wall column sequences for bioethanol recovery and purification from an actual lignocellulosic fermentation broth

    DEFF Research Database (Denmark)

    Torres-Ortega, Carlo Edgar; Rong, Ben-Guang

    2016-01-01

    Actual lignocellulosic fermentation broth has intrinsic multiphase and multicomponent nature and calls for complex separation systems in both bioethanol recovery and purification [Torres-Ortega, C. E.; Rong, B.-G. Ind. Eng. Chem. Res. 2016, 55, 210]. In this work, we present the synthesis...... of column sections as novel synthesis approaches to formulate hybrid units and divided wall columns. Rigorous simulation in Aspen Plus V8.0 was used to simulate the intensified separation systems. The new intensified alternatives achieved relevant savings, ranging from 17 to 23% in TAC (total annual costs......), and ranging from 18 to 28% in TEC (total energy consumption). Moreover, reduction of the number of separation units varied from the original eight units down to three units. Finally, we performed a sensitivity analysis varying the bioethanol concentration in the fermentation broth between the reference case...

  1. Highly efficient synthetic method onpyroacm resin using the boc SPPS protocol for C-terminal cysteine peptide synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Juvekar, Vinayak; Kim, Kang Tae; Gong, Young Dae [Innovative Drug Library Research Center, Dept. of Chemistry, College of Science, Dongguk University, Seoul (Korea, Republic of)

    2017-01-15

    A very effective process on Pyroacm resin was developed for solid-phase peptide synthesis (SPPS) of C-terminal cysteine and cysteine ester peptides. The process uses cysteine side chain anchoring to the Pyroacm resin and the Boc protocol for SPPS. The Pyroacm resin showed remarkable stability under standard trifluoromethanesulfonic acid (TFMSA) cleavage condition. TFMSA cleavage of protecting groups generates a peptide-linked resin, which can be subjected to peptide modification reactions. Finally, the peptide can be cleaved from the resin using methoxycarbonylsulfenyl chloride. The utility of this protocol was demonstrated by its applications to the synthesis of model peptides, key intermediates in the preparation of natural products riparin 1.2 and a-factor.

  2. Rumen microbial protein synthesis and nitrogen efficiency as affected by tanniferous and non-tanniferous forage legumes incubated individually or together in Rumen Simulation Technique.

    Science.gov (United States)

    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.

  3. BF3.SiO2: an efficient catalyst for the synthesis of azo dyes at room temperature

    Directory of Open Access Journals (Sweden)

    Bi Bi Fatemeh Mirjalili

    2012-07-01

    Full Text Available A rapid one-pot method has been developed for the synthesis of azo dyes via ‎sequential diazotization–diazo coupling of aromatic amines with coupling agents at room ‎temperature in the presence of BF3.SiO2 as acidic catalyst. The obtained aryl diazonium salts bearing silica supported boron tri-flouride counter ion‎ was sufficiently stable to be kept at room ‎temperature in the dry state.‎

  4. An efficient microwave-assisted synthesis and biological properties of polysubstituted pyrimidinyl- and 1,3,5-triazinylphosphonic acids

    Czech Academy of Sciences Publication Activity Database

    Jansa, Petr; Hradil, Ondřej; Baszczyňski, Ondřej; Dračínský, Martin; Klepetářová, Blanka; Holý, Antonín; Balzarini, J.; Janeba, Zlatko

    2012-01-01

    Roč. 68, č. 3 (2012), s. 865-871 ISSN 0040-4020 R&D Projects: GA AV ČR KJB400550903; GA MŠk 1M0508 Grant - others:K.U. Leuven(BE) GOA 10/014 Institutional research plan: CEZ:AV0Z40550506 Keywords : phosphonic acids * pyrimidines * 1,3,5-triazines * microwave-assisted synthesis * influenza virus Subject RIV: CC - Organic Chemistry Impact factor: 2.803, year: 2012

  5. Efficient synthesis of (+/-)-4-methyloctanoic acid, aggregation pheromone of rhinoceros beetles of the genus Oryctes (Coleoptera: Dynastidae, Scarabaeidae).

    Science.gov (United States)

    Ragoussis, Valentine; Giannikopoulos, Alexandros; Skoka, Efthymia; Grivas, Panagiotis

    2007-06-27

    (+/-)-4-Methyloctanoic acid and its ethyl ester are aggregation pheromones of many rhinoceros beetles of the genus Oryctes and are investigated for the control of these pests by olfactory trapping. A simple, economical, and high-yield (>50%) synthesis of (+/-)-4-methyloctanoic acid and its ethyl ester is presented starting from n-hexanal. The key step in this sequence is an orthoester Claisen rearrangement for the elongation of the carbon chain by two.

  6. Stereoselectivity in the salt-cocrystal products formed by phenylglycinol or phenylglycine with their respective sodium or hydrochloride salts.

    Science.gov (United States)

    Brittain, Harry G

    2013-01-01

    The salt and stereoselective cocrystal phenomena associated with 2-phenylglycinol and 2-phenylglycine have been studied using X-ray powder diffraction and differential scanning calorimetry. The chiral identities of the free acids and their sodium salts, or the free bases and their chloride salts, were found to play a determining role as to whether a salt-cocrystal product could or could not be formed. In particular, when cocrystallization of an enantiomerically pure basic or zwitterionic substance with its enantiomerically pure acid addition salt was attempted, a salt-cocrystal was only obtained when the absolute configuration of the two reactants is opposite. On the other hand, it has been found that no stereoselectivity in salt-cocrystal formation existed in the cocrystallization of an enantiomerically pure acidic or zwitterionic substance with its enantiomerically pure base addition salt. Copyright © 2012 Wiley Periodicals, Inc.

  7. Stereoselective and stereospecific effects in the formation of heteronuclear tartrate complexes of 3d- and 4f-elements from proton magnetic relaxation data

    International Nuclear Information System (INIS)

    Sal'nikov, Yu.I.; Chevela, V.V.

    1987-01-01

    A new approach to identification of stereoselective and stereospecific effects in the formation of heteronuclear tartrate complexes of 3d- and 4f-elements according to proton magnetic relaxation data is developed. At the first stage comparison of experimental dependences of the property measured (relaxation efficiency coefficient, Bjerrum function etc.) on the consentrational parameters is conducted. Their different course in systems with dH 4 L (d-tartaric acid) and dlH 4 L (dl-tartaric acid) points out to the presence of stereoeffects. Then, using mathematical simulation the most true stoichiometry of complex particles is determined as well as optimized values of their stability constants and intensity factors. The method is used when investigating the following systems: Fe 3+ -dH 4 L(dlH 4 L), Ln 3+ -dH 4 L(dlH 4 L), Fe 3+ -Ln 3+ -dH 4 L(dlH 4 L)(Ln 3+ -Gd 3+ , Ho 3+ , Er 3+ , Tm 3+ )

  8. Energy efficient methane tri-reforming for synthesis gas production over highly coke resistant nanocrystalline Ni–ZrO_2 catalyst

    International Nuclear Information System (INIS)

    Singha, Rajib Kumar; Shukla, Astha; Yadav, Aditya; Adak, Shubhadeep; Iqbal, Zafar; Siddiqui, Nazia; Bal, Rajaram

    2016-01-01

    Highlights: • Tri-reforming of methane is an energy efficient process to produce synthesis gas. • Nanocrystalline Ni–ZrO_2 catalyst is prepared for tri-reforming of methane. • Strong metal-support interaction is the driving force for high activity. • The process produces synthesis gas with H_2/CO ratio of around 2. • The produced synthesis gas can be used to synthesize methanol. - Abstract: We report the synthesis of nanocrystalline Ni–ZrO_2 catalyst for tri-reforming of methane (5CH_4 + O_2 + CO_2 + 2H_2O → 6CO + 12H_2) to produce synthesis gas with H_2/CO mole ratio ∼2. Nanocrystalline Ni–ZrO_2 catalyst of size between 10 and 40 nm was prepared by hydrothermal method using cetyltrimethylammonium bromide (CTAB) as a surfactant. The prepared catalysts were characterized by N_2-physisorption studies, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), temperature programmed reduction (TPR), H_2-chemisorpton, thermo-gravimetric analysis (TGA), Inductively coupled plasma atomic emission spectroscopy (ICP-AES) and X-ray photoelectron spectroscopy (XPS). The catalytic activity was monitored over temperature range between 500 and 800 °C. Different reaction parameters like temperature, Ni-loading, gas hourly space velocity (GHSV) and time on stream (TOS) were studied in detail. 4.8 wt% Ni loading for Ni–ZrO_2 catalyst was found to be the optimum Ni loading which showed the superior catalytic activity for methane tri-reforming. The catalyst was found to be stable for more than 100 h on time on stream with methane, carbon dioxide and steam conversion of ∼95% at 800 °C. The H_2/CO ratio was almost constant to 1.9 throughout the time on stream experiment. Highly dispersed nickel and the presence of strong metal support interaction were found to be the key factor for the superior activity of the catalyst. The effect of O_2 and H_2O concentration on reactant conversions and H_2/CO ratios were also

  9. An Efficient Protocol for the Synthesis of Quinoxaline Derivatives at Room Temperature Using Recyclable Alumina-Supported Heteropolyoxometalates

    Directory of Open Access Journals (Sweden)

    Diego M. Ruiz

    2012-01-01

    Full Text Available We report a suitable quinoxaline synthesis using molybdophosphovanadates supported on commercial alumina cylinders as catalysts. These catalysts were prepared by incipient wetness impregnation. The catalytic test was performed under different reaction conditions in order to know the performance of the synthesized catalysts. The method shows high yields of quinoxaline derivatives under heterogeneous conditions. Quinoxaline formation was obtained using benzyl, o-phenylenediamine, and toluene as reaction solvent at room temperature. The CuH2PMo11VO40 supported on alumina showed higher activity in the tested reaction. Finally, various quinoxalines were prepared under mild conditions and with excellent yields.

  10. Environment-friendly green chemistry approaches for an efficient synthesis of 1-amidoalkyl-2-naphthols catalyzed by tannic acid

    Directory of Open Access Journals (Sweden)

    Rajesh K. Singh

    2018-01-01

    Full Text Available A new, facile, cost-effective and environment-friendly protocol is reported for the synthesis of 1-amidoalkyl-2-naphthols exploring tannic acid as a novel, cheap and biodegradable catalyst. β-naphthol is condensed with substituted aromatic aldehydes and various amides using catalytic amount of tannic acid in the absence of solvent under thermal (hot plate and oil bath and microwave irradiation techniques. This green protocol offers many advantages such as short reaction time, use of environment-friendly and cheap catalyst and good to excellent yields.

  11. Efficient FeCl3/SiO2 as heterogeneous nanocatalysis for the synthesis of benzimidazoles under mild conditions

    Science.gov (United States)

    Taher, Mohammad Ali; Karami, Changiz; Arabi, Mehdi Sheikh; Ahmadian, Hossein; Karami, Yasaman

    2016-11-01

    Iron(III) supported on nano silica as a new catalyst has been synthesized. Structural properties of this complex have been studied by TEM, SEM and EDX. The average crystalline size of Iron(III) supported on nano silica is 30-50 nm. Catalytic activity of this catalyst has been investigated by synthesis of benzimidazoles from 1, 2-diaminobenzene and aromatic aldehydes, and also the other variables investigated such as the amount of catalyst, reaction temperature and the effect of various solvents are also studied. The present procedure offers several advantages such as short reaction time, simple workup, recovery and reusability of the catalyst.

  12. Efficient and Scalable Synthesis of 4-Carboxy-Pennsylvania Green Methyl Ester: A Hydrophobic Building Block for Fluorescent Molecular Probes.

    Science.gov (United States)

    Woydziak, Zachary R; Fu, Liqiang; Peterson, Blake R

    2014-01-01

    Fluorinated fluorophores are valuable tools for studies of biological systems. However, amine-reactive single-isomer derivatives of these compounds are often very expensive. To provide an inexpensive alternative, we report a practical synthesis of 4-carboxy-Pennsylvania Green methyl ester. Derivatives of this hydrophobic fluorinated fluorophore, a hybrid of the dyes Oregon Green and Tokyo Green, are often cell permeable, enabling labeling of intracellular targets and components. Moreover, the low pKa of Pennsylvania Green (4.8) confers bright fluorescence in acidic cellular compartments such as endosomes, enhancing its utility for chemical biology investigations. To improve access to the key intermediate 2,7-difluoro-3,6-dihydroxyxanthen-9-one, we subjected bis-(2,4,5-trifluorophenyl)methanone to iterative nucleophilic aromatic substitution by hydroxide on scales of > 40 g. This intermediate was used to prepare over 15 grams of pure 4-carboxy-Pennsylvania Green methyl ester in 28% overall yield without requiring chromatography. This compound can be converted into the amine reactive N -hydroxysuccinimidyl ester in essentially quantitative yield for the synthesis of a wide variety of fluorescent molecular probes.

  13. Recent advances in the synthesis of rare sugars using DHAP-dependent aldolases.

    Science.gov (United States)

    Li, Aimin; Cai, Li; Chen, Zhou; Wang, Mayan; Wang, Ning; Nakanishi, Hideki; Gao, Xiao-Dong; Li, Zijie

    2017-11-27

    The occurrence rates of non-communicable diseases like obesity, diabetes and hyperlipidemia have increased remarkably due to excessive consumption of a high-energy diet. Rare sugars therefore have become increasingly attractive owing to their unique nutritional properties. In the past two decades, various rare sugars have been successfully prepared guided by the "Izumoring strategy". As a valuable complement to the Izumoring approach, the controllable dihydroxyacetone phosphate (DHAP)-dependent aldolases have generally predictable regio- and stereoselectivity, which makes them powerful tools in C-C bond construction and rare sugar production. However, the main disadvantage for this group of aldolases is their strict substrate specificity toward the donor molecule DHAP, a very expensive and relatively unstable compound. Among the current methods involving DHAP, the one that couples DHAP production from inexpensive starting materials (for instance, glycerol, DL-glycerol 3-phosphate, dihydroxyacetone, and glucose) with aldol condensation appears to be the most promising. This review thus focuses on recent advances in the application of L-rhamnulose-1-phosphate aldolase (RhaD), L-fuculose-1-phosphate aldolase (FucA), and D-fructose-1,6-bisphosphate aldolase (FruA) for rare sugar synthesis in vitro and in vivo, while illustrating strategies for supplying DHAP in efficient and economical ways. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Efficient solar-driven synthesis, carbon capture, and desalinization, STEP: solar thermal electrochemical production of fuels, metals, bleach

    Energy Technology Data Exchange (ETDEWEB)

    Licht, S. [Department of Chemistry, George Washington University, Washington, DC (United States)

    2011-12-15

    STEP (solar thermal electrochemical production) theory is derived and experimentally verified for the electrosynthesis of energetic molecules at solar energy efficiency greater than any photovoltaic conversion efficiency. In STEP the efficient formation of metals, fuels, chlorine, and carbon capture is driven by solar thermal heated endothermic electrolyses of concentrated reactants occuring at a voltage below that of the room temperature energy stored in the products. One example is CO{sub 2}, which is reduced to either fuels or storable carbon at a solar efficiency of over 50% due to a synergy of efficient solar thermal absorption and electrochemical conversion at high temperature and reactant concentration. CO{sub 2}-free production of iron by STEP, from iron ore, occurs via Fe(III) in molten carbonate. Water is efficiently split to hydrogen by molten hydroxide electrolysis, and chlorine, sodium, and magnesium from molten chlorides. A pathway is provided for the STEP decrease of atmospheric carbon dioxide levels to pre-industrial age levels in 10 years. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Efficient synthesis of highly fluorescent nitrogen-doped carbon dots for cell imaging using unripe fruit extract of Prunus mume

    International Nuclear Information System (INIS)

    Atchudan, Raji; Edison, Thomas Nesakumar Jebakumar Immanuel; Sethuraman, Mathur Gopalakrishnan; Lee, Yong Rok

    2016-01-01

    Graphical abstract: The green synthesis of highly fluorescent N-CDs was achieved using the extract of unripe P. mume fruit as a carbon precursor by a one-pot simple hydrothermal-carbonization method. The resulting N-CDs were used as a staining agent for the fluorescence imaging of MDA-MB-231 cells. Display Omitted - Highlights: • The green synthesis of highly fluorescent N-CDs using the extract of unripe P. mume. • The N-CDs were synthesized by one-pot hydrothermal-carbonization method. • This method of synthesis is a simple, cost effective and eco-friendly route. • N-CDs will be a good alternative for fluorescent dyes and SQDs for bio-applications. - Abstract: Highly fluorescent nitrogen-doped carbon dots (N-CDs) were synthesized using the extract of unripe Prunus mume (P. mume) fruit by a simple one step hydrothermal-carbonization method. The N-CDs were synthesized at different pH ranges, 2.3, 5, 7, and 9. The pH of the P. mume extract was adjusted using an aqueous ammonia solution (25%). The optical properties of N-CDs were examined by UV–vis and fluorescence spectroscopy. The N-CDs synthesized at pH 9 emitted high fluorescence intensity compared to other obtained N-CDs. The N-CDs synthesized at pH 9 was further characterized by high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and Fourier transform-infra red (FT-IR) spectroscopy. HR-TEM showed that the average size of the synthesized N-CDs was approximately 9 nm and the interlayer distance was 0.21 nm, which was validated by XRD. The graphitic nature of the synthesized N-CDs were confirmed by Raman spectroscopy. XPS and FT-IR spectroscopy confirmed the doping of the nitrogen moiety over the synthesized CDs. The synthesized nitrogen doped CDs (N-CDs) were low toxicity and were used as a staining probe for fluorescence cell imaging.

  16. Efficient synthesis of highly fluorescent nitrogen-doped carbon dots for cell imaging using unripe fruit extract of Prunus mume

    Energy Technology Data Exchange (ETDEWEB)

    Atchudan, Raji; Edison, Thomas Nesakumar Jebakumar Immanuel [School of Chemical Engineering, Yeungnam University, Gyeongsan 38541 (Korea, Republic of); Sethuraman, Mathur Gopalakrishnan, E-mail: mgsethu@gmail.com [Department of Chemistry, Gandhigram Rural Institute-Deemed University, Gandhigram 624 302, Tamilnadu (India); Lee, Yong Rok, E-mail: yrlee@yu.ac.kr [School of Chemical Engineering, Yeungnam University, Gyeongsan 38541 (Korea, Republic of)

    2016-10-30

    Graphical abstract: The green synthesis of highly fluorescent N-CDs was achieved using the extract of unripe P. mume fruit as a carbon precursor by a one-pot simple hydrothermal-carbonization method. The resulting N-CDs were used as a staining agent for the fluorescence imaging of MDA-MB-231 cells. Display Omitted - Highlights: • The green synthesis of highly fluorescent N-CDs using the extract of unripe P. mume. • The N-CDs were synthesized by one-pot hydrothermal-carbonization method. • This method of synthesis is a simple, cost effective and eco-friendly route. • N-CDs will be a good alternative for fluorescent dyes and SQDs for bio-applications. - Abstract: Highly fluorescent nitrogen-doped carbon dots (N-CDs) were synthesized using the extract of unripe Prunus mume (P. mume) fruit by a simple one step hydrothermal-carbonization method. The N-CDs were synthesized at different pH ranges, 2.3, 5, 7, and 9. The pH of the P. mume extract was adjusted using an aqueous ammonia solution (25%). The optical properties of N-CDs were examined by UV–vis and fluorescence spectroscopy. The N-CDs synthesized at pH 9 emitted high fluorescence intensity compared to other obtained N-CDs. The N-CDs synthesized at pH 9 was further characterized by high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and Fourier transform-infra red (FT-IR) spectroscopy. HR-TEM showed that the average size of the synthesized N-CDs was approximately 9 nm and the interlayer distance was 0.21 nm, which was validated by XRD. The graphitic nature of the synthesized N-CDs were confirmed by Raman spectroscopy. XPS and FT-IR spectroscopy confirmed the doping of the nitrogen moiety over the synthesized CDs. The synthesized nitrogen doped CDs (N-CDs) were low toxicity and were used as a staining probe for fluorescence cell imaging.

  17. One-Step Nickel Foam Assisted Synthesis of Holey G-Carbon Nitride Nanosheets for Efficient Visible-light Photocatalytic H2 Evolution.

    Science.gov (United States)

    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.

  18. Facile and efficient one-pot solvothermal and microwave-assisted synthesis of stable colloidal solutions of MFe2O4 spinel magnetic nanoparticles

    International Nuclear Information System (INIS)

    Solano, Eduardo; Perez-Mirabet, Leonardo; Martinez-Julian, Fernando; Guzmán, Roger; Arbiol, Jordi; Puig, Teresa; Obradors, Xavier; Yañez, Ramón; Pomar, Alberto; Ricart, Susagna; Ros, Josep

    2012-01-01

    Well-defined synthesis conditions of high quality MFe 2 O 4 (M = Mn, Fe, Co, Ni, Zn, and Cu) spinel ferrite magnetic nanoparticles, with diameters below 10 nm, have been described based on facile and efficient one-pot solvothermal or microwave-assisted heating procedures. Both methods are reproducible and scalable and allow forming concentrated stable colloidal solutions in polar solvents, but microwave-assisted heating allows reducing 15 times the required annealing time and leads to an enhanced monodispersity of the nanoparticles. Non-agglomerated nanoparticles dispersions have been achieved using a simple one-pot approach where a single compound, triethyleneglycol, behaves at the same time as solvent and capping ligand. A narrow nanoparticle size distribution and high quality crystallinity have been achieved through selected nucleation and growth conditions. High resolution transmission electron microscopy images and electron energy loss spectroscopy analysis confirm the expected structure and composition and show that similar crystal faceting has been formed in both synthetic approaches. The spinel nanoparticles behave as ferrimagnets with a high saturation magnetization and are superparamagnetic at room temperature. The influence of synthesis route on phase purity and unconventional magnetic properties is discussed in some particular cases such as CuFe 2 O 4 , CoFe 2 O 4 , and ZnFe 2 O 4 .

  19. Synthesis of core-shell heterostructured Cu/Cu2O nanowires monitored by in situ XRD as efficient visible-light photocatalysts

    KAUST Repository

    Chen, Wei

    2013-01-01

    Core-shell heterostructured Cu/Cu2O nanowires with a high aspect ratio were synthesized from Cu foam using a novel oxidation/reduction process. In situ XRD was used as an efficient tool to acquire phase transformation details during the temperature-programmed oxidation of Cu foam and the subsequent reduction process. Based on knowledge of the crucial phase transformation, optimal synthesis conditions for producing high-quality CuO and core-shell Cu/Cu2O nanowires were determined. In favor of efficient charge separation induced by the special core-shell heterostructure and the advanced three-dimensional spatial configuration, Cu/Cu2O nanowires exhibited superior visible-light activity in the degradation of methylene blue. The present study illustrates a novel strategy for fabricating efficiently core-shell heterostructured nanowires and provides the potential for developing their applications in electronic devices, for environmental remediation and in solar energy utilization fields. This journal is © The Royal Society of Chemistry.

  20. Synthesis and Characterization of Antireflective ZnO Nanoparticles Coatings Used for Energy Improving Efficiency of Silicone Solar Cells

    Science.gov (United States)

    Pîslaru-Dǎnescu, Lucian; Chitanu, Elena; El-Leathey, Lucia-Andreea; Marinescu, Virgil; Marin, Dorian; Sbârcea, Beatrice-Gabriela

    2018-03-01

    The paper proposes a new and complex process for the synthesis of ZnO nanoparticles for antireflective coating corresponding to silicone solar cells applications. The process consists of two major steps: preparation of seed layer and hydrothermal growth of ZnO nanoparticles. Due to the fact that the seed layer morphology influences the ZnO nanoparticles proprieties, the process optimization of the seed layer preparation is necessary. Following the hydrothermal growth of the ZnO nanoparticles, antireflective coating of silicone solar cells is achieved. After determining the functional parameters of the solar cells provided either with glass or with ZnO, it is concluded that all the parameters values are superior in the case of solar cells with ZnO antireflection coating and are increasing along with the solar irradiance.

  1. In situ synthesis of CdS decorated titanate nanosheets with highly efficient visible-light-induced photoactivity

    International Nuclear Information System (INIS)

    Liu, Zhi; Fang, Pengfei; Liu, Fuwei; Zhang, Yupeng; Liu, Xinzhao; Lu, Dingze; Li, Delong; Wang, Shaojie

    2014-01-01

    Appropriately dispersed CdS nanoparticles were intimately embedded into titanate nanosheets (TNS) through ion-exchange and in situ sulfurization process. The sheet-like intermediates of titanate during the transforming process into nanotubes were firstly used as substrate for the decoration of CdS nanoparticles, and the synthesis route was achieved by ion-exchange process between titanate precursor and Cd 2+ ions solution, and the following sulfuration process by using Na 2 S solutions. The catalytic activity of the photocatalyst was investigated by photodegradation of Rhodamine B under visible light irradiation. With an optimal Cd/Ti molar ratio of 15%, the CdS/TNS composite exhibits the highest photocatalytic performance, which is approximately 5.4 times greater than that of pure TNS. The mechanism of the separation behavior of the photogenerated charges was also discussed.

  2. Novel approach for heterocyclization: a clean and efficient synthesis and biological evaluation of 4-oxothiazolidines under microwave technique

    International Nuclear Information System (INIS)

    Desai, Krunal G.; Desai, K.R.

    2006-01-01

    A new selective method has been developed for rapid synthesis of 2-(aryl)-3-[2-benzoimidazolythio)-acetamidyl]-4-oxothiazolidines 4a-j by the heterocyclization of 2-{(1H-benzemidazol)-ylthio}-N-benzylidene aceto hydrazide 3a-j with HSCH2COOH under microwave irradiation (MWI) is described. The reaction rate and yield is enhanced tremendously under MWI as compared to conventional methods. All the compounds have been screened for their antifungal activity against Candida albicans and Aspergillus niger, antibacterial activity against Escherchia coli and Staphylococcus aureus. In the primary screening, some of the compounds exhibited appreciable activity. The structures of the synthesized compounds 4a-j have been characterized on the basis of their elemental analysis, IR, HNMR and Mass spectral data. (author)

  3. Nb-Based Zeolites: Efficient bi-Functional Catalysts for the One-Pot Synthesis of Succinic Acid from Glucose

    Directory of Open Access Journals (Sweden)

    Magdi El Fergani

    2017-12-01

    Full Text Available The one-pot production of succinic acid from glucose was investigated in pure hot water as solvent using Nb (0.02 and 0.05 moles%-Beta zeolites obtained by a post-synthesis methodology. Structurally, they are comprised of residual framework Al-acid sites, extra-framework isolated Nb (V and Nb2O5 pore-encapsulated clusters. The Nb-modified Beta-zeolites acted as bi-functional catalysts in which glucose is dehydrated to levulinic acid (LA which, further, suffers an oxidation process to succinic acid (SA. After the optimization of the reaction conditions, that is, at 180 °C, 18 bar O2, and 12 h reaction time, the oxidation of glucose occurred with a selectivity to succinic acid as high as 84% for a total conversion.

  4. Gold Nanoparticles Supported on a Layered Double Hydroxide as Efficient Catalysts for the One-Pot Synthesis of Flavones.

    Science.gov (United States)

    Yatabe, Takafumi; Jin, Xiongjie; Yamaguchi, Kazuya; Mizuno, Noritaka

    2015-11-02

    Flavones are a class of natural products with diverse biological activities and have frequently been synthesized by step-by-step procedures using stoichiometric amounts of reagents. Herein, a catalytic one-pot procedure for the synthesis of flavone and its derivatives is developed. In the presence of gold nanoparticles supported on a Mg-Al layered double hydroxide (Au/LDH), various kinds of flavones can be synthesized starting from 2'-hydroxyacetophenones and benzaldehydes (or benzyl alcohols). The present one-pot procedure consists of a sequence of several reactions, and Au/LDH can catalyze all these different types of reactions. The catalysis is shown to be truly heterogeneous, and Au/LDH can be readily recovered and reused. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. OSU-6: A Highly Efficient, Metal-Free, Heterogeneous Catalyst for the Click Synthesis of 5-Benzyl and 5-Aryl-1H-tetrazoles

    Directory of Open Access Journals (Sweden)

    Baskar Nammalwar

    2015-12-01

    Full Text Available OSU-6, an MCM-41 type hexagonal mesoporous silica with mild Brönsted acid properties, has been used as an efficient, metal-free, heterogeneous catalyst for the click synthesis of 5-benzyl and 5-aryl-1H-tetrazoles from nitriles in DMF at 90 °C. This catalyst offers advantages including ease of operation, milder conditions, high yields, and reusability. Studies are presented that demonstrate the robust nature of the catalyst under the optimized reaction conditions. OSU-6 promotes the 1,3-dipolar addition of azides to nitriles without significant degradation or clogging of the nanoporous structure. The catalyst can be reused up to five times without a significant reduction in yield, and it does not require treatment with acid between reactions.

  6. Efficient continuous-flow synthesis of novel 1,2,3-triazole-substituted β-aminocyclohexanecarboxylic acid derivatives with gram-scale production

    Directory of Open Access Journals (Sweden)

    Sándor B. Ötvös

    2013-07-01

    Full Text Available The preparation of novel multi-substituted 1,2,3-triazole-modified β-aminocyclohexanecarboxylic acid derivatives in a simple and efficient continuous-flow procedure is reported. The 1,3-dipolar cycloaddition reactions were performed with copper powder as a readily accessible Cu(I source. Initially, high reaction rates were achieved under high-pressure/high-temperature conditions. Subsequently, the reaction temperature was lowered to room temperature by the joint use of both basic and acidic additives to improve the safety of the synthesis, as azides were to be handled as unstable reactants. Scale-up experiments were also performed, which led to the achievement of gram-scale production in a safe and straightforward way. The obtained 1,2,3-triazole-substituted β-aminocyclohexanecarboxylates can be regarded as interesting precursors for drugs with possible biological effects.

  7. Synthesis of POSS-based ionic conductors with low glass transition temperatures for efficient solid-state dye-sensitized solar cells.

    Science.gov (United States)

    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.

  8. An Efficient Solid-phase Parallel Synthesis of 2-Amino and 2-Amidobenzo[d]oxazole Derivatives via Cyclization Reactions of 2-Hydroxyphenylthiourea Resin

    International Nuclear Information System (INIS)

    Jung, Selin; Kim, Seulgi; Lee, Geehyung; Gong, Youngdae

    2012-01-01

    An efficient solid-phase methodology has been developed for the synthesis of 2-amino and 2-amidobenzo[d]-oxazole derivatives. The key step in this procedure involves the preparation of polymer-bound 2-aminobenzo-[d]oxazole resins 4 by cyclization reaction of 2-hydroxyphenylthiourea resin 3. The resin-bound 2-hydroxy-phenylthiourea 3 is produced by the addition of 2-aminophenol to the isothiocyanate-terminated resin 2 and serve as a key intermediate for the linker resin. This core skeleton 2-aminobenzo[d]oxazole resin 4 undergoes functionalization reaction with various electrophiles, such as alkylhalides and acid chlorides to generate 2-amino and 2-amidobenzo[d]oxazole resins 5 and 6 respectively. Finally, 2-amino and 2-amidobenzo[d]oxazole derivatives 7 and 8 are then generated in good yields and purities by cleavage of the respective resins 5 and 6 under trifluoroacetic acid (TFA) in dichloromethane (CH 2 Cl 2 )

  9. Efficient Enzymatic Routes for the Synthesis of New Eight-membered Cyclic β-Amino Acid and β-Lactam Enantiomers

    Directory of Open Access Journals (Sweden)

    Enikő Forró

    2017-12-01

    Full Text Available Efficient enzymatic resolutions are reported for the preparation of new eight-membered ring-fused enantiomeric β-amino acids [(1R,2S-9 and (1S,2R-9] and β-lactams [(1S,8R-3, (1R,8S-3 (1S,8R-4 and (1R,8S-7], through asymmetric acylation of (±-4 (E > 100 or enantioselective hydrolysis (E > 200 of the corresponding inactivated (±-3 or activated (±-4 β-lactams, catalyzed by PSIM or CAL-B in an organic solvent. CAL-B-catalyzed ring cleavage of (±-6 (E > 200 resulted in the unreacted (1S,8R-6, potential intermediate for the synthesis of enantiomeric anatoxin-a. The best strategies, in view of E, reaction rate and product yields, which underline the importance of substrate engineering, are highlighted.

  10. Simple and Efficient One-Pot Synthesis, Spectroscopic Characterization and Crystal Structure of Methyl 5-(4-Chlorobenzoyloxy-1-phenyl-1H-pyrazole-3-carboxylate

    Directory of Open Access Journals (Sweden)

    Imtiaz Khan

    2012-07-01

    Full Text Available A facile one-pot synthesis of methyl 5-(4-chlorobenzoyloxy-1-phenyl-1H-pyrazole-3-carboxylate (4 is described. The title compound was efficiently synthesized by the reaction of phenyl hydrazine, dimethyl acetylenedicarboxylate and 4-chlorobenzoyl chloride in dichloromethane under reflux in good yield. The structure of the target compound was deduced by modern spectroscopic and analytical techniques and unequivocally confirmed by a single crystal X-ray diffraction analysis. The crystal of the title compound belongs to orthorhombic system, space group P 21 21 21 with cell parameters a = 6.6491(3 Å, b = 7.9627(6 Å, c = 30.621(5 Å, α = β = γ = 90° and Z = 4. The crystal packing of the compound (4 is stabilized by an offset π-stacking between the planar benzoyl-substituted diazole moieties.

  11. [11C]PR04.MZ, a promising DAT ligand for low concentration imaging: synthesis, efficient 11C-O-methylation and initial small animal PET studies

    International Nuclear Information System (INIS)

    Riss, P.J.; Hooker, J.; Alexoff, D.; Kim, Sung-Won; Fowler, J.S.; Roesch, F.

    2009-01-01

    PR04.MZ was designed as a highly selective dopamine transporter inhibitor, derived from natural cocaine. Its binding profile indicates that [ 11 C]PR04.MZ may be suited as a PET radioligand for the non-invasive exploration of striatal and extrastriatal DAT populations. As a key feature, its structural design facilitates both, labelling with fluorine-18 at its terminally fluorinated butynyl moiety and carbon-11 at its methyl ester function. The present report concerns the efficient [ 11 C]MeI mediated synthesis of [ 11 C]PR04.MZ from an O-desmethyl precursor trifluoroacetic acid salt with Rb 2 CO 3 in DMF in up to 95 ± 5% labelling yield. A preliminary μPET-experiment demonstrates the reversible, highly specific binding of [ 11 C]PR04.MZ in the brain of a male Sprague-Dawley rat.

  12. Stereoselective biodegradation of tricyclic terpanes in heavy oils from the Bolivar Coastal Fields, Venezuela

    Energy Technology Data Exchange (ETDEWEB)

    Alberdi, M. [Stanford University (United States). Dept. of Geological and Environmental Sciences; PDVSA-Intevep, Caracas (Venezuela); Moldowan, J.M.; Dahl, J.E. [Stanford University (United States). Dept. of Geological and Environmental Sciences; Peters, K.E. [Mobil Technology Co., Dallas, TX (United States)

    2001-07-01

    Gas chromatography-mass spectrometry (GC-MS) and GC-MS-MS analyses of heavy oils from Bolivar Coastal Fields (Lagunillas Field) show a complete set of demethylated tricyclic terpanes. As is the case for the 25-norhopanes, the demethylated tricyclics are probably formed in reservoirs by microbially-mediated removal of the methyl group from the C-10 position, generating putative 17-nor-tricyclic terpanes. Diastereomeric pairs of tricyclic terpanes are resolved above C{sub 24} due to resolution of 22S and 22R epimers, but the elution order of the 22S and 22R epimers is unknown. Early-eluting diastereomers (EE) predominate over late-eluting diastereomers (LE) (C{sub 25}-C{sub 29}) in the heavily degraded oils, indicating a stereoselective preference for the LE stereoisomers during biodegradation. Conversely, the LE diastereomers predominate over the EE diastereomers in the 17-nor tricyclic series (C{sub 24}-C{sub 28}), indicating that tricyclic terpanes and 17-nor-tricyclic terpanes are directly linked as precursors and products, respectively. A good correlation exists between the destruction of steranes and the demethylation of hopanes and tricyclic terpanes. This suggests that terpane demethylation occurs during sterane destruction and hopane demethylation, although the rate is slower, indicating that tricyclic terpanes are more resistant to biodegradation. (Author)

  13. Comparing Different Strategies in Directed Evolution of Enzyme Stereoselectivity: Single- versus Double-Code Saturation Mutagenesis.

    Science.gov (United States)

    Sun, Zhoutong; Lonsdale, Richard; Li, Guangyue; Reetz, Manfred T

    2016-10-04

    Saturation mutagenesis at sites lining the binding pockets of enzymes constitutes a viable protein engineering technique for enhancing or inverting stereoselectivity. Statistical analysis shows that oversampling in the screening step (the bottleneck) increases astronomically as the number of residues in the randomization site increases, which is the reason why reduced amino acid alphabets have been employed, in addition to splitting large sites into smaller ones. Limonene epoxide hydrolase (LEH) has previously served as the experimental platform in these methodological efforts, enabling comparisons between single-code saturation mutagenesis (SCSM) and triple-code saturation mutagenesis (TCSM); these employ either only one or three amino acids, respectively, as building blocks. In this study the comparative platform is extended by exploring the efficacy of double-code saturation mutagenesis (DCSM), in which the reduced amino acid alphabet consists of two members, chosen according to the principles of rational design on the basis of structural information. The hydrolytic desymmetrization of cyclohexene oxide is used as the model reaction, with formation of either (R,R)- or (S,S)-cyclohexane-1,2-diol. DCSM proves to be clearly superior to the likewise tested SCSM, affording both R,R- and S,S-selective mutants. These variants are also good catalysts in reactions of further substrates. Docking computations reveal the basis of enantioselectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Stereoselective potencies and relative toxicities of γ-coniceine and N-methylconiine enantiomers.

    Science.gov (United States)

    Lee, Stephen T; Green, Benedict T; Welch, Kevin D; Jordan, Glenn T; Zhang, Qian; Panter, Kip E; Hughes, David; Chang, Cheng-Wei Tom; Pfister, James A; Gardner, Dale R

    2013-04-15

    γ-Coniceine, coniine, and N-methylconiine are toxic alkaloids present in poison hemlock (Conium maculatum). We previously reported the comparison of the relative potencies of (+)- and (-)-coniine enantiomers. In this study, we synthesized γ-coniceine and the enantiomers of N-methylconiine and determined the biological activity of γ-coniceine and each of the N-methylconiine enantiomers in vitro and in vivo. The relative potencies of these piperidine alkaloids on cells expressing human fetal muscle-type nicotinic acetylcholine receptors had the rank order of γ-coniceine > (-)-N-methylconiine > (±)-N-methylconiine > (+)-N-methylconiine. The relative lethalities of γ-coniceine and (-)-, (±)-, and (+)-N-methylconiine in vivo using a mouse bioassay were 4.4, 16.1, 17.8, and 19.2 mg/kg, respectively. The results from this study suggest γ-coniceine is a more potent agonist than the enantiomers of N-methylconiine and that there is a stereoselective difference in the in vitro potencies of the enantiomers of N-methylconiine that correlates with the relative toxicities of the enantiomers in vivo.

  15. Hammond Postulate Mirroring Enables Enantiomeric Enrichment of Phosphorus Compounds via Two Thermodynamically Interconnected Sequential Stereoselective Processes.

    Science.gov (United States)

    Rajendran, Kamalraj V; Nikitin, Kirill V; Gilheany, Declan G

    2015-07-29

    The dynamic resolution of tertiary phosphines and phosphine oxides was monitored by NMR spectroscopy. It was found that the stereoselectivity is set during the formation of the diastereomeric alkoxyphosphonium salts (DAPS), such that their initial diastereomeric excess (de) limits the final enantiomeric excess (ee) of any phosphorus products derived from them. However, (31)P NMR monitoring of the spontaneous thermal decomposition of the DAPS shows consistent diastereomeric self-enrichment, indicating a higher rate constant for decomposition of the minor diastereomer. This crucial observation was confirmed by reductive trapping of the unreacted enriched DAPS with lithium tri-sec-butylborohydride (commercially distributed as L-Selectride reagent) at different time intervals after the start of reaction, which gives progressively higher ee of the phosphine product with time. It is proposed that the Hammond postulate operates for both formation and decomposition of DAPS intermediate so that the lower rate of formation and faster subsequent collapse of the minor isomer are thermodynamically linked. This kinetic enhancement of kinetic resolution furnishes up to 97% ee product.

  16. Stereoselectivity in the disposition and metabolism of the uricosuric-diuretic agent, indacrinone, in Rhesus monkeys

    Energy Technology Data Exchange (ETDEWEB)

    Zacchei, A.G.; Dobrinska, M.R.; Wishousky, T.I.; Kwan, K.C.; White, S.D.

    The physiological disposition following intravenous dosing of the separate enantiomers of indacrinone-/sup 14/C (I), and of their major metabolite, 4'-hydroxyindacrinone-/sup 14/C (M), was studied in the rhesus monkey. Pharmacokinetic analysis indicated that the disposition of I and M was stereoselective. In the case of the enantiomers of I, the areas under the curves of plasma concentration vs. time were about sevenfold greater for the (S)(+)- as compared to the (R)(-)-enantiomer. Renal and plasma clearances of (R)(-)-I were five to seven times greater than those of (S)(+)-I. Total urinary recovery of unchanged drug and metabolite accounted for 70% of the administered dose of either enantiomer. The systemic availability of (R)(-)-M from (R)(-)-I was approximately 21% of the dose, whereas that of (S)(+)-M from (S)(+)-I was only 4%. More pronounced differences were noted in the kinetics of metabolite disposition. The AUC values were about 27 times greater for (S)(+)-M than (R)(-)-M, and the renal and plasma clearances were approximately 25-fold higher for (R)(-)-M as compared to (S)(+)-M. The volume of distribution of (S)(+)-M was only 12% of that observed with (R)(+)-M. There was no evidence of glucuronide or sulfate conjugates of any of the enantiomers. These findings are consistent with the pharmacological activity attributed to the different enantiomers.

  17. Stereoselective hydrogenation of olefins using rhodium-substituted carbonic anhydrase--a new reductase.

    Science.gov (United States)

    Jing, Qing; Okrasa, Krzysztof; Kazlauskas, Romas J

    2009-01-01

    One useful synthetic reaction missing from nature's toolbox is the direct hydrogenation of substrates using hydrogen. Instead nature uses cofactors like NADH to reduce organic substrates, which adds complexity and cost to these reductions. To create an enzyme that can directly reduce organic substrates with hydrogen, researchers have combined metal hydrogenation catalysts with proteins. One approach is an indirect link where a ligand is linked to a protein and the metal binds to the ligand. Another approach is direct linking of the metal to protein, but nonspecific binding of the metal limits this approach. Herein, we report a direct hydrogenation of olefins catalyzed by rhodium(I) bound to carbonic anhydrase (CA-[Rh]). We minimized nonspecific binding of rhodium by replacing histidine residues on the protein surface using site-directed mutagenesis or by chemically modifying the histidine residues. Hydrogenation catalyzed by CA-[Rh] is slightly slower than for uncomplexed rhodium(I), but the protein environment induces stereoselectivity favoring cis- over trans-stilbene by about 20:1. This enzyme is the first cofactor-independent reductase that reduces organic molecules using hydrogen. This catalyst is a good starting point to create variants with tailored reactivity and selectivity. This strategy to insert transition metals in the active site of metalloenzymes opens opportunities to a wider range of enzyme-catalyzed reactions.

  18. Stereoselectivity of the demethylation of nicotine piperidine homologues by Nicotiana plumbaginifolia cell suspension cultures.

    Science.gov (United States)

    Bartholomeusz, Trixie Ann; Molinié, Roland; Roscher, Albrecht; Felpin, François-Xavier; Gillet, Françoise; Lebreton, Jacques; Mesnard, François; Robins, Richard J

    2005-08-01

    The metabolism of (R,S)-N-methylanabasine and (R,S)-N-methylanatabine has been studied in a cell suspension culture of Nicotiana plumbaginifolia. Both substrates are effectively demethylated, anabasine or anatabine, respectively, accumulating in the medium. Similarly, there is strong stereoselectivity for the (R)-isomers of both substrates. The kinetics of metabolism of (R,S)-N-methylanabasine differ significantly from those of nicotine in that no further degradation of the initial demethylation product occurs. (R,S)-N-Methylanatabine, however, shows kinetics closer to those of nicotine, with loss of alkaloid from the system. Further more, (R,S)-N-methylanabasine does not diminish (S)-nicotine demethylation, indicating a lack of competition. However, the metabolism of (S)-nicotine is affected by the presence of (R,S)-N-methylanabasine. Hence, the demethylation of the piperidine homologues of nicotine is seen to be similar but not identical to that of the pyridine analogues. The implications of these different metabolic profiles in relation to the demethylation activity are discussed.

  19. Stereoselective in vitro metabolism of rhynchophylline and isorhynchophylline epimers of Uncaria rhynchophylla in rat liver microsomes.

    Science.gov (United States)

    Wang, Xin; Qiao, Zhou; Liu, Jia; Zheng, Mei; Liu, Wenyuan; Wu, Chunyong

    2017-11-10

    1. The objective was to investigate the underlying mechanism of the stereoselectivity in the metabolism of rhynchophylline (RIN) and isorhynchophylline (IRN) epimers in rat liver microsomes (RLM). 2. After incubation, eight metabolites of RIN (M1-5) and IRN (M6-8) reacted at A- and C-ring were identified using LC-Q-TOF/MS. Metabolic pathways included oxidation, hydroxylation, N-oxidation and dehydrogenation. In addition, hydroxylation at A-ring was the major metabolic pathway for RIN whereas the oxidation at C-ring was the major one for IRN. 3. Enzyme kinetics showed that the intrinsic clearance (CL int ) for IRN elimination was 1.9-fold higher than RIN and the degradation half-life (T 1/2 ) of RIN was 4.7-fold higher than that of IRN, indicating IRN was more favorable to be metabolized than RIN in RLM. 4. Data from chemical inhibition study demonstrated CYP3A was the predominant isoform involved in the metabolic elimination of both epimers, as well as the formation of M1-8. 5. In conclusion, data revealed that due to the spatial configurations at C-7 position, RIN and IRN epimers possessed different hepatic metabolic pathways and elimination rates which were mainly mediated by CYP3A.

  20. The tobacco carcinogen NNK is stereoselectively reduced by human pancreatic microsomes and cytosols.

    Science.gov (United States)

    Trushin, Neil; Leder, Gerhard; El-Bayoumy, Karam; Hoffmann, Dietrich; Beger, Hans G; Henne-Bruns, Doris; Ramadani, Marco; Prokopczyk, Bogdan

    2008-07-01

    Cigarette smoking increases the risk of cancer of the pancreas. The tobacco-specific nitrosamine 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) is the only known environmental compound that induces pancreatic cancer in laboratory animals. Concentrations of NNK are significantly higher in the pancreatic juice of smokers than in that of nonsmokers. The chiral NNK metabolite, (R,S)-4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) is itself a potent pancreatic carcinogen in rats. The carcinogenicity of NNAL is related to its stereochemistry; (S)-NNAL is a more potent lung tumorigen in the A/J mouse than is (R)-NNAL. In this study, we determined the potential of the human pancreas to convert NNK into NNAL. Human pancreatic microsomes and cytosols were incubated with [5-(3)H]NNK, and the metabolic products were determined by high-performance liquid chromatography (HPLC). (S)-NNAL was the predominant isomer formed in all cytosolic incubations. In ten microsomal samples, NNAL was formed at an average rate of 3.8 +/- 1.6 pmol/mg/min; (R)-NNAL was the predominant isomer in this group. The average rate of NNAL formation in 18 other microsomal samples was significantly lower, 0.13 +/- 0.12 pmol/mg/min (p < 0.001); (S)-NNAL was the predominant isomer formed in this group. In human pancreatic tissues, there is intraindividual variability regarding the capacity for, and stereoselectivity of, carbonyl reduction of NNK.

  1. Novel bipyridinyl oxadiazole-based metal coordination complexes: High efficient and green synthesis of 3,4-dihydropyrimidin-2(1H)-ones through the Biginelli reactions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jin-Hua; Zhang, E. [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Tang, Gui-Mei, E-mail: meiguit@163.com [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Wang, Yong-Tao, E-mail: ceswyt@qlu.edu.cn [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Cui, Yue-Zhi [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Ng, Seik Weng [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia)

    2016-09-15

    Three new metal coordination complexes, namely, [Co(BPO){sub 2}(H{sub 2}O){sub 4}](BS){sub 2}(H{sub 2}O){sub 2} (1), [Co(BPO){sub 2}(H{sub 2}O){sub 4}](ABS){sub 2}(H{sub 2}O){sub 2} (2), [Co(BPO){sub 2}(H{sub 2}O){sub 4}](MBS){sub 2}(H{sub 2}O){sub 2} (3) [BPO=2,5-di(pyridin-4-yl)-1,3,4-oxadiazole, BS=benzenesulphonate, ABS=4-aminobenzenesulphonate, MBS=4-methylbenzenesulphonate] were obtained under hydrothermal conditions. Complexes 1–3 were structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR and thermogravimetric analyses (TGA). All of them display a zero-dimensional motif, in which strong intermolecular hydrogen bonding interactions (O–H···O/N) and packing interactions (C–H···π and π···π) make them achieve a three-dimensional supramolecular architecture. The primary catalytic results of these three complexes show that high efficiency for the green synthesis of a variety of 3,4-dihydropyrimidin-2(1H)-ones was observed under solvent free conditions through Biginelli reactions. The present catalytic protocols exhibit advantages such as excellent yield, easy isolation, eco-friendly conditions, and short reaction time. - Graphical abstract: Three new metal coordination complexes with bipyridinyl-oxadiazole were obtained under hydrothermal conditions, which display a zero-dimensional motif, and show high efficiency for the green synthesis of a variety of 3,4-dihydropyrimidin-2(1H)-ones under solvent free conditions through Biginelli reactions. The present catalytic protocols exhibit advantages such as excellent yield, easy isolation, eco-friendly conditions, and short reaction time. Display Omitted.

  2. A Rapid and Efficient Sonogashira Protocol and Improved Synthesis of Free Fatty Acid 1 (FFA1) Receptor Agonists

    DEFF Research Database (Denmark)

    Christiansen, Elisabeth; Due-Hansen, Maria E; Ulven, Trond

    2010-01-01

    A protocol for rapid and efficient Pd/Cu-catalyzed coupling of aryl bromides and iodides to terminal alkynes has been developed with use of 2-(di-tert-butylphosphino)-N-phenylindole (cataCXium PIntB) as ligand in TMEDA and water. The new protocol successfully couples substrates which failed...

  3. An Efficient Synthesis of Substituted Quinolines via Indium(III) Chloride Catalyzed Reaction of Imines with Alkynes

    International Nuclear Information System (INIS)

    Zhu, Mei; Fu, Weijun; Xun, Chen; Zou, Guanglong

    2012-01-01

    An efficient synthetic method for the preparation of quinolines through indium(III) chloride-catalyzed tandem addition-cyclization-oxidation reactions of imines with alkynes was developed. The processes can provide a diverse range of quinoline derivatives in good yields from simple imines and alkynes

  4. An Efficient Synthesis of Phenols via Oxidative Hydroxylation of Arylboronic Acids Using (NH42S2O8

    Directory of Open Access Journals (Sweden)

    Claudia A. Contreras-Celedón

    2014-01-01

    Full Text Available A mild and efficient method for the ipso-hydroxylation of arylboronic acids to the corresponding phenols was developed using (NH42S2O8 as an oxidizing agent. The reactions were performed under metal-, ligand-, and base-free conditions.

  5. Synthesis and characterization of highly efficient and stable Pr6O11/Ag3PO4/Pt ternary hybrid structure

    International Nuclear Information System (INIS)

    Deng, Jiatao; Liu, Lin; Niu, Tongjun; Sun, Xiaosong

    2017-01-01

    Highlights: • Visible-light-driven Pr 6 O 11 /Ag 3 PO 4 /Pt photocatalysts were prepared. • Pr 6 O 11 /Ag 3 PO 4 /Pt showed highly efficient and stable photocatalystic activity. • The photocatalytic mechanism of Pr 6 O 11 /Ag 3 PO 4 /Pt composite was given. - Abstract: Ag 3 PO 4 is an excellent photocatalyst with high efficiency and quantum yield, but suffers from the fast recombination of photogenerated electron-hole pairs and photo-corrosion. Hereby, the highly efficient and stable visible-light-driven Pr 6 O 11 /Ag 3 PO 4 /Pt photocatalyst were prepared via a three-step wet chemical approach. The as-prepared Pr 6 O 11 /Ag 3 PO 4 /Pt composite was characterized by X-ray diffraction, US-vis diffuse reflectance spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, photoluminescence spectra and transient photocurrent as well. Comparing with single Pr 6 O 11 or Ag 3 PO 4 , the prepared Pr 6 O 11 /Ag 3 PO 4 /Pt composite exhibited much higher photocatalytic activity and stability for the degradation of Rhodamine B under visible light irradiation (>420 nm). The enhanced photocatalytic performance of Pr 6 O 11 /Ag 3 PO 4 /Pt composite has been attributed to the efficient separation of photo-generated electron-hole pairs through a scheme system composed of Pr 6 O 11, Ag 3 PO 4 and Pt.

  6. An efficient solvent-free synthesis of imidazolines and benzimidazoles using K 4[Fe(CN 6] catalysis

    Directory of Open Access Journals (Sweden)

    Kabeer A. Shaikh

    2012-01-01

    Full Text Available Imidazolines and Benzimidazoles have been efficiently synthesized in high yields by treatment of 1,2-diamine with aldehydes using the metal co-ordinate complex K 4[Fe(CN 6] as a catalysis. The method was carried out under solvent free condition via oxidation of carbon-nitrogen bond. The process is green, mild and inexpensive.

  7. Asymmetric synthesis with microbes; Biseibutsu wo katsuyoshita kogaku kassei kagobutsu no koritsutekina gosei

    Energy Technology Data Exchange (ETDEWEB)

    Kondo, S. [Ritsumeikan Univ., Tokyo (Japan). Faculty of Science and Engineering

    1996-02-01

    Use of microbial enzymes have been widely extended as an effective means for asymmetric synthesis. However, the asymmetric selectivity often decreases due to competitive catalysis among plural enzymes in a microbe. The author has been studied development of methods for control of the stereo-selectivity using subtle difference of enzyme characteristics. When Michaelis constant (Km) differs between two enzymes, one enzyme of lower Km becomes active with decrease in concentration of substrate, expressing its stereo-selectivity. Reduction of {alpha}-ketoesters in water by bread yeast (Saccharomyces cerevisiae) yields products of S-configuration, whereas those of R-configuration are obtained in an organic solvent in the presence of small amount of water. This is because reaction field of the yeast is in water and because R-configuration enzyme of lower Km works for substrate whose concentration in water has decreased due to two phase partition of organic solvent and water system. Further, use of difference of decrease in enzyme activity by inhibitors in stereo-selective synthesis of {alpha}-hydroxyketones (I) from {alpha}-diketone and use of difference of thermal endurance in improvement of formation ratio among I, are also introduced. 6 refs., 3 figs., 2 tabs.

  8. One pot synthesis of multi-functional tin oxide nanostructures for high efficiency dye-sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Wali, Qamar; Fakharuddin, Azhar; Yasin, Amina; Ab Rahim, Mohd Hasbi; Ismail, Jamil; Jose, Rajan, E-mail: rjose@ump.edu.my

    2015-10-15

    Photoanode plays a key role in dye sensitized solar cells (DSSCs) as a scaffold for dye molecules, transport medium for photogenerated electrons, and scatters light for improved absorption. Herein, tin oxide nanostructures unifying the above three characteristics were optimized by a hydrothermal process and used as photoanode in DSSCs. The optimized morphology is a combination of hollow porous nanoparticles of size ∼50 nm and micron sized spheres with BET surface area (up to 29 m{sup 2}/g) to allow large dye-loading and light scattering as well as high crystallinity to support efficient charge transport. The optimized morphology gave the highest photovoltaic conversion efficiency (∼7.5%), so far achieved in DSSCs with high open circuit voltage (∼700 mV) and short circuit current density (∼21 mA/cm{sup 2}) employing conventional N3 dye and iodide/triiodide electrolyte. The best performing device achieved an incident photon to current conversion efficiency of ∼90%. The performance of the optimized tin oxide nanostructures was comparable to that of conventional titanium based DSSCs fabricated at similar conditions. - Graphical abstract: Tin oxide hollow nanostructure simultaneously supporting improved light scattering, dye-loading, and charge transport yielded high photovoltaic conversion efficiency in dye-sensitized solar cells. - Highlights: • Uniformly and bimodelly distributed tin oxide hollow nanospheres (HNS) are synthesized. • Uniform HNS are of size ∼10 nm; bimodel HNS has additional size up to ∼800 nm. • They are evaluated as photoelectrodes in dye-sensitized solar cells (DSSCs). • The uniform HNS increase dye-loading and the larger increase light scattering in DSSCs. • Photo conversion efficiency ∼7.5% is achieved using bimodel HNS.

  9. Fully automated synthesis of (phosphopeptide arrays in microtiter plate wells provides efficient access to protein tyrosine kinase characterization

    Directory of Open Access Journals (Sweden)

    Goldstein David J

    2005-01-01

    Full Text Available Abstract Background Synthetic peptides have played a useful role in studies of protein kinase substrates and interaction domains. Synthetic peptide arrays and libraries, in particular, have accelerated the process. Several factors have hindered or limited the applicability of various techniques, such as the need for deconvolution of combinatorial libraries, the inability or impracticality of achieving full automation using two-dimensional or pin solid phases, the lack of convenient interfacing with standard analytical platforms, or the difficulty of compartmentalization of a planar surface when contact between assay components needs to be avoided. This paper describes a process for synthesis of peptides and phosphopeptides on microtiter plate wells that overcomes previous limitations and demonstrates utility in determination of the epitope of an autophosphorylation site phospho-motif antibody and utility in substrate utilization assays of the protein tyrosine kinase, p60c-src. Results The overall reproducibility of phospho-peptide synthesis and multiplexed EGF receptor (EGFR autophosphorylation site (pY1173 antibody ELISA (9H2 was within 5.5 to 8.0%. Mass spectrometric analyses of the released (phosphopeptides showed homogeneous peaks of the expected molecular weights. An overlapping peptide array of the complete EGFR cytoplasmic sequence revealed a high redundancy of 9H2 reactive sites. The eight reactive phospopeptides were structurally related and interestingly, the most conserved antibody reactive peptide motif coincided with a subset of other known EGFR autophosphorylation and SH2 binding motifs and an EGFR optimal substrate motif. Finally, peptides based on known substrate specificities of c-src and related enzymes were synthesized in microtiter plate array format and were phosphorylated by c-Src with the predicted specificities. The level of phosphorylation was proportional to c-Src concentration with sensitivities below 0.1 Units of

  10. Synthesis of fused tricyclic systems by thermal Cope rearrangement of furan-substituted vinyl cyclopropanes.

    Science.gov (United States)

    Klaus, Verena; Wittmann, Stéphane; Senn, Hans M; Clark, J Stephen

    2018-05-15

    A novel method for the stereoselective construction of hexahydroazuleno[4,5-b]furans from simple precursors has been developed. The route involves the use of our recently developed Brønsted acid catalysed cyclisation reaction of acyclic ynenones to prepare fused 1-furanyl-2-alkenylcyclopropanes that undergo highly stereoselective thermal Cope rearrangement to produce fused tricyclic products. Substrates possessing an E-alkene undergo smooth Cope rearrangement at 40 °C, whereas the corresponding Z-isomers do not react at this temperature. Computational studies have been performed to explain the difference in behaviour of the E- and Z-isomers in the Cope rearrangement reaction. The hexahydroazuleno[4,5-b]furans produced by Cope rearrangement have potential as advanced intermediates for the synthesis of members of the guaianolide family of natural products.

  11. Large-area snow-like MoSe2 monolayers: synthesis, growth mechanism, and efficient electrocatalyst application.

    Science.gov (United States)

    Huang, Jingwen; Liu, Huiqiang; Jin, Bo; Liu, Min; Zhang, Qingchun; Luo, Liqiong; Chu, Shijin; Chu, Sheng; Peng, Rufang

    2017-07-07

    This study explores the large-area synthesis of controllable morphology, uniform, and high-quality monolayer. MoSe 2 is essential for its potential application in optoelectronics, photocatalysis, and renewable energy sources. In this study, we successfully synthesized snow-like MoSe 2 monolayers using a simple chemical vapor deposition method. Results reveal that snow-like MoSe 2 is a single crystal with a hexagonal structure, a thickness of ∼0.9 nm, and a lateral dimension of up to 20 μm. The peak position of the photoluminescence spectra is ∼1.52 eV corresponding to MoSe 2 monolayer. The growth mechanism of the snow-like MoSe 2 monolayer was investigated and comprised a four-step process during growth. Finally, we demonstrate that the snow-like MoSe 2 monolayers are ideal electrocatalysts for hydrogen evolution reactions (HERs), reflected by a low Tafel slope of ∼68 mV/decade. Compared with the triangular-shaped MoSe 2 monolayer, the hexangular snow-like shape with plentiful edges is superior for perfect electrocatalysts for HERs or transmission devices of optoelectronic signals.

  12. Facile additive-free synthesis of iron oxide nanoparticles for efficient adsorptive removal of Congo red and Cr(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Tao; Yang, Chao; Rao, Xuehui; Wang, Jide [Ministry Key Laboratory of Oil and Gas Fine Chemicals, College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046 (China); Niu, Chunge, E-mail: ncg@petrochina.com.cn [Petrochemical Research Institute, Karamay Petrochemical Company, Karamay 834000 (China); Su, Xintai, E-mail: suxintai827@163.com [Ministry Key Laboratory of Oil and Gas Fine Chemicals, College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046 (China)

    2014-02-15

    The iron oxide nanoparticles had been successfully synthesized via an additive-free hydrolysis process at 75 °C for 12 h. The product was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and N{sub 2} adsorption–desorption. The results of XRD and N{sub 2} adsorption–desorption demonstrated that the as-prepared product was mainly α-Fe{sub 2}O{sub 3} with a large surface area of 164.1 m{sup 2} g{sup −1}. The TEM images illustrated that the as-prepared product was found to consist of a mixture of irregular spherical nanoparticles (a diameter of ∼50 nm) and nanowhiskers (a diameter of ∼50 nm and uneven length). The as-prepared product was used to investigate its promising applications in water treatment. Due to its small size and large surface area, the maximum adsorption capacities of Congo red and Cr(VI) have been determined using the Langmuir equation and found to reach up to 253.8 and 17.0 mg g{sup −1}, respectively. The facile synthesis method and the superior adsorption performance derived from the iron oxide nanoparticles display the potential applications for the removal of Congo red and Cr(VI) from aqueous solution.

  13. Highly Efficient One-Pot Synthesis of COS-Based Block Copolymers by Using Organic Lewis Pairs.

    Science.gov (United States)

    Yang, Jia-Liang; Cao, Xiao-Han; Zhang, Cheng-Jian; Wu, Hai-Lin; Zhang, Xing-Hong

    2018-01-31

    A one-pot synthesis of block copolymer with regioregular poly(monothiocarbonate) block is described via metal-free catalysis. Lewis bases such as guanidine, quaternary onium salts, and Lewis acid triethyl borane (TEB) were equivalently combined and used as the catalysts. By using polyethylene glycol (PEG) as the macromolecular chain transfer agent (CTA), narrow polydispersity block copolymers were obtained from the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO). The block copolymers had a poly(monothiocarbonate) block with perfect alternating degree and regioregularity. Unexpectedly, the addition of CTA to COS/PO copolymerization system could dramatically improve the turnover frequency (TOF) of PO (up to 240 h -1 ), higher than that of the copolymerization without CTA. In addition, the conversion of CTA could be up to 100% in most cases, as revealed by ¹H NMR spectra. Of consequence, the number-average molecular weights ( M n s) of the resultant block copolymers could be regulated by varying the feed ratio of CTA to PO. Oxygen-sulfur exchange reaction (O/S ER), which can generate randomly distributed thiocarbonate and carbonate units, was effectively suppressed in all of the cases in the presence of CTA, even at 80 °C. This work presents a versatile method for synthesizing sulfur-containing block copolymers through a metal-free route, providing an array of new block copolymers.

  14. An efficient rhythmic component expression and weighting synthesis strategy for classifying motor imagery EEG in a brain computer interface

    Science.gov (United States)

    Wang, Tao; He, Bin

    2004-03-01

    The recognition of mental states during motor imagery tasks is crucial for EEG-based brain computer interface research. We have developed a new algorithm by means of frequency decomposition and weighting synthesis strategy for recognizing imagined right- and left-hand movements. A frequency range from 5 to 25 Hz was divided into 20 band bins for each trial, and the corresponding envelopes of filtered EEG signals for each trial were extracted as a measure of instantaneous power at each frequency band. The dimensionality of the feature space was reduced from 200 (corresponding to 2 s) to 3 by down-sampling of envelopes of the feature signals, and subsequently applying principal component analysis. The linear discriminate analysis algorithm was then used to classify the features, due to its generalization capability. Each frequency band bin was weighted by a function determined according to the classification accuracy during the training process. The present classification algorithm was applied to a dataset of nine human subjects, and achieved a success rate of classification of 90% in training and 77% in testing. The present promising results suggest that the present classification algorithm can be used in initiating a general-purpose mental state recognition based on motor imagery tasks.

  15. Facile synthesis of thiol-polyethylene glycol functionalized magnetic titania nanomaterials for highly efficient enrichment of N-linked glycopeptides.

    Science.gov (United States)

    Wang, Jiawen; Yao, Jizong; Sun, Nianrong; Deng, Chunhui

    2017-08-25

    As protein N-glycosylation involved in generation and development of various cancers and diseases, it is vital to capture glycopeptides from complex biological samples for biomarker discovery. In this work, by taking advantages of the interaction between titania and thiol groups, thiol-polyethylene glycol functionalized magnetic titania nanomaterials (denoted as Fe 3 O 4 @TiO 2 @PEG) were firstly fabricated as an excellent hydrophilic adsorbent of N-linked glycopeptides. On one hand, the special interaction of titanium-thiol makes the synthetic manipulation simple and provides a new idea for design and synthesis of novel nanomaterials; on the other hand, strong magnetic response could realize rapid separation and the outstanding hydrophilicity of polyethylene glycol makes Fe 3 O 4 @TiO 2 @PEG nanomaterials show superior performance for glycopeptides enrichment with ultralow limit of detection (0.1mol/μL) and high selectivity (1:100). As a result, 24 and 33 glycopeptides enriched from HRP and IgG digests were identified respectively by MALDI-TOF MS, and 300 glycopeptides corresponding to 106 glycoproteins were recognized from merely 2μL human serum, indicating a great potential of Fe 3 O 4 @TiO 2 @PEG nanomaterials for glycoproteomic research. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Regiospecific and stereoselective hydroxylation of 1-indanone and 2-indanone by naphthalene dioxygenase and toluene dioxygenase.

    Science.gov (United States)

    Resnick, S M; Torok, D S; Lee, K; Brand, J M; Gibson, D T

    1994-09-01

    The biotransformation of 1-indanone and 2-indanone to hydroxyindanones was examined with bacterial strains expressing naphthalene dioxygenase (NDO) and toluene dioxygenase (TDO) as well as with purified enzyme components. Pseudomonas sp. strain 9816/11 cells, expressing NDO, oxidized 1-indanone to a mixture of 3-hydroxy-1-indanone (91%) and 2-hydroxy-1-indanone (9%). The (R)-3-hydroxy-1-indanone was formed in 62% enantiomeric excess (ee) (R:S, 81:19), while the 2-hydroxy-1-indanone was racemic. The same cells also formed 2-hydroxy-1-indanone from 2-indanone. Purified NDO components oxidized 1-indanone and 2-indanone to the same products produced by strain 9816/11. P. putida F39/D cells, expressing TDO, oxidized 2-indanone to (S)-2-hydroxy-1-indanone of 76% ee (R:S, 12:88) but did not oxidize 1-indanone efficiently. Purified TDO components also oxidized 2-indanone to (S)-2-hydroxy-1-indanone of 90% ee (R:S, 5:95) and failed to oxidize 1-indanone. Oxidation of 1- and 2-indanone in the presence of [18O]oxygen indicated that the hydroxyindanones were formed by the incorporation of a single atom of molecular oxygen (monooxygenation) rather than by the dioxygenation of enol tautomers of the ketone substrates. As alternatives to chemical synthesis, these biotransformations represent direct routes to 3-hydroxy-1-indanone and 2-hydroxy-1-indanone as the major products from 1-indanone and 2-indanone, respectively.

  17. Design and efficient synthesis of novel haptens and complete antigens for the AOZ, a toxic metabolite of furazolidone

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A good strategy was brought forward for designing efficient haptens and complete antigens for 3-amino-2-oxazolidinone (AOZ).Haptens designed newly were achieved facilely in good yield by using LiCl-N(Et)3 as new catalysis system, the structure of which was elucidated by spectroscopy analysis, such as NMR and MS. Novel antigens for AOZ were prepared successfully by convenient indicated that the haptens with a short unsaturated side chain can evoke specific immune response effectively.

  18. Polyvinylpolypyrrolidone-Supported Boron Trifluoride; Highly Efficient Catalyst for the Synthesis of N-tert-Butyl Amides

    Directory of Open Access Journals (Sweden)

    Masoud Mokhtary

    2012-01-01

    Full Text Available Highly efficient method for the preparation of N-tert-butyl amides by reaction of nitriles with tert-butyl acetate is described using polyvinylpolypyrrolidone-supported boron trifluoride (PVPP-BF3 at 70°C in good to excellent yields. Selective amidation of benzonitrile in the presence of acetonitrile was also achieved. polyvinylpolypyrrolidone-boron trifluoride complex shows non-corrosive and stable solid catalyst elevated Lewis acid property.

  19. Synthesis of Zero Valent Iron Nanoparticles (nZVI and its Efficiency in Arsenic Removal from Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Ali Reza Rahmani

    2011-03-01

    Full Text Available The aim of this study to synthesize nanoparticle zero valent iron and to determine its efficiency in arsenic removal from aqueous solutions. Nanoparticles were synthesized by reduction of ferric chloride using sodium borohydrid. The experiments were conducted in a batch system and the effects of pH, contact time, and the concentrations of arsenit, arsenat, and nano zero valent iron were investigated. SEM and XRD were applied for the determination of particle size and characterization of the nanoparticles synthesized. SEM results revealed that synthesized particles were of nano size (1-100 nanometers. At pH=7.0, 99% of arsenit and arsenat was removed when nano zero valent iron concentration was 1 (g L-1  over a retention time of  10 min. Based on the results obtained, the removal efficiency was enhanced with increasing nano zero valent iron dosage and reaction time, but decreased with increasing initial concentration and initial solution pH. The significant removal efficiency, high rate of process and short reaction time showed that iron nano particles are of a significant potential for the removal of arsenic from aqueous solutions.

  20. Solvothermal synthesis of InP quantum dots and their enhanced luminescent efficiency by post-synthetic treatments.

    Science.gov (United States)

    Byun, Ho-June; Lee, Ju Chul; Yang, Heesun

    2011-03-01

    InP quantum dots (QDs) were solvothermally synthesized by using a greener phosphorus source of P(N(CH(3))(2))(3) instead of highly toxic P(TMS)(3) widely used, and subsequently subjected to a size-sorting processing. While as-grown QDs showed an undetectably low emission intensity, post-synthetic treatments such as photo-etching, photo-radiation, and photo-assisted ZnS shell coating gave rise to a substantial increase in emission efficiency due to the effective removal and passivation of surface states. The emission efficiency of the photo-etched QDs was further enhanced by a consecutive UV photo-radiation, attributable to the photo-oxidation at QD surface. Furthermore, a relatively thick ZnS shell on the surface of InP QDs that were surface-modified with hydrophilic ligands beforehand was photochemically generated in an aqueous solution at room temperature. The resulting InP/ZnS core/shell QDs, emitting from blue to red wavelengths, were more efficient than the above photo-treated InP QDs, and their luminescent properties (emission bandwidth and quantum yield) were comparable to those of InP QDs synthesized with P(TMS)(3). Structural, size, and compositional analyses on InP/ZnS QDs were also conducted to elucidate their core/shell structure. Copyright © 2010 Elsevier Inc. All rights reserved.