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Sample records for highly enantioselective direct

  1. Direct enantioselective conjugate addition of carboxylic acids with chiral lithium amides as traceless auxiliaries.

    Science.gov (United States)

    Lu, Ping; Jackson, Jeffrey J; Eickhoff, John A; Zakarian, Armen

    2015-01-21

    Michael addition is a premier synthetic method for carbon-carbon and carbon-heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B.

  2. Direct Enantioselective Conjugate Addition of Carboxylic Acids with Chiral Lithium Amides as Traceless Auxiliaries

    Science.gov (United States)

    2016-01-01

    Michael addition is a premier synthetic method for carbon–carbon and carbon–heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B. PMID:25562717

  3. Direct, enantioselective α-alkylation of aldehydes using simple olefins.

    Science.gov (United States)

    Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

    2017-11-01

    Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

  4. 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.

  5. Enantioselective Direct α-Amination of Aldehydes via a Photoredox Mechanism: A Strategy for Asymmetric Amine Fragment Coupling

    OpenAIRE

    Cecere, Giuseppe; Koenig, Christian M.; Alleva, Jennifer L.; MacMillan, David W. C.

    2013-01-01

    The direct, asymmetric α-amination of aldehydes has been accomplished via a combination of photoredox and organocatalysis. Photon-generated, nitrogen-centered radicals undergo enantioselective α-addition to catalytically formed chiral enamines to directly produce stable α-amino aldehyde adducts bearing synthetically useful amine substitution patterns. Incorporation of a photolabile group on the amine precursor obviates the need to employ a photoredox catalyst in this transformation. Important...

  6. Enantioselective analysis of drugs: contributions of high-performance liquid chromatography and capillary electrophoresis

    OpenAIRE

    Bonato, Pierina Sueli; Jabor, Valquíria Aparecida Polisel; Gaitani, Cristiane Masetto de

    2005-01-01

    The demand for analytical methods suitable for accurate and reproducible determination of drug enantiomers has increased significantly in the last years. High-performance liquid chromatography (HPLC) using chiral stationary phases and capillary electrophoresis (CE) are the most important techniques used for this purpose. In this paper, the fundamental aspects of chiral separations using both techniques are presented. Some important aspects for the development of enantioselective methods, part...

  7. Lipase-catalyzed highly enantioselective kinetic resolution of boron-containing chiral alcohols.

    Science.gov (United States)

    Andrade, Leandro H; Barcellos, Thiago

    2009-07-16

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

  8. Calcium(ii)-catalyzed enantioselective conjugate additions of amines.

    Science.gov (United States)

    Uno, Brice E; Dicken, Rachel D; Redfern, Louis R; Stern, Charlotte M; Krzywicki, Greg G; Scheidt, Karl A

    2018-02-14

    The direct enantioselective chiral calcium(ii)·phosphate complex (Ca[CPA] 2 )-catalyzed conjugate addition of unprotected alkyl amines to maleimides was developed. This mild catalytic system represents a significant advance towards the general convergent asymmetric amination of α,β-unsaturated electrophiles, providing medicinally relevant chiral aminosuccinimide products in high yields and enantioselectivities. Furthermore, the catalyst can be reused directly from a previously chromatographed reaction and still maintain both high yield and selectivity.

  9. Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol Reagents

    Directory of Open Access Journals (Sweden)

    Gennari Cesare

    1998-01-01

    Full Text Available We have recently described the development of a quantitative transition state model for the prediction of stereoselectivity in the boron-mediated aldol reaction. This model provides qualitative insights into the factors contributing to the stereochemical outcome of a variety of reactions of synthetic importance. The force field model was used to assist the design and preparation of new chiral boron ligands derived from menthone. The chiral boron enolates were employed in various stereoselective processes, including the addition to chiral aldehydes and the reagent-controlled total synthesis of (3S,4S-statine. The chiral enolates derived from alpha-halo and alpha-oxysubstituted thioacetates were added to aldehydes and imines. Addition to imines leads to the enantioselective synthesis of chiral aziridines, a formal total synthesis of (+-thiamphenicol, and a new highly efficient synthesis of the paclitaxel (taxol® C-13 side-chain and taxol semisynthesis from baccatin III. The stereochemical outcome of the addition to imines was rationalised with the aid of computational studies. Enantioselective addition reactions of the chiral boron enolate derived from thioacetate have successfully been applied to solid phase bound aldehydes to give aldol products in comparable yields and enantioselectivities to the usual solution conditions.

  10. Cyclic aldimines as superior electrophiles for Cu-catalyzed decarboxylative Mannich reaction of β-ketoacids with a broad scope and high enantioselectivity.

    Science.gov (United States)

    Zhang, Heng-Xia; Nie, Jing; Cai, Hua; Ma, Jun-An

    2014-05-02

    A novel Cu-catalyzed enantioselective decarboxylative Mannich reaction of cyclic aldimines with β-ketoacids is described. The cyclic structure of these aldimines, in which the C═N bond is constrained in the Z geometry, appears to be important, allowing Mannich condensation to proceed in high yields with excellent enantioselectivities. A chiral chroman-4-amine was synthesized from the decarboxylative Mannich product in several steps without loss of enantioselectivity.

  11. P(O)R2-Directed Enantioselective C-H Olefination toward Chiral Atropoisomeric Phosphine-Olefin Compounds.

    Science.gov (United States)

    Li, Shi-Xia; Ma, Yan-Na; Yang, Shang-Dong

    2017-04-07

    An effective synthesis of chiral atropoisomeric biaryl phosphine-olefin compounds via palladium-catalyzed enantioselective C-H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value. Notably, P(O)R 2 not only acts as the directing group to direct C-H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.

  12. Synthesis of 3-fluoro-3-aryl oxindoles: Direct enantioselective α arylation of amides

    KAUST Repository

    Wu, Linglin; Falivene, Laura; Drinkel, Emma E.; Grant, Sharday; Linden, Anthony; Cavallo, Luigi; Dorta, Reto

    2012-01-01

    Modus operandi: Catalytic access to the title compounds through a new asymmetric α-arylation protocol is reported (see scheme). These products are formed in good yields and excellent enantioselectivities by using a new and easily synthesized chiral N-heterocyclic carbene (NHC) ligand. Advanced DFT calculations reveal the properties of the NHC ligand and the mode of operation of the catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synthesis of 3-fluoro-3-aryl oxindoles: Direct enantioselective α arylation of amides

    KAUST Repository

    Wu, Linglin

    2012-02-06

    Modus operandi: Catalytic access to the title compounds through a new asymmetric α-arylation protocol is reported (see scheme). These products are formed in good yields and excellent enantioselectivities by using a new and easily synthesized chiral N-heterocyclic carbene (NHC) ligand. Advanced DFT calculations reveal the properties of the NHC ligand and the mode of operation of the catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. The Brønsted Acid-Catalyzed, Enantioselective Aza-Diels-Alder Reaction for the Direct Synthesis of Chiral Piperidones.

    Science.gov (United States)

    Weilbeer, Claudia; Sickert, Marcel; Naumov, Sergei; Schneider, Christoph

    2017-01-12

    We disclose herein the first enantioselective aza-Diels-Alder reaction of β-alkyl-substituted vinylketene silyl-O,O-acetals and imines furnishing a broad range of optically highly enriched 4-alkyl-substituted 2-piperidones. As a catalyst for this one-pot reaction we employed a chiral phosphoric acid which effects a vinylogous Mannich reaction directly followed by ring-closure to the lactam. Subsequent fully diastereoselective transformations including hydrogenation, enolate alkylation, and lactam alkylation/reduction processes converted the cycloadducts into various highly substituted piperidines of great utility for the synthesis of natural products and medicinally active compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Structural basis for high substrate-binding affinity and enantioselectivity of 3-quinuclidinone reductase AtQR

    International Nuclear Information System (INIS)

    Hou, Feng; Miyakawa, Takuya; Kataoka, Michihiko; Takeshita, Daijiro; Kumashiro, Shoko; Uzura, Atsuko; Urano, Nobuyuki; Nagata, Koji; Shimizu, Sakayu; Tanokura, Masaru

    2014-01-01

    Highlights: • Crystal structure of AtQR has been determined at 1.72 Å. • NADH binding induces the formation of substrate binding site. • AtQR possesses a conserved hydrophobic wall for stereospecific binding of substrate. • Additional Glu197 residue is critical to the high binding affinity. - Abstract: (R)-3-Quinuclidinol, a useful compound for the synthesis of various pharmaceuticals, can be enantioselectively produced from 3-quinuclidinone by 3-quinuclidinone reductase. Recently, a novel NADH-dependent 3-quinuclidionone reductase (AtQR) was isolated from Agrobacterium tumefaciens, and showed much higher substrate-binding affinity (>100 fold) than the reported 3-quinuclidionone reductase (RrQR) from Rhodotorula rubra. Here, we report the crystal structure of AtQR at 1.72 Å. Three NADH-bound protomers and one NADH-free protomer form a tetrameric structure in an asymmetric unit of crystals. NADH not only acts as a proton donor, but also contributes to the stability of the α7 helix. This helix is a unique and functionally significant part of AtQR and is related to form a deep catalytic cavity. AtQR has all three catalytic residues of the short-chain dehydrogenases/reductases family and the hydrophobic wall for the enantioselective reduction of 3-quinuclidinone as well as RrQR. An additional residue on the α7 helix, Glu197, exists near the active site of AtQR. This acidic residue is considered to form a direct interaction with the amine part of 3-quinuclidinone, which contributes to substrate orientation and enhancement of substrate-binding affinity. Mutational analyses also support that Glu197 is an indispensable residue for the activity

  16. Structural basis for high substrate-binding affinity and enantioselectivity of 3-quinuclidinone reductase AtQR

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Feng; Miyakawa, Takuya [Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 (Japan); Kataoka, Michihiko [Division of Applied Life Sciences, Graduate School of Life and Environmental Sciences, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai 559-8531 (Japan); Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502 (Japan); Takeshita, Daijiro [Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 (Japan); Kumashiro, Shoko [Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502 (Japan); Uzura, Atsuko [Research and Development Center, Nagase and Co., Ltd., 2-2-3 Muratani, Nishi-ku, Kobe 651-2241 (Japan); Urano, Nobuyuki [Division of Applied Life Sciences, Graduate School of Life and Environmental Sciences, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai 559-8531 (Japan); Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502 (Japan); Nagata, Koji [Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 (Japan); Shimizu, Sakayu [Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502 (Japan); Faculty of Bioenvironmental Science, Kyoto Gakuen University, Sogabe-cho, Kameoka 621-8555 (Japan); Tanokura, Masaru, E-mail: amtanok@mail.ecc.u-tokyo.ac.jp [Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 (Japan)

    2014-04-18

    Highlights: • Crystal structure of AtQR has been determined at 1.72 Å. • NADH binding induces the formation of substrate binding site. • AtQR possesses a conserved hydrophobic wall for stereospecific binding of substrate. • Additional Glu197 residue is critical to the high binding affinity. - Abstract: (R)-3-Quinuclidinol, a useful compound for the synthesis of various pharmaceuticals, can be enantioselectively produced from 3-quinuclidinone by 3-quinuclidinone reductase. Recently, a novel NADH-dependent 3-quinuclidionone reductase (AtQR) was isolated from Agrobacterium tumefaciens, and showed much higher substrate-binding affinity (>100 fold) than the reported 3-quinuclidionone reductase (RrQR) from Rhodotorula rubra. Here, we report the crystal structure of AtQR at 1.72 Å. Three NADH-bound protomers and one NADH-free protomer form a tetrameric structure in an asymmetric unit of crystals. NADH not only acts as a proton donor, but also contributes to the stability of the α7 helix. This helix is a unique and functionally significant part of AtQR and is related to form a deep catalytic cavity. AtQR has all three catalytic residues of the short-chain dehydrogenases/reductases family and the hydrophobic wall for the enantioselective reduction of 3-quinuclidinone as well as RrQR. An additional residue on the α7 helix, Glu197, exists near the active site of AtQR. This acidic residue is considered to form a direct interaction with the amine part of 3-quinuclidinone, which contributes to substrate orientation and enhancement of substrate-binding affinity. Mutational analyses also support that Glu197 is an indispensable residue for the activity.

  17. Catalytic Enantioselective Alkylation of β-Keto Esters with Xanthydrol in the Presence of Chiral Palladium Complex

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kyu Yeon; Kim, Dae Young [Soonchunhyang Univ., Asan (Korea, Republic of)

    2016-01-15

    Our research interest has been directed toward the development of synthetic methods for the enantioselective construction of stereogenic carbon centers. Recently, we explored the catalytic enantioselective functionalization of active methines in the presence of chiral palladium(II) complexes. In conclusion, we have accomplished the efficient catalytic enantioselective alkylation of β-keto esters 1 with xanthydrol 2 with high yields and excellent enantioselectivity (up to 98% ee). It should be noted that this alkyaltion reaction proceeds well using air- and moisture-stable chiral palladium com- plexes with low loading (1 mol%)

  18. Highly Enantioselective Production of (R-Halohydrins with Whole Cells of Rhodotorula rubra KCh 82 Culture

    Directory of Open Access Journals (Sweden)

    Tomasz Janeczko

    2014-12-01

    Full Text Available Biotransformation of ten α-haloacetophenones in the growing culture of the strain Rhodotorula rubra KCh 82 has been carried out. Nine of the substrates underwent an effective enantioselective reduction to the respective (R-alcohols according to Prelog’s rule, with the exception of 2-chloro-1,2-diphenylethan-1-one that was not transformed by this strain. The expected reduction proceeded without dehalogenation, leading to the respective (R-halohydrins in high yields. The use of this biocatalyst yielded (R-2-bromo-1-phenyl-ethan-1-ol (enantiomeric excess (ee = 97% and its derivatives: 4'-Bromo- (ee = 99%; 4'-Chloro- (ee > 99%; 4'-Methoxy- (ee = 96%; 3'-Methoxy- (ee = 93%; 2'-Methoxy- (ee = 98%. There were also obtained and characterized 2,4'-dichloro-, 2,2',4'-trichloro- and 2-chloro-4'-fluoro-phenyetan-1-ol with >99% of enantiomeric excesses.

  19. Highly enantioselective production of (R)-halohydrins with whole cells of Rhodotorula rubra KCh 82 culture.

    Science.gov (United States)

    Janeczko, Tomasz; Dymarska, Monika; Kostrzewa-Susłow, Edyta

    2014-12-04

    Biotransformation of ten α-haloacetophenones in the growing culture of the strain Rhodotorula rubra KCh 82 has been carried out. Nine of the substrates underwent an effective enantioselective reduction to the respective (R)-alcohols according to Prelog's rule, with the exception of 2-chloro-1,2-diphenylethan-1-one that was not transformed by this strain. The expected reduction proceeded without dehalogenation, leading to the respective (R)-halohydrins in high yields. The use of this biocatalyst yielded (R)-2-bromo-1-phenyl-ethan-1-ol (enantiomeric excess (ee) = 97%) and its derivatives: 4'-Bromo- (ee = 99%); 4'-Chloro- (ee > 99%); 4'-Methoxy- (ee = 96%); 3'-Methoxy- (ee = 93%); 2'-Methoxy- (ee = 98%). There were also obtained and characterized 2,4'-dichloro-, 2,2',4'-trichloro- and 2-chloro-4'-fluoro-phenyetan-1-ol with >99% of enantiomeric excesses.

  20. Highly enantioselective rhodium(I)-catalyzed carbonyl carboacylations initiated by C-C bond activation.

    Science.gov (United States)

    Souillart, Laetitia; Cramer, Nicolai

    2014-09-01

    The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom-economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of CC bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)-catalyzed transformation is induced by an enantiotopic CC bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Spin-Center Shift-Enabled Direct Enantioselective α-Benzylation of Aldehydes with Alcohols.

    Science.gov (United States)

    Nacsa, Eric D; MacMillan, David W C

    2018-03-07

    Nature routinely engages alcohols as leaving groups, as DNA biosynthesis relies on the removal of water from ribonucleoside diphosphates by a radical-mediated "spin-center shift" (SCS) mechanism. Alcohols, however, remain underused as alkylating agents in synthetic chemistry due to their low reactivity in two-electron pathways. We report herein an enantioselective α-benzylation of aldehydes using alcohols as alkylating agents based on the mechanistic principle of spin-center shift. This strategy harnesses the dual activation modes of photoredox and organocatalysis, engaging the alcohol by SCS and capturing the resulting benzylic radical with a catalytically generated enamine. Mechanistic studies provide evidence for SCS as a key elementary step, identify the origins of competing reactions, and enable improvements in chemoselectivity by rational photocatalyst design.

  2. Regioconvergent and Enantioselective Rhodium-Catalyzed Hydroamination of Internal and Terminal Alkynes: A Highly Flexible Access to Chiral Pyrazoles.

    Science.gov (United States)

    Haydl, Alexander M; Hilpert, Lukas J; Breit, Bernhard

    2016-05-04

    The rhodium-catalyzed asymmetric N-selective coupling of pyrazole derivatives with internal and terminal alkynes features an utmost chemo-, regio-, and enantioselective access to enantiopure allylic pyrazoles, readily available for incorporation in small-molecule pharmaceuticals. This methodology is distinguished by a broad substrate scope, resulting in a remarkable compatability with a variety of different functional groups. It furthermore exhibits an intriguing case of regio-, position-, and enantioselectivity in just one step, underscoring the sole synthesis of just one out of up to six possible products in a highly flexible approach to allylated pyrazoles by emanating from various internal and terminal alkynes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Efficient and highly enantioselective formation of the all-carbon quaternary stereocentre of lyngbyatoxin A

    DEFF Research Database (Denmark)

    Vital, Paulo J.V.; Tanner, David

    2006-01-01

    Indole 25, an advanced intermediate in a projected enantioselective total synthesis of lyngbyatoxin A 1, was prepared from allylic alcohol 11 in 9 steps and >95% ee, key transformations being the enantiospecific rearrangement of vinyl epoxide 14 and the Hemetsberger-Knittel reaction of azide 24....

  4. Rhodium/chiral diene-catalyzed asymmetric 1,4-addition of arylboronic acids to chromones: a highly enantioselective pathway for accessing chiral flavanones.

    Science.gov (United States)

    He, Qijie; So, Chau Ming; Bian, Zhaoxiang; Hayashi, Tamio; Wang, Jun

    2015-03-01

    Chromone has been noted to be one of the most challenging substrates in the asymmetric 1,4-addition of α,β-unsaturated carbonyl compounds. By employing the rhodium complex associated with a chiral diene ligand, (R,R)-Ph-bod*, the 1,4-addition of a variety of arylboronic acids was realized to give high yields of the corresponding flavanones with excellent enantioselectivities (≥97% ee, 99% ee for most substrates). Ring-opening side products, which would lead to erosion of product enantioselectivity, were not observed under the stated reaction conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Palladium-Catalyzed Enantioselective C-H Olefination of Diaryl Sulfoxides through Parallel Kinetic Resolution and Desymmetrization.

    Science.gov (United States)

    Zhu, Yu-Chao; Li, Yan; Zhang, Bo-Chao; Zhang, Feng-Xu; Yang, Yi-Nuo; Wang, Xi-Sheng

    2018-03-07

    The first example of Pd II -catalyzed enantioselective C-H olefination with non-chiral or racemic sulfoxides as directing groups was developed. A variety of chiral diaryl sulfoxides were synthesized with high enantioselectivity (up to 99 %) through both desymmetrization and parallel kinetic resolution (PKR). This is the first report of Pd II -catalyzed enantioselective C(sp 2 )-H functionalization through PKR, and it represents a novel strategy to construct sulfur chiral centers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Exo selective enantioselective nitrone cycloadditions.

    Science.gov (United States)

    Sibi, Mukund P; Ma, Zhihua; Jasperse, Craig P

    2004-01-28

    We have developed a novel method for accessing exo adducts with high enantioselectivity in nitrone cycloadditions to enoates. Pyrazolidinones proved to be effective achiral templates in the cycloadditions, providing exo adducts typically in >15:1 selectivity and 90-98% ee. The use of Lewis acids that form square planar complexes, such as copper triflate, was important for obtaining high exo selectivity.

  7. Enantioselective addition of nitrones to activated cyclopropanes.

    Science.gov (United States)

    Sibi, Mukund P; Ma, Zhihua; Jasperse, Craig P

    2005-04-27

    In this paper, we demonstrate the first examples of chiral Lewis acid catalysis in the formation of tetrahydro-1,2-oxazines with very high enantioselectivity starting with diactivated cyclopropanes and nitrones (>90% yields and ee). Reactions with racemic substituted cyclopropanes provide approximately 1:1 diastereomeric tetrahydro-1,2-oxazine products with high enantioselectivity. Mechanistic information for the formation of the tetrahydro-1,2-oxazines is also detailed.

  8. Enantioselective synthesis of alpha,beta-disubstituted-beta-amino acids.

    Science.gov (United States)

    Sibi, Mukund P; Prabagaran, Narayanasamy; Ghorpade, Sandeep G; Jasperse, Craig P

    2003-10-01

    Highly diastereoselective and enantioselective addition of N-benzylhydroxylamine to imides 17 and 20-30 produces alpha,beta-trans-disubstituted N-benzylisoxazolidinones 19 and 31-41. These reactions proceed in 60-96% ee with 93-99% de's using 5 mol % of Mg(NTf2)2 and ligand 18. The product isoxazolidinones can be hydrogenolyzed directly to provide alpha,beta-disubstituted-beta-amino acids.

  9. High enantioselective Novozym 435-catalyzed esterification of (R,S)-flurbiprofen monitored with a chiral stationary phase.

    Science.gov (United States)

    Siódmiak, Tomasz; Mangelings, Debby; Vander Heyden, Yvan; Ziegler-Borowska, Marta; Marszałł, Michał Piotr

    2015-03-01

    Lipases form Candida rugosa and Candida antarctica were tested for their application in the enzymatic kinetic resolution of (R,S)-flurbiprofen by enantioselective esterification. Successful chromatographic separation with well-resolved peaks of (R)- and (S)-flurbiprofen and their esters was achieved in one run on chiral stationary phases by high-performance liquid chromatography (HPLC). In this study screening of enzymes was performed, and Novozym 435 was selected as an optimal catalyst for obtaining products with high enantiopurity. Additionally, the influence of organic solvents (dichloromethane, dichloroethane, dichloropropane, and methyl tert-butyl ether), primary alcohols (methanol, ethanol, n-propanol, and n-butanol), reaction time, and temperature on the enantiomeric ratio and conversion was tested. The high values of enantiomeric ratio (E in the range of 51.3-90.5) of the esterification of (R,S)-flurbiprofen were obtained for all tested alcohols using Novozym 435, which have a great significance in the field of biotechnological synthesis of drugs. The optimal temperature range for the performed reactions was from 37 to 45 °C. As a result of the optimization, (R)-flurbiprofen methyl ester was obtained with a high optical purity, eep = 96.3 %, after 96 h of incubation. The enantiomeric ratio of the reaction was E = 90.5 and conversion was C = 35.7 %.

  10. Evaluation of achiral templates with fluxional Brønsted basic substituents in enantioselective conjugate additions.

    Science.gov (United States)

    Adachi, Shinya; Takeda, Norihiko; Sibi, Mukund P

    2014-12-19

    Enantioselective conjugate addition of malononitrile to pyrazolidinone-derived enoates proceeds in excellent yields and high enantioselectivities. A comparison of fluxional substituents with and without a Brønsted basic site and their impact on selectivity is detailed. Molecular sieves as an additive were found to be essential to achieve high enantioselectivity.

  11. Asymmetric NHC-catalyzed aza-Diels-Alder reactions: Highly enantioselective route to α-amino acid derivatives and DFT calculations

    KAUST Repository

    Yang, Limin; Wang, Fei; Lee, Richmond; Lv, Yunbo; Huang, Kuo-Wei; Zhong, Guofu

    2014-01-01

    A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study

  12. Paralogous gene analysis reveals a highly enantioselective 1,2-O-isopropylideneglycerol caprylate esterase of Bacillus subtilis

    NARCIS (Netherlands)

    Droge, MJ; Bos, R; Quax, WJ

    Carboxylesterase NP of Bacillus subtilis Thai 1-8, characterized in 1992 as a very enantioselective (S)-naproxen esterase, was found to show no enantiopreference towards (S)-1,2-O-isopropylideneglycerol (IPG) esters. The ybfK gene was identified by the B. subtilis genome project as an unknown gene

  13. Chiral amides via copper-catalysed enantioselective conjugate addition

    NARCIS (Netherlands)

    Schoonen, Anne K.; Fernández-Ibáñez, M. Ángeles; Fañanás-Mastral, Martín; Teichert, Johannes F.; Feringa, Bernard

    2014-01-01

    A highly enantioselective one pot procedure for the synthesis of beta-substituted amides was developed starting from the corresponding alpha,beta-unsaturated esters. This new methodology is based on the copper-catalysed enantioselective conjugate addition of Grignard reagents to

  14. A chiral Brønsted acid-catalyzed highly enantioselective Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines.

    Science.gov (United States)

    Unhale, Rajshekhar A; Sadhu, Milon M; Ray, Sumit K; Biswas, Rayhan G; Singh, Vinod K

    2018-04-03

    A chiral phosphoric acid-catalyzed asymmetric Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines, derived from 3-hydroxyisoindolinones has been demonstrated in this communication. A variety of isoindolinone-based α-amino diazo esters bearing a quaternary stereogenic center were afforded in high yields (up to 99%) with excellent enantioselectivities (up to 99% ee). Furthermore, the synthetic utility of the products has been depicted by the hydrogenation of the diazo moiety of adducts.

  15. Enantioselective Effects of Metalaxyl Enantiomers on Breast Cancer Cells Metabolic Profiling Using HPLC-QTOF-Based Metabolomics

    Directory of Open Access Journals (Sweden)

    Ping Zhang

    2017-01-01

    Full Text Available In this study, an integrative high-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (HPLC-QTOF based metabolomics approach was performed to evaluate the enantioselective metabolic perturbations in MCF-7 cells after treatment with R-metalaxyl and S-metalaxyl, respectively. Untargeted metabolomics profile, multivariate pattern recognition, metabolites identification, and pathway analysis were determined after metalaxyl enantiomer exposure. Principal component analysis (PCA and partitial least-squares discriminant analysis (PLS-DA directly reflected the enantioselective metabolic perturbations induced by metalaxyl enantiomers. On the basis of multivariate statistical results, a total of 49 metabolites including carbohydrates, amino acids, nucleotides, fatty acids, organic acids, phospholipids, indoles, derivatives, etc. were found to be the most significantly changed metabolites and metabolic fluctuations caused by the same concentration of R-metalaxyl and S-metalaxyl were enantioselective. Pathway analysis indicated that R-metalaxyl and S-metalaxyl mainly affected the 7 and 10 pathways in MCF-7 cells, respectively, implying the perturbed pathways induced by metalaxyl enantiomers were also enantioselective. Furthermore, the significantly perturbed metabolic pathways were highly related to energy metabolism, amino acid metabolism, lipid metabolism, and antioxidant defense. Such results provide more specific insights into the enantioselective metabolic effects of chiral pesticides in breast cancer progression, reveal the underlying mechanisms, and provide available data for the health risk assessments of chiral environmental pollutants at the molecular level.

  16. Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.

    Science.gov (United States)

    Sharma, Ankit; Hartwig, John F

    2013-11-27

    We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by the catalytic diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S, or C-C bond at the allylic position in good yield with a high branched-to-linear selectivity and excellent enantioselectivity (ee ≤97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.

  17. Highly enantioselective catalytic cross-dehydrogenative coupling of N-carbamoyl tetrahydroisoquinolines and terminal alkynes.

    Science.gov (United States)

    Sun, Shutao; Li, Chengkun; Floreancig, Paul E; Lou, Hongxiang; Liu, Lei

    2015-04-03

    The first catalytic asymmetric cross-dehydrogenative coupling of cyclic carbamates and terminal alkynes has been established. The reaction features high enantiocontrol and excellent functional group tolerance and displays a wide range of structurally and electronically diverse carbamates as well as terminal alkynes. N-Acyl hemiaminals were identified as the reactive intermediates through preliminary control experiments. Employing readily removable carbamates as substrates rather than traditionally adopted N-aryl amines allows applications in complex molecule synthesis and therefore advances the C-H functionalization strategy to a synthetically useful level.

  18. Enantioselective biotransformations of nitriles in organic synthesis.

    Science.gov (United States)

    Wang, Mei-Xiang

    2015-03-17

    The hydration and hydrolysis of nitriles are valuable synthetic methods used to prepare carboxamides and carboxylic acids. However, chemical hydration and hydrolysis of nitriles involve harsh reaction conditions, have low selectivity, and generate large amounts of waste. Therefore, researchers have confined the scope of these reactions to simple nitrile substrates. However, biological transformations of nitriles are highly efficient, chemoselective, and environmentally benign, which has led synthetic organic chemists and biotechologists to study these reactions in detail over the last two decades. In nature, biological systems degrade nitriles via two distinct pathways: nitrilases catalyze the direct hydrolysis of nitriles to afford carboxylic acids with release of ammonia, and nitrile hydratases catalyze the conversion of nitriles into carboxamides, which then furnish carboxylic acids via hydrolysis in the presence of amidases. Researchers have subsequently developed biocatalytic methods into useful industrial processes for the manufacture of commodity chemicals, including acrylamide. Since the late 1990s, research by my group and others has led to enormous progress in the understanding and application of enantioselective biotransformations of nitriles in organic synthesis. In this Account, I summarize the important advances in enantioselective biotransformations of nitriles and amides, with a primary focus on research from my laboratory. I describe microbial whole-cell-catalyzed kinetic resolution of various functionalized nitriles, amino- and hydroxynitriles, and nitriles that contain small rings and the desymmetrization of prochiral and meso dinitriles and diamides. I also demonstrate how we can apply the biocatalytic protocol to synthesize natural products and bioactive compounds. These nitrile biotransformations offer an attractive and unique protocol for the enantioselective synthesis of polyfunctionalized organic compounds that are not readily obtainable by

  19. Enantioselective Copper-Catalyzed Carboetherification of Unactivated Alkenes**

    Science.gov (United States)

    Bovino, Michael T.; Liwosz, Timothy W.; Kendel, Nicole E.; Miller, Yan; Tyminska, Nina

    2014-01-01

    Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein is reported a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols that terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition state calculations support a cis-oxycupration stereochemistry-determining step. PMID:24798697

  20. Direct Enantioselective Reaction between Hemiacetals and Phosphorus Ylides: Important Role of a By-Product in the Asymmetric Transformation.

    Science.gov (United States)

    Wang, Rui; Wang, Linqing; Yang, Dongxu; Li, Dan; Liu, Xihong; Wang, Pengxin; Wang, Kezhou; Zhu, Haiyong; Bai, Lutao

    2018-05-16

    By employing a simple in-situ generated magnesium catalyst, the direct asymmetric reaction between hemiacetals and P-ylides is achieved via a tandem Wittig-oxa-Michael reaction sequence. Enantioenriched chromans, isochromans and tetrahydropyrans can be obtained in good chemical yields. (-)-Erythrococcamide B can be asymmetrically synthesized through this synthetic technique. In this work, the by-product, TPO, was identified as a necessary additive in this asymmetric synthetic method. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Enantioselective determination of (R)-zopiclone and (S)-zopiclone (eszopiclone) in human hair by micropulverized extraction and chiral liquid chromatography/high resolution mass spectrometry.

    Science.gov (United States)

    Miyaguchi, Hajime; Kuwayama, Kenji

    2017-10-13

    Zopiclone and its (S)-enantiomer (eszopiclone) are commonly prescribed for insomnia. Despite the high demand for enantioselective differentiation, the chiral analysis of zopiclone in hair has not been reported. In this study, a method for the enantioselective quantification of zopiclone in human hair was developed. The extraction medium and duration were optimized using real eszopiclone-positive hair samples. Specifically, micropulverized extraction with 3.0M ammonium phosphate buffer (pH 8.4) involving salting-out assisted liquid-liquid extraction with acetonitrile was utilized to minimize the degradation of zopiclone and for rapid and facile operation. On the other hand, recovery of the conventional solid-liquid extraction involved overnight soaking in 3.0M ammonium phosphate buffer (pH 8.4) was only 0.58±0.12% of the maximum recovery achieved by the present method due to the decomposition in the phosphate buffer. An excellent chiral separation (Rs=5.0) was achieved using a chiral stationary phase comprising cellulose tris(3,5-dichlorophenylcarbamate) and a volatile mobile phase of 10mM ammonium carbonate (pH 8.0)-acetonitrile (25:75, v/v). Detection was carried out using liquid chromatography/high resolution mass spectrometry (LC/HRMS) with electrospray ionization. A Q Exactive mass spectrometer equipped with a quadrupole-Orbitrap analyzer was used for detection. The concentration of 0.50pg/mg was defined as the lowest limit of quantification using 5mg of hair sample. Using the developed approach, the concentration of eszopiclone in hair after a single 2-mg dose was found to be 441pg/mg, which was higher than all the reported values regarding a single administration of zopiclone. After daily administration of racemic zopiclone (3.75mg/day), the concentrations of (R)-enantiomer and (S)-enantiomer in the black hair were 5.30-8.31ng/mg and 7.96-12.8ng/mg, respectively, and the concentration of the (S)-enantiomer was always higher than that of the (R

  2. Kinetic mechanism and enantioselectivity of halohydrin dehalogenase from Agrobacterium radiobacter

    NARCIS (Netherlands)

    Tang, Lixia; Lutje Spelberg, Jeffrey H.; Fraaije, Marco W.; Janssen, DB

    2003-01-01

    Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the reversible intramolecular nucleophilic displacement of a halogen by a hydroxyl group in vicinal haloalcohols, producing the corresponding epoxides. The enzyme displays high enantioselectivity toward some aromatic

  3. Rhodium(II)-catalyzed enantioselective synthesis of troponoids.

    Science.gov (United States)

    Murarka, Sandip; Jia, Zhi-Jun; Merten, Christian; Daniliuc, Constantin-G; Antonchick, Andrey P; Waldmann, Herbert

    2015-06-22

    We report a rhodium(II)-catalyzed highly enantioselective 1,3-dipolar cycloaddition reaction between the carbonyl moiety of tropone and carbonyl ylides to afford troponoids in good to high yields with excellent enantioselectivity. We demonstrate that α-diazoketone-derived carbonyl ylides, in contrast to carbonyl ylides derived from diazodiketoesters, undergo [6+3] cycloaddition reactions with tropone to yield the corresponding bridged heterocycles with excellent stereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Enantioselective cyclizations and cyclization cascades of samarium ketyl radicals

    Science.gov (United States)

    Kern, Nicolas; Plesniak, Mateusz P.; McDouall, Joseph J. W.; Procter, David J.

    2017-12-01

    The rapid generation of molecular complexity from simple starting materials is a key challenge in synthesis. Enantioselective radical cyclization cascades have the potential to deliver complex, densely packed, polycyclic architectures, with control of three-dimensional shape, in one step. Unfortunately, carrying out reactions with radicals in an enantiocontrolled fashion remains challenging due to their high reactivity. This is particularly the case for reactions of radicals generated using the classical reagent, SmI2. Here, we demonstrate that enantioselective SmI2-mediated radical cyclizations and cascades that exploit a simple, recyclable chiral ligand can convert symmetrical ketoesters to complex carbocyclic products bearing multiple stereocentres with high enantio- and diastereocontrol. A computational study has been used to probe the origin of the enantioselectivity. Our studies suggest that many processes that rely on SmI2 can be rendered enantioselective by the design of suitable ligands.

  5. Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

    KAUST Repository

    Behenna, Douglas C.; Mohr, Justin T.; Sherden, Nathaniel H.; Marinescu, Smaranda C.; Harned, Andrew M.; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Nová k, Zoltá n; Krout, Michael R.; McFadden, Ryan M.; Roizen, Jennifer L.; Enquist, John A.; White, David E.; Levine, Samantha R.; Petrova, Krastina V.; Iwashita, Akihiko; Virgil, Scott C.; Stoltz, Brian M.

    2011-01-01

    α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center.

  6. Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

    Science.gov (United States)

    Behenna, Douglas C.; Mohr, Justin T.; Sherden, Nathaniel H.; Marinescu, Smaranda C.; Harned, Andrew M.; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Novák, Zoltán; Krout, Michael R.; McFadden, Ryan M.; Roizen, Jennifer L.; Enquist, John A.; White, David E.; Levine, Samantha R.; Petrova, Krastina V.; Iwashita, Akihiko; Virgil, Scott C.; Stoltz, Brian M.

    2012-01-01

    α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursors: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center. PMID:22083969

  7. Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

    KAUST Repository

    Behenna, Douglas C.

    2011-11-14

    α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center.

  8. Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement

    OpenAIRE

    Liu, Wen-Bo; Okamoto, Noriko; Alexy, Eric J.; Hong, Allen Y.; Tran, Kristy; Stoltz, Brian M.

    2016-01-01

    A catalytic, enantioselective ? -alkylation of ?,?-unsaturated malonates and ketoesters is reported. This strategy entails a highly regio- and enantioselective iridium-catalyzed ?-alkylation of an extended enolate, and a subsequent translocation of chirality to the ?-position via a Cope rearrangement.

  9. HIGHLY ENANTIOSELECTIVE CATALYTIC DIRECT ADDITION OF ALKYNES TO IMINES IN WATER. (R828129)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  10. Asymmetric NHC-catalyzed aza-Diels-Alder reactions: Highly enantioselective route to α-amino acid derivatives and DFT calculations

    KAUST Repository

    Yang, Limin

    2014-08-01

    A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study showed that cis-TSa, formed from a top face approach of oxodiazene to cis-IIa, is the most favorable transition state and is consistent with the experimental observations. © 2014 American Chemical Society.

  11. Highly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings

    KAUST Repository

    Wang, Tianli

    2015-06-02

    Phosphine-catalyzed highly enantioselective γ-additions of 5H-thiazol-4-ones and 5H-oxazol-4-ones to allenoates have been developed for the first time. With the employment of amino-acid derived bifunctional phosphines, a wide range of substituted 5H-thiazol-4-one and 5H-oxazol-4-one derivatives bearing heteroarom (S or O)-containing tertiary chiral centers were constructed in high yields and excellent enantioselectivities. The reported method provides a facile access to enantioenriched tertiary thioether/alcohols. The mechanism of γ-addition reaction was investigated by performing DFT calculations, and the hydrogen bonding interactions between the Brønsted acid moiety of the phosphine catalysts and the “C=O” unit of donor molecules were shown to be crucial in asymmetric induction.

  12. Highly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings

    KAUST Repository

    Wang, Tianli; Yu, Zhaoyuan; Hoon, Ding Long; Huang, Kuo-Wei; Lan, Yu; Lu, Yixin

    2015-01-01

    Phosphine-catalyzed highly enantioselective γ-additions of 5H-thiazol-4-ones and 5H-oxazol-4-ones to allenoates have been developed for the first time. With the employment of amino-acid derived bifunctional phosphines, a wide range of substituted 5H-thiazol-4-one and 5H-oxazol-4-one derivatives bearing heteroarom (S or O)-containing tertiary chiral centers were constructed in high yields and excellent enantioselectivities. The reported method provides a facile access to enantioenriched tertiary thioether/alcohols. The mechanism of γ-addition reaction was investigated by performing DFT calculations, and the hydrogen bonding interactions between the Brønsted acid moiety of the phosphine catalysts and the “C=O” unit of donor molecules were shown to be crucial in asymmetric induction.

  13. Chiral Nickel(II) Complex Catalyzed Enantioselective Doyle-Kirmse Reaction of α-Diazo Pyrazoleamides.

    Science.gov (United States)

    Lin, Xiaobin; Tang, Yu; Yang, Wei; Tan, Fei; Lin, Lili; Liu, Xiaohua; Feng, Xiaoming

    2018-03-07

    Although high enantioselectivity of [2,3]-sigmatropic rearrangement of sulfonium ylides (Doyle-Kirmse reaction) has proven surprisingly elusive using classic chiral Rh(II) and Cu(I) catalysts, in principle it is due to the difficulty in fine discrimination of the heterotopic lone pairs of sulfur and chirality inversion at sulfur of sulfonium ylides. Here, we show that the synergistic merger of new α-diazo pyrazoleamides and a chiral N, N'-dioxide-nickel(II) complex catalyst enables a highly enantioselective Doyle-Kirmse reaction. The pyrazoleamide substituent serves as both an activating and a directing group for the ready formation of a metal-carbene- and Lewis-acid-bonded ylide intermediate in the assistance of a dual-tasking nickel(II) complex. An alternative chiral Lewis-acid-bonded ylide pathway greatly improves the product enantiopurity even for the reaction of a symmetric diallylsulfane. The majority of transformations over a series of aryl- or vinyl-substituted α-diazo pyrazoleamindes and sulfides proceed rapidly (within 5-20 min in most cases) with excellent results (up to 99% yield and 96% ee), providing a breakthrough in enantioselective Doyle-Kirmse reaction.

  14. Enantioselective carbenoid insertion into C(sp3–H bonds

    Directory of Open Access Journals (Sweden)

    J. V. Santiago

    2016-05-01

    Full Text Available The enantioselective carbenoid insertion into C(sp3–H bonds is an important tool for the synthesis of complex molecules due to the high control of enantioselectivity in the formation of stereogenic centers. This paper presents a brief review of the early issues, related mechanistic studies and recent applications on this chemistry area.

  15. Copper(II)-catalyzed exo and enantioselective cycloadditions of azomethine imines.

    Science.gov (United States)

    Sibi, Mukund P; Rane, Digamber; Stanley, Levi M; Soeta, Takahiro

    2008-07-17

    A strategy for exo and enantioselective 1,3-dipolar cycloaddition of azomethine imines to 2-acryloyl-3-pyrazolidinone is described. The corresponding cycloadducts are isolated with high diastereoselectivities (up to >96:4 exo/endo) and enantioselectivities (up to 98% ee).

  16. Highly Enantioselective Production of Chiral Secondary Alcohols Using Lactobacillus paracasei BD101 as a New Whole Cell Biocatalyst and Evaluation of Their Antimicrobial Effects.

    Science.gov (United States)

    Yılmaz, Durmuşhan; Şahin, Engin; Dertli, Enes

    2017-11-01

    Chiral secondary alcohols are valuable intermediates for many important enantiopure pharmaceuticals and biologically active molecules. In this work, we studied asymmetric reduction of aromatic ketones to produce the corresponding chiral secondary alcohols using lactic acid bacteria (LAB) as new biocatalysts. Seven LAB strains were screened for their ability to reduce acetophenones to their corresponding alcohols. Among these strains, Lactobacillus paracasei BD101 was found to be the most successful at reducing the ketones to the corresponding alcohols. The reaction conditions were further systematically optimized for this strain and high enantioselectivity (99%) and very good yields were obtained. These secondary alcohols were further tested for their antimicrobial activities against important pathogens and significant levels of antimicrobial activities were observed although these activities were altered depending on the secondary alcohols as well as their enantiomeric properties. The current methodology demonstrates a promising and alternative green approach for the synthesis of chiral secondary alcohols of biological importance in a cheap, mild, and environmentally useful process. © 2017 Wiley-VHCA AG, Zurich, Switzerland.

  17. Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

    Science.gov (United States)

    Bovino, Michael T; Liwosz, Timothy W; Kendel, Nicole E; Miller, Yan; Tyminska, Nina; Zurek, Eva; Chemler, Sherry R

    2014-06-16

    Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition-state calculations support a cis-oxycupration stereochemistry-determining step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Enantioselective Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds.

    Science.gov (United States)

    Hari, Durga Prasad; Waser, Jerome

    2017-06-28

    Enantioselective catalytic methods allowing the addition of both a nucleophile and an electrophile onto diazo compounds give a fast access into important building blocks. Herein, we report the highly enantioselective oxyalkynylation of diazo compounds using ethynylbenziodoxol-(on)e reagents and a simple copper bisoxazoline catalyst. The obtained α-benzoyloxy propargylic esters are useful building blocks, which are difficult to synthesize in enantiopure form using other methods. The obtained products could be efficiently transformed into vicinal diols and α-hydroxy propargylic esters without loss in enantiopurity.

  19. Pentanidium-catalyzed enantioselective phase-transfer conjugate addition reactions

    KAUST Repository

    Ma, Ting

    2011-03-09

    A new chiral entity, pentanidium, has been shown to be an excellent chiral phase-transfer catalyst. The enantioselective Michael addition reactions of tert-butyl glycinate-benzophenone Schiff base with various α,β- unsaturated acceptors provide adducts with high enantioselectivities. A successful gram-scale experiment at a low catalyst loading of 0.05 mol % indicates the potential for practical applications of this methodology. Phosphoglycine ester analogues can also be utilized as the Michael donor, affording enantioenriched α-aminophosphonic acid derivatives and phosphonic analogues of (S)-proline. © 2011 American Chemical Society.

  20. Enantioselective radical addition/trapping reactions with alpha,beta-disubstituted unsaturated imides. Synthesis of anti-propionate aldols.

    Science.gov (United States)

    Sibi, Mukund P; Petrovic, Goran; Zimmerman, Jake

    2005-03-02

    This manuscript describes a highly diastereo- and enantioselective intermolecular radical addition/hydrogen atom transfer to alpha,beta-disubstituted enoates. Additionally, we show that anti-propionate aldol-like products can be easily prepared from alpha-methyl-beta-acyloxyenoates in good yields and high diastereo- and enantioselectivities.

  1. Enantioselective synthesis of α-oxy amides via Umpolung amide synthesis.

    Science.gov (United States)

    Leighty, Matthew W; Shen, Bo; Johnston, Jeffrey N

    2012-09-19

    α-Oxy amides are prepared through enantioselective synthesis using a sequence beginning with a Henry addition of bromonitromethane to aldehydes and finishing with Umpolung Amide Synthesis (UmAS). Key to high enantioselection is the finding that ortho-iodo benzoic acid salts of the chiral copper(II) bis(oxazoline) catalyst deliver both diastereomers of the Henry adduct with high enantiomeric excess, homochiral at the oxygen-bearing carbon. Overall, this approach to α-oxy amides provides an innovative complement to alternatives that focus almost entirely on the enantioselective synthesis of α-oxy carboxylic acids.

  2. Nickel-catalyzed regio- and enantioselective aminolysis of 3,4-epoxy alcohols.

    Science.gov (United States)

    Wang, Chuan; Yamamoto, Hisashi

    2015-04-08

    The first catalytic regio- and enantioselective aminolysis of 3,4-epoxy alcohols has been accomplished. Under the catalysis of Ni(ClO4)2·6H2O, the C4 selective ring opening of various 3,4-epoxy alcohols proceeded in a stereospecific manner with high regioselectivities. Furthermore, with the Ni-BINAM catalytic system the enantioselective ring opening of 3,4-epoxy alcohols furnished various γ-hydroxy-δ-amino alcohols as products with complete regiocontrol and high enantioselectivities (up to 94% ee).

  3. Enantioselective Access to Spirocyclic Sultams by Chiral Cp(x) -Rhodium(III)-Catalyzed Annulations.

    Science.gov (United States)

    Pham, Manh V; Cramer, Nicolai

    2016-02-12

    Chiral spirocyclic sultams are a valuable compound class in organic and medicinal chemistry. A rapid entry to this structural motif involves a [3+2] annulation of an N-sulfonyl ketimine and an alkyne. Although the directing-group properties of the imino group for C-H activation have been exploited, the developments of related asymmetric variants have remained very challenging. The use of rhodium(III) complexes equipped with a suitable atropchiral cyclopentadienyl ligand, in conjunction with a carboxylic acid additive, enables an enantioselective and high yielding access to such spirocyclic sultams. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Pyrones to pyrans: enantioselective radical additions to acyloxy pyrones.

    Science.gov (United States)

    Sibi, Mukund P; Zimmerman, Jake

    2006-10-18

    This paper describes a highly site-, diastereo-, and enantioselective intermolecular radical addition/hydrogen atom transfer to hydroxypyrone pyromeconic and kojic acids. The methodology can be extended to the formation of chiral quaternary centers. The products obtained are densely functionalized pyran moieties. The products contain structural features amenable for the introduction of additional substituents.

  5. Guanidine-catalyzed enantioselective desymmetrization of meso-aziridines

    KAUST Repository

    Zhang, Yan

    2011-01-01

    An amino-indanol derived chiral guanidine was developed as an efficient Brønsted base catalyst for the desymmetrization of meso-aziridines with both thiols and carbamodithioic acids as nucleophiles, which provided 1,2-difunctionalized ring-opened products in high yields and enantioselectivities. © The Royal Society of Chemistry.

  6. Cyclopalladated complexes in enantioselective catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Dunina, Valeria V; Gorunova, Olga N; Zykov, P A; Kochetkov, Konstantin A

    2011-01-31

    The results of the use of optically active palladacycles in enantioselective catalysis of [3,3]-sigmatropic rearrangements, aldol condensation, the Michael reaction and cross-coupling are analyzed. Reactions with allylic substrates or reagents and some other transformations are considered.

  7. Infrared-thermographic screening of the activity and enantioselectivity of enzymes.

    Science.gov (United States)

    Reetz, M T; Hermes, M; Becker, M H

    2001-05-01

    The infrared radiation caused by the heat of reaction of an enantioselective enzyme-catalyzed transformation can be detected by modern photovoltaic infrared (IR)-thermographic cameras equipped with focal-plane array detectors. Specifically, in the lipase-catalyzed enantioselective acylation of racemic 1-phenylethanol, the (R)- and (S)-substrates are allowed to react separately in the wells of microtiter plates, the (R)-alcohol showing hot spots in the IR-thermographic images. Thus, highly enantioselective enzymes can be identified at kinetic resolution.

  8. Integrative assessment of enantioselectivity in endocrine disruption and immunotoxicity of synthetic pyrethroids

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Meirong [Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Chen Fang [College of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310018 (China); Wang Cui; Zhang Quan [Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Gan Jianying [Department of Environmental Sciences, University of California, Riverside, CA 92521 (United States); Liu Weiping, E-mail: wliu@zjut.edu.c [Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China)

    2010-05-15

    The increasing release of chiral chemicals into the environment dictates attention to a better understanding of enantioselectivity in their human and ecotoxicological effects. Although enantioselectivity has been considered in many recent studies, there is little effort for discerning the connection between different processes, and as such, our current knowledge about chiral contaminants is rather scattered and incoherent. In this study, we simultaneously evaluated enantioselectivity of two chiral pesticides, lambda-cyhalothrin (LCT) and (Z)-cis-bifenthrin (cis-BF), in immunotoxicity to macrophage cells (RAW264.7), and endocrine disruption activity in human breast carcinoma cell line MCF-7. Analysis of cell proliferation, cell viability, apoptosis, and receptor gene expression showed significant differences between the enantiomers of LCT or cis-BF in estrogenic potential and immunocytotoxicity. The selectivity in these effects consistently followed the same direction, with (-)-LCT or 1S-cis-BF displaying a greater activity than its counterpart. The consistency was attributed to interplaying mechanisms in the closely interacting immune and endocrine systems. The underlying interplays suggest that other chiral xenobiotics may also show a directional enantioselectivity in immunotoxicity and endocrine toxicity. Given that many biological processes are inter-related, enantioselectivity may follow specific patterns that can be revealed via integrative assessments as demonstrated in this study. - Chiral contaminants should consider multiple effects and relate directions of enantioselectivity to their interplaying processes.

  9. Integrative assessment of enantioselectivity in endocrine disruption and immunotoxicity of synthetic pyrethroids

    International Nuclear Information System (INIS)

    Zhao Meirong; Chen Fang; Wang Cui; Zhang Quan; Gan Jianying; Liu Weiping

    2010-01-01

    The increasing release of chiral chemicals into the environment dictates attention to a better understanding of enantioselectivity in their human and ecotoxicological effects. Although enantioselectivity has been considered in many recent studies, there is little effort for discerning the connection between different processes, and as such, our current knowledge about chiral contaminants is rather scattered and incoherent. In this study, we simultaneously evaluated enantioselectivity of two chiral pesticides, lambda-cyhalothrin (LCT) and (Z)-cis-bifenthrin (cis-BF), in immunotoxicity to macrophage cells (RAW264.7), and endocrine disruption activity in human breast carcinoma cell line MCF-7. Analysis of cell proliferation, cell viability, apoptosis, and receptor gene expression showed significant differences between the enantiomers of LCT or cis-BF in estrogenic potential and immunocytotoxicity. The selectivity in these effects consistently followed the same direction, with (-)-LCT or 1S-cis-BF displaying a greater activity than its counterpart. The consistency was attributed to interplaying mechanisms in the closely interacting immune and endocrine systems. The underlying interplays suggest that other chiral xenobiotics may also show a directional enantioselectivity in immunotoxicity and endocrine toxicity. Given that many biological processes are inter-related, enantioselectivity may follow specific patterns that can be revealed via integrative assessments as demonstrated in this study. - Chiral contaminants should consider multiple effects and relate directions of enantioselectivity to their interplaying processes.

  10. Cu(I)-Catalyzed Enantioselective Friedel-Crafts Alkylation of Indoles with 2-Aryl-N-sulfonylaziridines as Alkylating Agents.

    Science.gov (United States)

    Ge, Chen; Liu, Ren-Rong; Gao, Jian-Rong; Jia, Yi-Xia

    2016-07-01

    A highly enantioselective Friedel-Crafts alkylation of indoles with N-sulfonylaziridines as alkylating agents has been developed by utilizing the complex of Cu(CH3CN)4BF4/(S)-Segphos as a catalyst. A range of optically active tryptamine derivatives are obtained in good to excellent yields and enantioselectivities (up to >99% ee) via a kinetic resolution process.

  11. Rhodium-Catalyzed Enantioselective Cyclopropanation of Olefins with N-Sulfonyl 1,2,3-Triazoles

    Science.gov (United States)

    Chuprakov, Stepan; Kwok, Sen Wai; Zhang, Li; Lercher, Lukas; Fokin, Valery V.

    2009-01-01

    N-Sulfonyl 1,2,3-triazoles readily form rhodium(II) azavinyl carbenes, which react with olefins to produce cyclopropanes with excellent diastereo- and enantioselectivity and in high yield. PMID:19928917

  12. Catalytic enantioselective Reformatsky reaction with ketones

    NARCIS (Netherlands)

    Fernandez-Ibanez, M. Angeles; Macia, Beatriz; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    Chiral tertiary alcohols were obtained with good yields and enantioselectivities via a catalytic Reformatsky reaction with ketones, including the challenging diaryl ketones, using chiral BINOL derivatives.

  13. Enantioselective Total Synthesis of Antibiotic CJ-16,264, Synthesis and Biological Evaluation of Designed Analogues, and Discovery of Highly Potent and Simpler Antibacterial Agents.

    Science.gov (United States)

    Nicolaou, K C; Pulukuri, Kiran Kumar; Rigol, Stephan; Buchman, Marek; Shah, Akshay A; Cen, Nicholas; McCurry, Megan D; Beabout, Kathryn; Shamoo, Yousif

    2017-11-08

    An improved and enantioselective total synthesis of antibiotic CJ-16,264 through a practical kinetic resolution and an iodolactonization reaction to form the iodo pyrrolizidinone fragment of the molecule is described. A series of racemic and enantiopure analogues of CJ-16,264 was designed and synthesized through the developed synthetic technologies and tested against drug-resistant bacterial strains. These studies led to interesting structure-activity relationships and the identification of a number of simpler, and yet equipotent, or even more potent, antibacterial agents than the natural product, thereby setting the foundation for further investigations in the quest for new anti-infective drugs.

  14. Enantioselective 1,3-dipolar cycloadditions of diazoacetates with electron-deficient olefins.

    Science.gov (United States)

    Sibi, Mukund P; Stanley, Levi M; Soeta, Takahiro

    2007-04-12

    [reaction: see text] A general strategy for highly enantioselective 1,3-dipolar cycloaddition of diazoesters to beta-substituted, alpha-substituted, and alpha,beta-disubstituted alpha,beta-unsaturated pyrazolidinone imides is described. Cycloadditions utilizing less reactive alpha,beta-disubstituted dipolarophiles require elevated reaction temperatures, but still provide the corresponding pyrazolines with excellent enantioselectivities. Finally, an efficient synthesis of (-)-manzacidin A employing this cycloaddition methodology as a key step is illustrated.

  15. The enantioselective total synthesis of (+)-clusianone.

    Science.gov (United States)

    Horeischi, Fiene; Guttroff, Claudia; Plietker, Bernd

    2015-02-11

    (+)-Clusianone, an exo-type B PPAP with reported anti-HIV and chemoprotective activities, was synthesized in eleven steps with 97% ee starting from acetylacetone. An enantioselective decarboxylative Tsuji-Trost-allylation and a Ru-catalyzed ring-closing metathesis-decarboxylative allylation were used to control both diastereo- and enantioselectivity.

  16. Asymmetric allylation of α-ketoester-derived N-benzoylhydrazones promoted by chiral sulfoxides/N-oxides Lewis bases: highly enantioselective synthesis of quaternary α-substituted α-allyl-α-amino acids.

    Science.gov (United States)

    Reyes-Rangel, Gloria; Bandala, Yamir; García-Flores, Fred; Juaristi, Eusebio

    2013-09-01

    Chiral sulfoxides/N-oxides (R)-1 and (R,R)-2 are effective chiral promoters in the enantioselective allylation of α-keto ester N-benzoylhydrazone derivatives 3a-g to generate the corresponding N-benzoylhydrazine derivatives 4a-g, with enantiomeric excesses as high as 98%. Representative hydrazine derivatives 4a-b were subsequently treated with SmI2, and the resulting amino esters 5a-b with LiOH to obtain quaternary α-substituted α-allyl α-amino acids 6a-b, whose absolute configuration was assigned as (S), with fundament on chemical correlation and electronic circular dichroism (ECD) data. © 2013 Wiley Periodicals, Inc.

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

    KAUST Repository

    Lee, Richmond

    2013-01-01

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

  18. Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

    KAUST Repository

    Thomas, Renee M.

    2010-11-24

    A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.

  19. Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

    KAUST Repository

    Thomas, Renee M.; Widger, Peter C. B.; Ahmed, Syud M.; Jeske, Ryan C.; Hirahata, Wataru; Lobkovsky, Emil B.; Coates, Geoffrey W.

    2010-01-01

    A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.

  20. Enantioselective Alkylation of 2-Oxindoles Catalyzed by a Bifunctional Phase-Transfer Catalyst: Synthesis of (-)-Debromoflustramine B.

    Science.gov (United States)

    Craig, Ryan; Sorrentino, Emiliano; Connon, Stephen J

    2018-03-26

    A new bifunctional phase-transfer catalyst that employs hydrogen bonding as a control element was developed to promote efficient enantioselective S N 2 reactions for the construction all-carbon quaternary stereocenters in high yield and excellent enantioselectivity (up to 97 % ee) utilizing the alkylation of a malleable oxindole substrate. The utility of the methodology was demonstrated through a concise and highly enantioselective synthesis of (-)-debromoflustramine B. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Enantioselective conjugate radical addition to alpha'-hydroxy enones.

    Science.gov (United States)

    Lee, Sunggi; Lim, Chae Jo; Kim, Sunggak; Subramaniam, Rajesh; Zimmerman, Jake; Sibi, Mukund P

    2006-09-14

    Enantioselective conjugate radical addition to alpha'-hydroxy alpha,beta-unsaturated ketones, compounds containing bidentate donors, has been investigated. It has been found that radical additions to alpha'-hydroxy alpha,beta-unsaturated ketones in the presence of Mg(NTf2)2 and bisoxazoline ligand 5a proceeded cleanly, yielding the addition products in high chemical yields and good enantiomeric excesses.

  2. Quinine-Promoted, Enantioselective Boron-Tethered Diels-Alder Reaction by Anomeric Control of Transition State Conformation.

    Science.gov (United States)

    Scholl, Katie; Dillashaw, John; Timpy, Evan; Lam, Yu-Hong; DeRatt, Lindsey; Benton, Tyler R; Powell, Jacqueline P; Houk, Kendall N; Morgan, Jeremy B

    2018-05-01

    Diels-Alder reactions of tethered vinyl-metal species offer the opportunity to fashion highly functionalized diol intermediates for synthesis. We have developed the first enantioselective boron-tethered Diels-Alder reaction using quinine as a chiral promoter. Quinine recovery, enantioselectivity enhancement, and manipulation of the cyclohexene core are also investigated. DFT modeling calculations confirm the role of quinine as a bidentate ligand enhancing reaction rates. The enantioselectivity of the cycloaddition is proposed to originate from a boron-centered anomeric effect.

  3. Enantioselective synthesis of tetrafluorinated ribose and fructose.

    Science.gov (United States)

    Linclau, Bruno; Boydell, A James; Timofte, Roxana S; Brown, Kylie J; Vinader, Victoria; Weymouth-Wilson, Alexander C

    2009-02-21

    A perfluoroalkylidene lithium mediated cyclisation approach for the enantioselective synthesis of a tetrafluorinated aldose (ribose) and of a tetrafluorinated ketose (fructose), both in the furanose and in the pyranose form, is described.

  4. Kinetic investigation on enantioselective hydrolytic resolution of ...

    African Journals Online (AJOL)

    Kinetic investigation on enantioselective hydrolytic resolution of epichlorohydrin by crude epoxide hydrolase from domestic duck liver. X Ling, D Lu, J Wang, J Chen, L Ding, J Chen, H Chai, P Ouyang ...

  5. Enantiomerization and enantioselective bioaccumulation of metalaxyl in Tenebrio molitor larvae.

    Science.gov (United States)

    Gao, Yongxin; Wang, Huili; Qin, Fang; Xu, Peng; Lv, Xiaotian; Li, Jianzhong; Guo, Baoyuan

    2014-02-01

    The enantiomerization and enantioselective bioaccumulation of metalaxyl by a single dose of exposure to Tenebrio molitor larvae under laboratory condition were studied by high-performance liquid chromatography tandem mass spectroscopy (HPLC-MS/MS) based on a ChiralcelOD-3R [cellulosetris-tris-(3, 5-dichlorophenyl-carbamate)] column. Exposure of enantiopure R-metalaxyl and S-metalaxyl in Tenebrio molitor larvae exhibited significant enantiomerization, with formation of the R enantiomers from the S enantiomers, and vice versa, which might be attributed to the chiral pesticide catalyzed by a certain enzyme in Tenebrio molitor larvae. Enantiomerization was not observed in wheat bran during the period of 21 d. In addition, bioaccumulation of rac-metalaxyl in Tenebrio molitor larvae was enantioselective with a preferential accumulation of S-metalaxyl. These results showed that enantioselectivity was caused not only by actual degradation and metabolism but also by enantiomerization, which was an important process in the environmental fate and behavior of metalaxyl enantiomers. Copyright © 2013 Wiley Periodicals, Inc.

  6. Enantioselective Cytotoxicity Profile of o,p’-DDT in PC 12 Cells

    Science.gov (United States)

    Zhang, Chunlong; Wen, Yuezhong; Liu, Weiping

    2012-01-01

    Background The continued uses of dichlordiphenyltrichloroethane (DDT) for indoor vector control in some developing countries have recently fueled intensive debates toward the global ban of this persistent legacy contaminant. Current approaches for ecological and health risk assessment has ignored the chiral nature of DDT. In this study by employing an array of cytotoxicity related endpoints, we investigated the enantioselective cytotoxicity of o,p’-DDT. Principal Findings we demonstrated for the first time that R-(−)-o,p’-DDT caused more neuron cell death by inducing more severe oxidative stress, which selectively imbalanced the transcription of stress-related genes (SOD1, SOD2, HSP70) and enzyme (superoxide dismutase and lactate dehydrogenase) activities, and greater cellular apoptosis compared to its enantiomer S-(+)-o,p’-DDT at the level comparable to malaria area exposure (parts per million). We further elucidated enantioselective modes of action using microarray combined with enzyme-linked immunosorbent assay. The enantioselective apoptosis might involve three signaling pathways via caspase 3, tumor protein 53 (p53) and NFkB. Conclusions Based on DDT stereochemistry and results reported for other chiral pesticides, our results pointed to the same directional enantioselectivity of chiral DDT toward mammalian cells. We proposed that risk assessment on DDT should consider the enantiomer ratio and enantioselectivities. PMID:22937105

  7. The Catalytic Enantioselective Total Synthesis of (+)‐Liphagal

    DEFF Research Database (Denmark)

    Day, Joshua J.; McFadden, Ryan M.; Virgil, Scott C.

    2011-01-01

    Ring a ding: The first catalytic enantioselective total synthesis of the meroterpenoid natural product (+)-liphagal is disclosed. The approach showcases a variety of technology including enantioselective enolate alkylation, a photochemical alkyne-alkene [2+2] reaction, microwaveassisted metal...

  8. Enantioselective synthesis of chiral 3-aryl-1-indanones through rhodium-catalyzed asymmetric intramolecular 1,4-addition.

    Science.gov (United States)

    Yu, Yue-Na; Xu, Ming-Hua

    2013-03-15

    Enantioselective synthesis of potentially useful chiral 3-aryl-1-indanones was achieved through a rhodium-catalyzed asymmetric intramolecular 1,4-addition of pinacolborane chalcone derivatives using extraordinary simple MonoPhos as chiral ligand under relatively mild conditions. This novel protocol offers an easy access to a wide variety of enantioenriched 3-aryl-1-indanone derivatives in high yields (up to 95%) with excellent enantioselectivities (up to 95% ee).

  9. L-Threonine-derived novel bifunctional phosphine-sulfonamide catalyst-promoted enantioselective aza-morita-Baylis-Hillman reaction

    KAUST Repository

    Zhong, Fangrui

    2011-03-18

    A series of novel bifunctional phosphine-sulfonamide organic catalysts were designed and readily prepared from natural amino acids, and they were utilized to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions. l-Threonine-derived phosphine-sulfonamide 9b was found to be the most efficient catalyst, affording the desired aza-MBH adducts in high yields and with excellent enantioselectivities. © 2011 American Chemical Society.

  10. Catalytic Enantioselective Synthesis of 3,4-Unsubstituted Thiochromenes through Sulfa-Michael/Julia-Kocienski Olefination Cascade Reaction.

    Science.gov (United States)

    Simlandy, Amit Kumar; Mukherjee, Santanu

    2017-05-05

    A highly enantioselective cascade sulfa-Michael/Julia-Kocienski olefination reaction between 2-mercaptobenzaldehydes and β-substituted vinyl PT-sulfones has been realized for the synthesis of 3,4-unsubstituted 2H-thiochromenes. This reaction, catalyzed by diphenylprolinol TMS ether, proceeds through an aromatic iminium intermediate and furnishes a wide range of 2-substiuted 2H-thiochromenes with excellent enantioselectivities (up to 99:1 er).

  11. Silica-Supported Catalyst for Enantioselective Arylation of Aldehydes under Batch and Continuous-Flow Conditions.

    Science.gov (United States)

    Watanabe, Satoshi; Nakaya, Naoyuki; Akai, Junichiro; Kanaori, Kenji; Harada, Toshiro

    2018-05-04

    A silica-supported 3-aryl H 8 -BINOL-derived titanium catalyst exhibited high performance in the enantioselective arylation of aromatic aldehydes using Grignard and organolithium reagents not only under batch conditions but also under continuous-flow conditions. Even with a simple pipet reactor packed with the heterogeneous catalyst, the enantioselective production of chiral diarylmethanols could be achieved through a continuous introduction of aldehydes and mixed titanium reagents generated from the organometallic precursors. The pipet reactor could be used repeatedly in different reactions without appreciable deterioration of the activity.

  12. Application of Phosphine-Phosphite Ligands in the Iridium Catalyzed Enantioselective Hydrogenation of 2-Methylquinoline

    Directory of Open Access Journals (Sweden)

    Miguel Rubio

    2010-10-01

    Full Text Available The hydrogenation of 2-methylquinoline with Ir catalysts based on chiral phosphine-phosphites has been investigated. It has been observed that the reaction is very sensitive to the nature of the ligand. Optimization of the catalyst, allowed by the highly modular structure of these phosphine-phosphites, has improved the enantioselectivity of the reaction up to 73% ee. The influence of additives in this reaction has also been investigated. Contrary to the beneficial influence observed in related catalytic systems, iodine has a deleterious effect in the present case. Otherwise, aryl phosphoric acids produce a positive impact on catalyst activity without a decrease on enantioselectivity.

  13. An entry to a chiral dihydropyrazole scaffold: enantioselective [3 + 2] cycloaddition of nitrile imines.

    Science.gov (United States)

    Sibi, Mukund P; Stanley, Levi M; Jasperse, Craig P

    2005-06-15

    We have developed a versatile strategy to access dihydropyrazoles in highly enantioenriched form. Dipolar cycloaddition of electron-deficient acceptors and in situ-generated nitrile imines proceeds with high regio- and enantioselectivity using 10 mol % chiral Lewis acid catalyst. A variety of dihydropyrazoles that incorporate functionality for further manipulation have been prepared.

  14. Enantioselective Evans-Tishchenko Reduction of b-Hydroxyketone Catalyzed by Lithium Binaphtholate

    Directory of Open Access Journals (Sweden)

    Makoto Nakajima

    2011-06-01

    Full Text Available Lithium diphenylbinaphtholate catalyzed the enantioselective Evans-Tishchenko reduction of achiral b-hydroxyketones to afford monoacyl-protected 1,3-diols with high stereoselectivities. In the reaction of racemic b-hydroxyketones, kinetic optical resolution occurred in a highly stereoselective manner.

  15. Enantioselective Biotransformation of Chiral Persistent Organic Pollutants.

    Science.gov (United States)

    Zhang, Ying; Ye, Jing; Liu, Min

    2017-01-01

    Enantiomers of chiral compounds commonly undergo enantioselective transformation in most biologically mediated processes. As chiral persistent organic pollutants (POPs) are extensively distributed in the environment, differences between enantiomers in biotransformation should be carefully considered to obtain exact enrichment and specific health risks. This review provides an overview of in vivo biotransformation of chiral POPs currently indicated in the Stockholm Convention and their chiral metabolites. Peer-reviewed journal articles focused on the research question were thoroughly searched. A set of inclusion and exclusion criteria were developed to identify relevant studies. We mainly compared the results from different animal models under controlled laboratory conditions to show the difference between enantiomers in terms of distinct transformation potential. Interactions with enzymes involved in enantioselective biotransformation, especially cytochrome P450 (CYP), were discussed. Further research areas regarding this issue were proposed. Limited evidence for a few POPs has been found in 30 studies. Enantioselective biotransformation of α-hexachlorocyclohexane (α-HCH), chlordane, dichlorodiphenyltrichloroethane (DDT), heptachlor, hexabromocyclododecane (HBCD), polychlorinated biphenyls (PCBs), and toxaphene, has been investigated using laboratory mammal, fish, bird, and worm models. Tissue and excreta distributions, as well as bioaccumulation and elimination kinetics after administration of racemate and pure enantiomers, have been analyzed in these studies. Changes in enantiomeric fractions have been considered as an indicator of enantioselective biotransformation of chiral POPs in most studies. Results of different laboratory animal models revealed that chiral POP biotransformation is seriously affected by chirality. Pronounced results of species-, tissue-, gender-, and individual-dependent differences are observed in in vivo biotransformation of chiral POPs

  16. Influence of biochar on the enantioselective behavior of the chiral fungicide metalaxyl in soil

    Science.gov (United States)

    Gámiz, Beatriz; Pignatello, Joseph J.; Hermosín, María Carmen; Cox, Lucía; Celis, Rafael

    2015-04-01

    Chiral pesticides comprise an emerging and important class of organic pollutants currently, accounting for more than a quarter of used pesticides. Consequently, the contamination problems caused by chiral pesticides are concern matter and factors affecting enantioselective processes of chiral pesticides in soil need to be understood. For example, certain soil management practices, such as the use of organic amendments, can affect the enantioselective behavior of chiral pesticides in soils. Recently, biochar (BC), i.e. organic matter subjected to pyrolysis, has been proposed as organic amendment due to beneficial properties such as its high stability against decay in soil environments and its apparent ability to influence the availability of nutrients. BC is considered to be more biologically inert as compared to otherforms of organic carbon. However, its side-effects on the enantioselectivity of processes affecting the fate of chiral pesticides is unknown. The aim of this study was to assess the effect of biochar (BC) on the enantioselectivity of sorption, degradation, and leaching of the chiral fungicide metalaxyl in an agricultural soil. Amending the soil with BC (2% w/w) resulted in 3 times higher sorption of metalaxyl enantiomers compared to unamended soil, but no enantioselectivity in the process was observed. Moreover, both enantiomers showed some resistance to be desorbed in BC-amended soil compared to unamended soil. Dissipation studies revealed that the degradation of metalaxylwas more enantioselective in the unamended soil than in BC-amended soil. In unamended soil, R-metalaxyl(biologically active) and S- metalaxyl had half-lives (t1/2) of 3 and 34 days, respectively. BC enhanced the persistence of both enantiomers in the soil, with R-metalaxyl being degraded faster (t1/2=43 days) than S-metalaxyl (t1/2= 100 days). The leaching of both S-and R-metalaxyl was almost suppressed after amending the soil with BC; less than 10% of the fungicide applied to soil

  17. 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.

  18. Stereospecific nickel-catalyzed cross-coupling reactions of alkyl ethers: enantioselective synthesis of diarylethanes.

    Science.gov (United States)

    Taylor, Buck L H; Swift, Elizabeth C; Waetzig, Joshua D; Jarvo, Elizabeth R

    2011-01-26

    Secondary benzylic ethers undergo stereospecific substitution reactions with Grignard reagents in the presence of nickel catalysts. Reactions proceed with inversion of configuration and high stereochemical fidelity. This reaction allows for facile enantioselective synthesis of biologically active diarylethanes from readily available optically enriched carbinols.

  19. Iridium-Catalyzed Asymmetric Intramolecular Allylic Amidation : Enantioselective Synthesis of Chiral Tetrahydroisoquinolines and Saturated Nitrogen Heterocycles

    NARCIS (Netherlands)

    Teichert, Johannes F.; Fañanás-Mastral, Martín; Feringa, Bernard

    2011-01-01

    For the first time iridium catalysis has been used for the synthesis of chiral tetrahydroisoquinolines with excellent yields and high enantioselectivities (see scheme; cod=1,5-cyclooctadiene, DBU=1,8-diazabicyclo[5.4.0]undec-7-ene). These products are important chiral building blocks for the

  20. Combining silver- and organocatalysis: an enantioselective sequential catalytic approach towards pyrano-annulated pyrazoles.

    Science.gov (United States)

    Hack, Daniel; Chauhan, Pankaj; Deckers, Kristina; Mizutani, Yusuke; Raabe, Gerhard; Enders, Dieter

    2015-02-11

    A one-pot asymmetric Michael addition/hydroalkoxylation sequence, catalyzed by a sequential catalytic system consisting of a squaramide and a silver salt, provides a new series of chiral pyrano-annulated pyrazole derivatives in excellent yields (up to 95%) and high enantioselectivities (up to 97% ee).

  1. The Catalytic Enantioselective Total Synthesis of (+)-Liphagal

    KAUST Repository

    Day, Joshua J.

    2011-06-10

    Ring a ding: The meroterpenoid natural product (+)-liphagal has been synthesized enantioselectively in 19 steps from commercially available materials. The trans-homodecalin system was achieved by ring expansion followed by stereoselective hydrogenation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. The Catalytic Enantioselective Total Synthesis of (+)-Liphagal

    KAUST Repository

    Day, Joshua J.; McFadden, Ryan M.; Virgil, Scott C.; Kolding, Helene; Alleva, Jennifer L.; Stoltz, Brian M.

    2011-01-01

    Ring a ding: The meroterpenoid natural product (+)-liphagal has been synthesized enantioselectively in 19 steps from commercially available materials. The trans-homodecalin system was achieved by ring expansion followed by stereoselective hydrogenation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Enantioselective properties of induced lipases from Geotrichum

    Czech Academy of Sciences Publication Activity Database

    Zarevúcka, Marie; Kejík, Z.; Šaman, David; Wimmer, Zdeněk; Demnerová, K.

    2005-01-01

    Roč. 37, - (2005), s. 481-486 ISSN 0141-0229 R&D Projects: GA MŠk(CZ) OC D30.001; GA MŠk(CZ) OC D13.10 Institutional research plan: CEZ:AV0Z40550506 Keywords : Geotrichum * lipase * enantioselectivity Subject RIV: CC - Organic Chemistry Impact factor: 1.705, year: 2005

  4. Enantioselective pharmacokinetics of sibutramine in rat.

    Science.gov (United States)

    Noh, Keumhan; Bae, Kyoungjin; Min, Bokyoung; Kim, Eunyoung; Kwon, Kwang-il; Jeong, Taecheon; Kang, Wonku

    2010-02-01

    Racemic sibutramine is widely used to treat obesity owing to its inhibition of serotonin and noradrenaline reuptake in synapses. Although the enantioselective effects of sibutramine and its two active desmethyl-metabolites, monodesmethylsibutramine (MDS) and didesmethylsibutramine (DDS), on anorexia and energy expenditure have been elucidated, the enantioselective pharmacokinetics of sibutramine are still unclear. Therefore, we aimed to characterize the enantioselective pharmacokinetics of sibutramine and its metabolites in plasma and urine following an intravenous and a single oral administration of sibutramine in rats. The absolute bioavailability of sibutramine was only about 7%. The pharmacologically less effective S-isomer of DDS was predominant in the plasma: the C ( max ) and the AUC ( inf ) were 28 and 30 times higher than those of the R-isomer, respectively (psibutramine metabolites MDS and DDS were present at lower concentrations, owing to their rapid biotransformation to hydroxylated and/or carbamoylglucuronized forms and their faster excretion in the urine. The present study is the first to elucidate the enantioselective pharmacokinetics of sibutramine in rats.

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

    KAUST Repository

    Lee, Richmond; Zhong, Fangrui; Zheng, Bin; Meng, Yuezhong; Lu, Yixin; Huang, Kuo-Wei

    2013-01-01

    in inducing a high degree of stereochemical control in both the enolate addition to imine and the subsequent proton transfer step, affording aza-MBH reactions with excellent enantioselectivity. © 2013 The Royal Society of Chemistry.

  6. Análise enantiosseletiva de fármacos: contribuições da cromatografia líquida de alta eficiência e eletroforese capilar Enantioselective analysis of drugs: contributions of high-performance liquid chromatography and capillary electrophoresis

    Directory of Open Access Journals (Sweden)

    Pierina Sueli Bonato

    2005-08-01

    Full Text Available The demand for analytical methods suitable for accurate and reproducible determination of drug enantiomers has increased significantly in the last years. High-performance liquid chromatography (HPLC using chiral stationary phases and capillary electrophoresis (CE are the most important techniques used for this purpose. In this paper, the fundamental aspects of chiral separations using both techniques are presented. Some important aspects for the development of enantioselective methods, particularly for the analysis of drugs and metabolites in biological samples, are also discussed.

  7. Future directions for high-spin studies

    International Nuclear Information System (INIS)

    Stephens, F.S.

    1982-11-01

    Some future directions for experimental high-spin studies are discussed, concentrating mainly on the region above I -- 30h, where the γ-ray spectra are currently unresolvable. The 4π NaI balls offer a means to exploit the temperature effects recently shown to exist in such spectra. Large arrays of Compton-suppressed Ge detectors, on the other and, lead to higher effective resolution as it becomes possible to study triple and quadruple coincident events

  8. Enantioselectivity in environmental risk assessment of modern chiral pesticides

    International Nuclear Information System (INIS)

    Ye Jing; Zhao Meirong; Liu Jing; Liu Weiping

    2010-01-01

    Chiral pesticides comprise a new and important class of environmental pollutants nowadays. With the development of industry, more and more chiral pesticides will be introduced into the market. But their enantioselective ecotoxicology is not clear. Currently used synthetic pyrethroids, organophosphates, acylanilides, phenoxypropanoic acids and imidazolinones often behave enantioselectively in agriculture use and they always pose unpredictable enantioselective ecological risks on non-target organisms or human. It is necessary to explore the enantioselective toxicology and ecological fate of these chiral pesticides in environmental risk assessment. The enantioselective toxicology and the fate of these currently widely used pesticides have been discussed in this review article. - Chiral pesticides could pose unpredictable enantioselective toxicity on non-target organisms.

  9. Diastereoselective and enantioselective reduction of tetralin-1,4-dione

    Directory of Open Access Journals (Sweden)

    2008-10-01

    Full Text Available BackgroundThe chemistry of tetralin-1,4-dione, the stable tautomer of 1,4-dihydroxynaphthalene, has not been explored previously. It is readily accessible and offers interesting opportunities for synthesis.ResultsThe title reactions were explored. L-Selectride reduced the diketone to give preferentially the cis-diol (d.r. 84 : 16. Red-Al gave preferentially the trans-diol (d.r. 13 : 87. NaBH4, LiAlH4, and BH3 gave lower diastereoselectivities (yields: 76–98%. Fractional crystallization allowed isolation of the cis-diol and the trans-diol (55% and 66% yield, respectively. Borane was used to cleanly give the mono-reduction product. Highly enantioselective CBS reductions afforded the trans-diol (72% yield, 99% ee and the mono-reduction product (81%, 95% ee.ConclusionDiastereoselective and enantioselective reductions of the unexplored tetralin-1,4-dione provides a very convenient entry into a number of synthetically highly attractive 1,4-tetralindiols and 4-hydroxy-1-tetralone.

  10. Diastereoselective and enantioselective reduction of tetralin-1,4-dione.

    Science.gov (United States)

    Kündig, E Peter; Enriquez-Garcia, Alvaro

    2008-01-01

    The chemistry of tetralin-1,4-dione, the stable tautomer of 1,4-dihydroxynaphthalene, has not been explored previously. It is readily accessible and offers interesting opportunities for synthesis. The title reactions were explored. L-Selectride reduced the diketone to give preferentially the cis-diol (d.r. 84 : 16). Red-Al gave preferentially the trans-diol (d.r. 13 : 87). NaBH(4), LiAlH(4), and BH(3) gave lower diastereoselectivities (yields: 76-98%). Fractional crystallization allowed isolation of the cis-diol and the trans-diol (55% and 66% yield, respectively). Borane was used to cleanly give the mono-reduction product. Highly enantioselective CBS reductions afforded the trans-diol (72% yield, 99% ee) and the mono-reduction product (81%, 95% ee). Diastereoselective and enantioselective reductions of the unexplored tetralin-1,4-dione provides a very convenient entry into a number of synthetically highly attractive 1,4-tetralindiols and 4-hydroxy-1-tetralone.

  11. Ultra-high temperature direct propulsion

    International Nuclear Information System (INIS)

    Araj, K.J.; Slovik, G.; Powell, J.R.; Ludewig, H.

    1987-01-01

    Potential advantages of ultra-high exhaust temperature (3000 K - 4000 K) direct propulsion nuclear rockets are explored. Modifications to the Particle Bed Reactor (PBR) to achieve these temperatures are described. Benefits of ultra-high temperature propulsion are discussed for two missions - orbit transfer (ΔV = 5546 m/s) and interplanetary exploration (ΔV = 20000 m/s). For such missions ultra-high temperatures appear to be worth the additional complexity. Thrust levels are reduced substantially for a given power level, due to the higher enthalpy caused by partial disassociation of the hydrogen propellant. Though technically challenging, it appears potentially feasible to achieve such ultra high temperatures using the PBR

  12. A general enantioselective route to the chamigrene natural product family

    KAUST Repository

    White, David E.

    2010-06-01

    Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

  13. A general enantioselective route to the chamigrene natural product family

    KAUST Repository

    White, David E.; Stewart, Ian C.; Seashore-Ludlow, Brinton A.; Grubbs, Robert H.; Stoltz, Brian M.

    2010-01-01

    Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

  14. Chiral separation and enantioselective degradation of vinclozolin in soils.

    Science.gov (United States)

    Liu, Hui; Liu, Donghui; Shen, Zhigang; Sun, Mingjing; Zhou, Zhiqiang; Wang, Peng

    2014-03-01

    Vinclozolin is a chiral fungicide with potential environmental problems. The chiral separation of the enantiomers and enantioselective degradation in soil were investigated in this work. The enantiomers were separated by high-performance liquid chromatography (HPLC) on Chiralpak IA, IB, and AZ-H chiral columns under normal phase and the influence of the mobile phase composition on the separation was also studied. Complete resolutions were obtained on all three chiral columns under optimized conditions with the same elution order of (+)/(-). The residual analysis of the enantiomers in soil was conducted using accelerate solvent extraction followed by HPLC determination. The recoveries of the enantiomers ranged from 85.7-105.7% with relative standard deviation (SD) of 0.12-3.83%, and the limit of detection (LOD) of the method was 0.013 µg/g. The results showed that the degradations of vinclozolin enantiomers in the soils followed first-order kinetics. Preferential degradation of the (-)-enantiomer was observed only in one soil with the largest |ES| value of 0.047, and no obvious enantioselective degradation was observed in other soils. It was found that the persistence of vinclozolin in soil was related to pH values based on the half-lives. The two enantiomers disappeared about 8 times faster in basic soils than that in neutral or acidic soils. © 2014 Wiley Periodicals, Inc.

  15. Regio-, Diastereo-, and Enantioselective Nitroso-Diels-Alder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids.

    Science.gov (United States)

    Pous, Jonathan; Courant, Thibaut; Bernadat, Guillaume; Iorga, Bogdan I; Blanchard, Florent; Masson, Géraldine

    2015-09-23

    Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.

  16. Vancomycin Molecular Interactions: Antibiotic and Enantioselective Mechanisms

    Science.gov (United States)

    Ward, Timothy J.; Gilmore, Aprile; Ward, Karen; Vowell, Courtney

    Medical studies established that vancomycin and other related macrocyclic antibiotics have an enhanced antimicrobial activity when they are associated as dimers. The carbohydrate units attached to the vancomycin basket have an essential role in the dimerization reaction. Covalently synthesized dimers were found active against vancomycin-resistant bacterial strains. A great similarity between antibiotic potential and enantioselectivity was established. A covalent vancomycin dimer was studied in capillary electrophoresis producing excellent chiral separation of dansyl amino acids. Balhimycin is a macrocyclic glycopeptide structurally similar to vancomycin. The small differences are, however, responsible for drastic differences in enantioselectivity in the same experimental conditions. Contributions from studies examining vancomycin's mechanism for antimicrobial activity have substantially aided our understanding of its mechanism in chiral recognition.

  17. High Pressure Diels Alder Reactions of 1-Vinyl-2,2,6-trimethylcyclohexene Catalyzed by Chiral Lewis Acids; An Enantioselective Route to a Drimane Sesquiterpene Precursor.

    NARCIS (Netherlands)

    Knol, Joop; Meetsma, Auke; Feringa, Bernard

    1995-01-01

    The Diels Alder reaction of 1-vinyl-2,2,6-trimethylcyclohexene and 3-((E)-3-(methoxycarbonyl)propenoyl)-1,3-oxazolidin-2-one under high pressure, catalyzed by a chiral bis-imine copper(II) complex, yields a drimane sesquiterpene precursor in a highly regio- and diastereoselective manner with

  18. Continuous-flow enantioselective α-aminoxylation of aldehydes catalyzed by a polystyrene-immobilized hydroxyproline

    Directory of Open Access Journals (Sweden)

    Xacobe C. Cambeiro

    2011-10-01

    Full Text Available The application of polystyrene-immobilized proline-based catalysts in packed-bed reactors for the continuous-flow, direct, enantioselective α-aminoxylation of aldehydes is described. The system allows the easy preparation of a series of β-aminoxy alcohols (after a reductive workup with excellent optical purity and with an effective catalyst loading of ca. 2.5% (four-fold reduction compared to the batch process working at residence times of ca. 5 min.

  19. Fluxional additives: a second generation control in enantioselective catalysis.

    Science.gov (United States)

    Sibi, Mukund P; Manyem, Shankar; Palencia, Hector

    2006-10-25

    The concept of "fluxional additives", additives that can adopt enantiomeric conformations depending on the chiral information in the ligand, is demonstrated in enantioselective Diels-Alder and nitrone cycloaddition reactions. The additive design is modular, and diverse structures are accessible in three steps. Chiral Lewis acids from main group and transition metals show enhancements in enantioselectivity in the presence of these additives.

  20. Tin-free enantioselective radical reactions using silanes.

    Science.gov (United States)

    Sibi, Mukund P; Yang, Yong-Hua; Lee, Sunggi

    2008-12-04

    Readily available hexyl silane is an excellent choice as a H-atom donor and a chain carrier in Lewis acid mediated enantioselective radical reactions. Conjugate radical additions to alpha,beta-unsaturated imides at room temperature proceed in good yields and excellent enantioselectivities.

  1. Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system.

    Science.gov (United States)

    Huang, Xiaoqiang; Luo, Shipeng; Burghaus, Olaf; Webster, Richard D; Harms, Klaus; Meggers, Eric

    2017-10-01

    We report an unusual reaction design in which a chiral bis-cyclometalated rhodium(iii) complex enables the stereocontrolled chemistry of photo-generated carbon-centered radicals and at the same time catalyzes an enantioselective sulfonyl radical addition to an alkene. Specifically, employing inexpensive and readily available Hantzsch esters as the photoredox mediator, Rh-coordinated prochiral radicals generated by a selective photoinduced single electron reduction are trapped by allyl sulfones in a highly stereocontrolled fashion, providing radical allylation products with up to 97% ee. The hereby formed fragmented sulfonyl radicals are utilized via an enantioselective radical addition to form chiral sulfones, which minimizes waste generation.

  2. Phytotoxicity of chiral herbicide bromacil: Enantioselectivity of photosynthesis in Arabidopsis thaliana

    International Nuclear Information System (INIS)

    Chen, Zunwei; Zou, Yuqin; Wang, Jia; Li, Meichao; Wen, Yuezhong

    2016-01-01

    With the wide application of chiral herbicides and the frequent detection of photosystem II (PSII) herbicides, it is of great importance to assess the direct effects of PSII herbicides on photosynthesis in an enantiomeric level. In the present study, the enantioselective phytotoxicity of bromacil (BRO), typical photosynthesis inhibition herbicide, on Arabidopsis thaliana was investigated. The results showed that S-BRO exhibited a greater inhibition of electron transmission in photosystem I (PSI) of A. thaliana than R-BRO by inhibiting the transcription of fnr 1. S-BRO also changed the chlorophyll fluorescence parameters Y (II), Y (NO), and Y (NPQ) to a greater extent than R-Bro. Transcription of genes psbO2, Lhcb3 and Lhcb6 was down-regulated in an enantioselective rhythm and S-BRO caused more serious influence, indicating that S-BRO did worse damage to the photosystem II (PSII) of A. thaliana than R-BRO. This study suggested that S-BRO disturbed the photosynthesis of plants to a larger extent than R-BRO and provided a new sight to evaluate the phytotoxicity of chiral herbicides. - Highlights: • It is necessary to assess the direct effects of PSII herbicides on photosynthesis. • Phytotoxicity of bromacil is investigated in an enantiomeric level. • Bromacil disturbed enantioselectively the photosystem II of Arabidopsis thaliana. • S-bromacil caused severer damage to photosynthesis of Arabidopsis than R-bromacil. • Photosynthesis should be considered for phytotoxicity assessment of herbicides.

  3. Phytotoxicity of chiral herbicide bromacil: Enantioselectivity of photosynthesis in Arabidopsis thaliana

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Zunwei; Zou, Yuqin; Wang, Jia [MOE Key Laboratory of Environmental Remediation & Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Li, Meichao [Research Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310032 (China); Wen, Yuezhong, E-mail: wenyuezhong@zju.edu.cn [MOE Key Laboratory of Environmental Remediation & Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China)

    2016-04-01

    With the wide application of chiral herbicides and the frequent detection of photosystem II (PSII) herbicides, it is of great importance to assess the direct effects of PSII herbicides on photosynthesis in an enantiomeric level. In the present study, the enantioselective phytotoxicity of bromacil (BRO), typical photosynthesis inhibition herbicide, on Arabidopsis thaliana was investigated. The results showed that S-BRO exhibited a greater inhibition of electron transmission in photosystem I (PSI) of A. thaliana than R-BRO by inhibiting the transcription of fnr 1. S-BRO also changed the chlorophyll fluorescence parameters Y (II), Y (NO), and Y (NPQ) to a greater extent than R-Bro. Transcription of genes psbO2, Lhcb3 and Lhcb6 was down-regulated in an enantioselective rhythm and S-BRO caused more serious influence, indicating that S-BRO did worse damage to the photosystem II (PSII) of A. thaliana than R-BRO. This study suggested that S-BRO disturbed the photosynthesis of plants to a larger extent than R-BRO and provided a new sight to evaluate the phytotoxicity of chiral herbicides. - Highlights: • It is necessary to assess the direct effects of PSII herbicides on photosynthesis. • Phytotoxicity of bromacil is investigated in an enantiomeric level. • Bromacil disturbed enantioselectively the photosystem II of Arabidopsis thaliana. • S-bromacil caused severer damage to photosynthesis of Arabidopsis than R-bromacil. • Photosynthesis should be considered for phytotoxicity assessment of herbicides.

  4. Enantioselective organo-photocatalysis mediated by atropisomeric thiourea derivatives.

    Science.gov (United States)

    Vallavoju, Nandini; Selvakumar, Sermadurai; Jockusch, Steffen; Sibi, Mukund P; Sivaguru, Jayaraman

    2014-05-26

    Can photocatalysis be performed without electron or energy transfer? To address this, organo-photocatalysts that are based on atropisomeric thioureas and display lower excited-state energies than the reactive substrates have been developed. These photocatalysts were found to be efficient in promoting the [2+2] photocycloaddition of 4-alkenyl-substituted coumarins, which led to the corresponding products with high enantioselectivity (77-96% ee) at low catalyst loading (1-10 mol%). The photocatalytic cycle proceeds by energy sharing via the formation of both static and dynamic complexes (exciplex formation), which is aided by hydrogen bonding. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Enantioselective bioaccumulation of diniconazole in Tenebrio molitor larvae.

    Science.gov (United States)

    Liu, Chen; LV, Xiao Tian; Zhu, Wen Xue; QU, Hao Yang; Gao, Yong Xin; Guo, Bao Yuan; Wang, Hui Li

    2013-12-01

    The enantioselective bioaccumulation of diniconazole in Tenebrio molitor Linne larva was investigated with liquid chromatography tandem mass spectrometry based on the ChiralcelOD-3R[cellulose tri-(3,5-dimethylphenyl carbamate)] column. In this study we documented the effects of dietary supplementation with wheat bran contaminated by racemic diniconazole at two dose levels of 20 mg kg(-1) and 2 mg kg(-1) (dry weight) in Tenebrio molitor. The results showed that both doses of diniconazole were taken up by Tenebrio molitor rapidly in the first few days, the concentrations of R-enantiomer and S-enantiomer at high doses reached the highest level of 0.55 mg kg(-1) and 0.48 mg kg(-1) , respectively, on the 1(st) d, and the concentrations of them obtained a maxima of 0.129 mg kg(-1) and 0.128 mg kg(-1) at low dose, respectively, on the 3(rd) d, which means that the concentration of diniconazole was proportional to the time of achieving the highest accumulated level. It afterwards attained equilibrium after a sharp decline at both 20 mg kg(-1) and 2 mg kg(-1) of diniconazole. The determination results from the feces of Tenebrio molitor demonstrated that the extraction recovery (ER) values of the high dose group were higher than that of the low dose group and the values were all above 1; therefore, it could be inferred that enantiomerization existed in Tenebrio molitor. Additionally, the biota accumulation factor was used to evaluate the bioaccumulation of diniconazole enantiomers, showing that the bioaccumulation of diniconazole in Tenebrio molitor was enantioselective with preferential accumulation of S-enantiomer. © 2013 Wiley Periodicals, Inc.

  6. Enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated esters.

    Science.gov (United States)

    Gammack Yamagata, Adam D; Datta, Swarup; Jackson, Kelvin E; Stegbauer, Linus; Paton, Robert S; Dixon, Darren J

    2015-04-13

    A new catalytic asymmetric desymmetrization reaction for the synthesis of enantioenriched derivatives of 2-azabicyclo[3.3.1]nonane, a key motif common to many alkaloids, has been developed. Employing a cyclohexanediamine-derived primary amine organocatalyst, a range of prochiral cyclohexanone derivatives possessing an α,β-unsaturated ester moiety linked to the 4-position afforded the bicyclic products, which possess three stereogenic centers, as single diastereoisomers in high enantioselectivity (83-99% ee) and in good yields (60-90%). Calculations revealed that stepwise C-C bond formation and proton transfer via a chair-shaped transition state dictate the exclusive endo selectivity and enabled the development of a highly enantioselective primary amine catalyst. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. High precision studies of directional correlations

    International Nuclear Information System (INIS)

    El-khosht, M.

    1980-01-01

    Two applications of the method of directional correlations are described. The first part deals with gamma-gamma directional correlations measurements. A total of 27 cascades have been studied in 97 Tc, 206 Pb and 206 Bi. Information is obtained on the angular momenta of levels, multipolarities of electromagnetic transitions and further, reduced transition probabilities. The later part of this thesis describes a determination of anisotropic directional correlation between gamma-rays and LX-rays in 160 Dy. To the authors' knowledge this is the first observation of an anisotropic correlation between gamma rays and X-rays following internal conversion. (Auth.)

  8. Lewis base catalyzed enantioselective allylic hydroxylation of Morita-Baylis-Hillman carbonates with water

    KAUST Repository

    Zhu, Bo

    2011-08-19

    A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using 18O-labeling experiments. © 2011 American Chemical Society.

  9. Enantioselective synthesis of the novel chiral sulfoxide derivative as a glycogen synthase kinase 3beta inhibitor.

    Science.gov (United States)

    Saitoh, Morihisa; Kunitomo, Jun; Kimura, Eiji; Yamano, Toru; Itoh, Fumio; Kori, Masakuni

    2010-09-01

    Glycogen synthase kinase 3beta (GSK-3beta) inhibitors are expected to be attractive therapeutic agents for the treatment of Alzheimer's disease (AD). Recently we discovered sulfoxides (S)-1 as a novel GSK-3beta inhibitor having in vivo efficacy. We investigated practical asymmetric preparation methods for the scale-up synthesis of (S)-1. The highly enantioselective synthesis of (S)-1 (94% ee) was achieved by titanium-mediated oxidation with D-(-)-diethyl tartrate on gram scale.

  10. Enantioselective copper-catalysed propargylic substitution: synthetic scope study and application in formal total syntheses of (+)-anisomycin and (-)-cytoxazone

    NARCIS (Netherlands)

    Detz, R.J.; Abiri, Z.; le Griel, R.; Hiemstra, H.; van Maarseveen, J.H.

    2011-01-01

    A copper catalyst with a chiral pyridine-2,6-bisoxazoline (pybox) ligand was used to convert a variety of propargylic esters with different side chains (R=Ar, Bn, alkyl) into their amine counterparts in very high yields and with good enantioselectivities (up to 90 % enantiomeric excess (ee)).

  11. Kinetic and dynamic kinetic resolution of secondary alcohols with ionic-surfactant-coated Burkholderia cepacia lipase: substrate scope and enantioselectivity.

    Science.gov (United States)

    Kim, Cheolwoo; Lee, Jusuk; Cho, Jeonghun; Oh, Yeonock; Choi, Yoon Kyung; Choi, Eunjeong; Park, Jaiwook; Kim, Mahn-Joo

    2013-03-15

    Forty-four different secondary alcohols, which can be classified into several types (II-IX), were tested as the substrates of ionic surfactant-coated Burkholderia cepacia lipase (ISCBCL) to see its substrate scope and enantioselectivity in kinetic and dynamic kinetic resolution (KR and DKR). They include 6 boron-containing alcohols, 24 chiral propargyl alcohols, and 14 diarylmethanols. The results from the studies on KR indicate that ISCBCL accepted most of them with high enantioselectivity at ambient temperature and with useful to high enantioselectivity at elevated temperatures. In particular, ISCBCL displayed high enantioselectivity toward sterically demanding secondary alcohols (types VIII and IX) which have two bulky substituents at the hydroxymethine center. DKR reactions were performed by the combination of ISCBCL with a ruthenium-based racemization catalyst at 25-60 °C. Forty-one secondary alcohols were tested for DKR. About half of them were transformed into their acetates of high enantiopurity (>90% ee) with good yields (>80%). It is concluded that ISCBCL appears to be a superb enzyme for the KR and DKR of secondary alcohols.

  12. Enantioselective construction of quaternary N-heterocycles by palladium-catalysed decarboxylative allylic alkylation of lactams

    KAUST Repository

    Behenna, Douglas C.

    2011-12-18

    The enantioselective synthesis of nitrogen-containing heterocycles (N-heterocycles) represents a substantial chemical research effort and resonates across numerous disciplines, including the total synthesis of natural products and medicinal chemistry. In this Article, we describe the highly enantioselective palladium-catalysed decarboxylative allylic alkylation of readily available lactams to form 3,3-disubstituted pyrrolidinones, piperidinones, caprolactams and structurally related lactams. Given the prevalence of quaternary N-heterocycles in biologically active alkaloids and pharmaceutical agents, we envisage that our method will provide a synthetic entry into the de novo asymmetric synthesis of such structures. As an entry for these investigations we demonstrate how the described catalysis affords enantiopure quaternary lactams that intercept synthetic intermediates previously used in the synthesis of the Aspidosperma alkaloids quebrachamine and rhazinilam, but that were previously only available by chiral auxiliary approaches or as racemic mixtures. © 2012 Macmillan Publishers Limited. All rights reserved.

  13. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui

    2018-02-05

    Axially chiral molecules are among the most valuable substrates in organic synthesis. They are typically used as chiral ligands or catalysts in asymmetric reactions. Recent progress for the construction of these chiral molecules is mainly focused on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a catalytic C–C bond formation occurs, providing axially chiral α-pyrone−aryls in moderate to good yields and with high enantioselectivities. Control experiments indicated that alkynyl acyl azoliums, acting as active intermediates, are employed to atroposelectively assemble chiral biaryls and such a methodology may be creatively applied to other useful NHC-catalyzed asymmetric transformations.

  14. Enantioselective cytotoxicity of the insecticide bifenthrin on a human amnion epithelial (FL) cell line

    International Nuclear Information System (INIS)

    Liu Huigang; Zhao Meirong; Zhang Cong; Ma Yun; Liu Weiping

    2008-01-01

    Synthetic pyrethroids (SPs) are used in preference to organochlorines and organophosphates due to their high efficiency, low toxicity to mammals, and ready biodegradability. Previous studies reported that enantioselective toxicity of SPs occurs in aquatic toxicity. Several studies have indicated that SPs could lead to oxidative damage in humans or animals which was associated with their toxic effects. Little is known about the differences in the effects of chronic toxicity induced by individual stereoisomers of chiral SPs. The present study was therefore undertaken to evaluate the enantioselectivity in cytotoxicity, genotoxicity caused by bifenthrin (BF) on human amnion epithelial (FL) cell lines and pesticidal activity on target organism. The cell proliferation and cytoflow analysis indicated that 1S-cis-BF presented more toxic effects than 1R-cis-BF above the concentration of 7.5 mg L -1 (p > 0.05). FL cells incubated with 1S-cis-BF exhibited a dose-dependent accumulation of intracellular reactive oxygen species (ROS). In the comet assay, the number of cells with damaged DNA incubated with 1S-cis-BF was more than that with 1R-cis-BF (p 50 values of enantiomer to the target pest on Pieris rapae L. show that 1R-cis-BF was 300 times more active than 1S-cis-BF. These results indicate that the enantioselective toxicity and activity of BF between non-target organism and target organism was reversal. These implications together suggest that assessment of the environmental safety and new pesticides development with chiral centers should consider enantioselectivity

  15. Enantioselective Characteristics and Montmorillonite-Mediated Removal Effects of α-Hexachlorocyclohexane in Laying Hens.

    Science.gov (United States)

    Liu, Xueke; Shen, Zhigang; Wang, Peng; Liu, Chang; Yao, Guojun; Zhou, Zhiqiang; Liu, Donghui

    2016-06-07

    α-Hexachlorocyclohexane (α-HCH) is a chiral organochlorine pesticide that is often ubiquitously detected in various environmental matrices and may be absorbed by the human body via food consumption, with serious detriments to human health. In this study, enantioselective degradation kinetics and residues of α-HCH in laying hens were investigated after a single dose of exposure to the pesticide, whereas enantioselectivity and residues of α-HCH in eggs, droppings, and various tissues were investigated after long-term exposure. Meanwhile, montmorillonite (MMT), a feed additive with high capacity of adsorption, was investigated for its ability to remove α-HCH from laying hens. Most non-brain tissues enantioselectively accumulated (-)-α-HCH, while (+)-α-HCH was preferentially accumulated in the brain. The enantiomer fractions (EFs) in most tissues gradually decreased, implying continuous depletion of (+)-α-HCH in laying hens. After 30 days of exposure and 31 days of elimination, the concentration of α-HCH in eggs and tissues of laying hens with MMT-containing feed was lower than that with MMT-free feed, indicating the removal effects of MMT for α-HCH in laying hens. The findings presented herein suggest that modified MMT may potentially be useful in reducing the enrichment of α-HCH in laying hens and eggs, thus lowering the risk of human intake of α-HCH.

  16. Exploiting nanospace for asymmetric catalysis: confinement of immobilized, single-site chiral catalysts enhances enantioselectivity.

    Science.gov (United States)

    Thomas, John Meurig; Raja, Robert

    2008-06-01

    In the mid-1990s, it became possible to prepare high-area silicas having pore diameters controllably adjustable in the range ca. 20-200 Å. Moreover, the inner walls of these nanoporous solids could be functionalized to yield single-site, chiral, catalytically active organometallic centers, the precise structures of which could be determined using in situ X-ray absorption and FTIR and multinuclear magic angle spinning (MAS) NMR spectroscopy. This approach opened up the prospect of performing heterogeneous enantioselective conversions in a novel manner, under the spatial restrictions imposed by the nanocavities within which the reactions occur. In particular, it suggested an alternative method for preparing pharmaceutically and agrochemically useful asymmetric products by capitalizing on the notion, initially tentatively perceived, that spatial confinement of prochiral reactants (and transition states formed at the chiral active center) would provide an altogether new method of boosting the enantioselectivity of the anchored chiral catalyst. Initially, we anchored chiral single-site heterogeneous catalysts to nanopores covalently via a ligand attached to Pd(II) or Rh(I) centers. Later, we employed a more convenient and cheaper electrostatic method, relying in part on strong hydrogen bonding. This Account provides many examples of these processes, encompassing hydrogenations, oxidations, and aminations. Of particular note is the facile synthesis from methyl benzoylformate of methyl mandelate, which is a precursor in the synthesis of pemoline, a stimulant of the central nervous system; our procedure offers several viable methods for reducing ketocarboxylic acids. In addition to relying on earlier (synchrotron-based) in situ techniques for characterizing catalysts, we have constructed experimental procedures involving robotically controlled catalytic reactors that allow the kinetics of conversion and enantioselectivity to be monitored continually, and we have access to

  17. Combinatorial library based engineering of Candida antarctica lipase A for enantioselective transacylation of sec-alcohols in organic solvent.

    Science.gov (United States)

    Wikmark, Ylva; Svedendahl Humble, Maria; Bäckvall, Jan-E

    2015-03-27

    A method for determining lipase enantioselectivity in the transacylation of sec-alcohols in organic solvent was developed. The method was applied to a model library of Candida antarctica lipase A (CalA) variants for improved enantioselectivity (E values) in the kinetic resolution of 1-phenylethanol in isooctane. A focused combinatorial gene library simultaneously targeting seven positions in the enzyme active site was designed. Enzyme variants were immobilized on nickel-coated 96-well microtiter plates through a histidine tag (His6-tag), screened for transacylation of 1-phenylethanol in isooctane, and analyzed by GC. The highest enantioselectivity was shown by the double mutant Y93L/L367I. This enzyme variant gave an E value of 100 (R), which is a dramatic improvement on the wild-type CalA (E=3). This variant also showed high to excellent enantioselectivity for other secondary alcohols tested. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

  18. Bidirectional enantioselective effects of the GABAB receptor agonist baclofen in two mouse models of excessive ethanol consumption.

    Science.gov (United States)

    Kasten, Chelsea R; Blasingame, Shelby N; Boehm, Stephen L

    2015-02-01

    The GABAB receptor agonist baclofen has been studied extensively in preclinical models of alcohol-use disorders, yet results on its efficacy have been uncertain. Racemic baclofen, which is used clinically, can be broken down into separate enantiomers of the drug. Baclofen has been shown to produce enantioselective effects in behavioral assays, including those modeling reflexive and sexual behavior. The current studies sought to characterize the enantioselective effects of baclofen in two separate models of ethanol consumption. The first was a Drinking-in-the-Dark procedure that provides "binge-like" ethanol access to mice by restricting access to a 2-h period, 3 h into the dark cycle. The second was a two-bottle choice procedure that utilized selectively bred High Alcohol Preferring 1 (HAP1) mice to model chronic ethanol access. HAP1 mice are selectively bred to consume pharmacologically relevant amounts of ethanol in a 24-h two-bottle choice paradigm. The results showed that baclofen yields enantioselective effects on ethanol intake in both models, and that these effects are bidirectional. Total ethanol intake was decreased by R(+)-baclofen, while total intake was increased by S(-)-baclofen in the binge-like and chronic drinking models. Whereas overall binge-like saccharin intake was significantly reduced by R(+)-baclofen, chronic intake was not significantly altered. S(-)-baclofen did not significantly alter saccharin intake. Neither enantiomer significantly affected locomotion during binge-like reinforcer consumption. Collectively, these results demonstrate that baclofen produces enantioselective effects on ethanol consumption. More importantly, the modulation of consumption is bidirectional. The opposing enantioselective effects may explain some of the variance seen in published baclofen literature. Copyright © 2015 Elsevier Inc. All rights reserved.

  19. The role of the achiral template in enantioselective transformations. Radical conjugate additions to alpha-methacrylates followed by hydrogen atom transfer.

    Science.gov (United States)

    Sibi, Mukund P; Sausker, Justin B

    2002-02-13

    We have evaluated various achiral templates (1a-g, 10, and 16) in conjunction with chiral Lewis acids in the conjugate addition of nucleophilic radicals to alpha-methacrylates followed by enantioselective H-atom transfer. Of these, a novel naphthosultam template (10) gave high enantioselectivity in the H-atom-transfer reactions with ee's up to 90%. A chiral Lewis acid derived from MgBr(2) and bisoxazoline (2) gave the highest selectivity in the enantioselective hydrogen-atom-transfer reactions. Non-C(2) symmetric oxazolines (20-25) have also been examined as ligands, and of these, compound 25 gave optimal results (87% yield and 80% ee). Insights into rotamer control in alpha-substituted acrylates and the critical role of the tetrahedral sulfone moiety in realizing high selectivity are discussed.

  20. A Tunable and Enantioselective Hetero-Diels-Alder Reaction Provides Access to Distinct Piperidinoyl Spirooxindoles.

    Science.gov (United States)

    Jayakumar, Samydurai; Louven, Kathrin; Strohmann, Carsten; Kumar, Kamal

    2017-12-11

    The active complexes of chiral N,N'-dioxide ligands with dysprosium and magnesium salts catalyze the hetero-Diels-Alder reaction between 2-aza-3-silyloxy-butadienes and alkylidene oxindoles to selectively form 3,3'- and 3,4'-piperidinoyl spirooxindoles, respectively, in very high yields and with excellent enantioselectivities. The exo-selective asymmetric cycloaddition successfully regaled the construction of sp 3 -rich and highly substituted natural-product-based spirooxindoles supporting many chiral centers, including contiguous all-carbon quaternary centers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Enantioselective N-Heterocyclic Carbene Catalysis via the Dienyl Acyl Azolium.

    Science.gov (United States)

    Gillard, Rachel M; Fernando, Jared E M; Lupton, David W

    2018-04-16

    Herein we report the enantioselective N-heterocyclic carbene catalyzed (4+2) annulation of the dienyl acyl azolium with enolates. The reaction exploits readily accessible acyl fluorides and TMS enol ethers to give a range of highly enantio- and diastereo-enriched cyclohexenes (most >97:3 er and >20:1 dr). The reaction was found to require high nucleophilicity NHC catalysts with mechanistic studies supporting a stepwise 1,6-addition/β-lactonization. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Copper(II)-catalyzed enantioselective hydrosilylation of halo-substituted alkyl aryl and heteroaryl ketones: asymmetric synthesis of (R)-fluoxetine and (S)-duloxetine.

    Science.gov (United States)

    Zhou, Ji-Ning; Fang, Qiang; Hu, Yi-Hu; Yang, Li-Yao; Wu, Fei-Fei; Xie, Lin-Jie; Wu, Jing; Li, Shijun

    2014-02-14

    A set of reaction conditions has been established to facilitate the non-precious copper-catalyzed enantioselective hydrosilylation of a number of structurally diverse β-, γ- or ε-halo-substituted alkyl aryl ketones and α-, β- or γ-halo-substituted alkyl heteroaryl ketones under air to afford a broad spectrum of halo alcohols in high yields and good to excellent enantioselectivities (up to 99% ee). The developed procedure has been successfully applied to the asymmetric synthesis of antidepressant drugs (R)-fluoxetine and (S)-duloxetine, which highlighted its synthetic utility.

  3. Application of a Heterogeneous Chiral Titanium Catalyst Derived from Silica-Supported 3-Aryl H8-BINOL to Enantioselective Alkylation and Arylation of Aldehydes.

    Science.gov (United States)

    Akai, Junichiro; Watanabe, Satoshi; Michikawa, Kumiko; Harada, Toshiro

    2017-07-07

    A 3-aryl H 8 -BINOL was grafted on the surface of silica gel using a hydrosilane derivative as a precursor, and the resulting silica-supported ligand (6 mol %) was employed in the enantioselective alkylation and arylation of aldehydes in the presence of Ti(O i Pr) 4 . The reactions using Et 2 Zn, Et 3 B, and aryl Grignard reagents all afforded the corresponding adducts in high enantioselectivities and yields. The silica-immobilized titanium catalyst could be reused up to 14 times without appreciable deterioration of the activity.

  4. Rhodium-Catalyzed Asymmetric N-H Functionalization of Quinazolinones with Allenes and Allylic Carbonates: The First Enantioselective Formal Total Synthesis of (-)-Chaetominine.

    Science.gov (United States)

    Zhou, Yirong; Breit, Bernhard

    2017-12-22

    An unprecedented asymmetric N-H functionalization of quinazolinones with allenes and allylic carbonates was successfully achieved by rhodium catalysis with the assistance of chiral bidentate diphosphine ligands. The high efficiency and practicality of this method was demonstrated by a low catalyst loading of 1 mol % as well as excellent chemo-, regio-, and enantioselectivities with broad functional group compatibility. Furthermore, this newly developed strategy was applied as key step in the first enantioselective formal total synthesis of (-)-chaetominine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. An ylide transformation of rhodium(I) carbene: enantioselective three-component reaction through trapping of rhodium(I)-associated ammonium ylides by β-nitroacrylates.

    Science.gov (United States)

    Ma, Xiaochu; Jiang, Jun; Lv, Siying; Yao, Wenfeng; Yang, Yang; Liu, Shunying; Xia, Fei; Hu, Wenhao

    2014-11-24

    The chiral Rh(I)-diene-catalyzed asymmetric three-component reaction of aryldiazoacetates, aromatic amines, and β-nitroacrylates was achieved to obtain γ-nitro-α-amino-succinates in good yields and with high diastereo- and enantioselectivity. This reaction is proposed to proceed through the enantioselective trapping of Rh(I)-associated ammonium ylides by nitroacrylates. This new transformation represents the first example of Rh(I)-carbene-induced ylide transformation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Enantioselective epoxidation with chiral MN(III)(salen) catalysts: kinetic resolution of aryl-substituted allylic alcohols.

    Science.gov (United States)

    Adam, W; Humpf, H U; Roschmann, K J; Saha-Möller, C R

    2001-08-24

    A set of aryl-substituted allylic alcohols rac-2 has been epoxidized by chiral Mn(salen*) complexes 1 as the catalyst and iodosyl benzene (PhIO) as the oxygen source. Whereas one enantiomer of the allylic alcohol 2 is preferentially epoxidized to give the threo- or cis-epoxy alcohol 3 (up to 80% ee) as the main product (dr up to >95:5), the other enantiomer of 2 is enriched (up to 53% ee). In the case of 1,1-dimethyl-1,2-dihydronaphthalen-2-ol (2c), the CH oxidation to the enone 4c proceeds enantioselectively and competes with the epoxidation. The absolute configurations of the allylic alcohols 2 and their epoxides 3 have been determined by chemical correlation or CD spectroscopy. The observed diastereo- and enantioselectivities in the epoxidation reactions are rationalized in terms of a beneficial interplay between the hydroxy-directing effect and the attack along the Katsuki trajectory.

  7. 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.

  8. Regio- and Enantioselective N-Allylations of Imidazole, Benzimidazole, and Purine Heterocycles Catalyzed by Single-Component Metallacyclic Iridium Complexes

    Science.gov (United States)

    Stanley, Levi M.

    2010-01-01

    Highly regio- and enantioselective iridium-catalyzed N-allylations of benzimidazoles, imidazoles, and purines have been developed. N-Allylated benzimidazoles and imidazoles were isolated in high yields (up to 97%) with high branched-to-linear selectivity (up to 99:1) and enantioselectivity (up to 98% ee) from the reactions of benzimidazole and imidazole nucleophiles with unsymmetrical allylic carbonates in the presence of single component, ethylene-bound, metallacyclic iridium catalysts. N-Allylated purines were also obtained in high yields (up to 91%) with high N9:N7 selectivity (up to 96:4), high branched-to-linear selectivity (98:2), and high enantioselectivity (up to 98% ee) under similar conditions. The reactions encompass a range of benzimidazole, imidazole, and purine nucleophiles, as well as a variety of unsymmetrical aryl, heteroaryl, and aliphatic allylic carbonates. Competition experiments between common amine nucleophiles and the heterocyclic nitrogen nucleophiles studied in this work illustrate the effect of nucleophile pKa on the rate of iridium-catalyzed N-allylation reactions. Kinetic studies on the allylation of benzimidazole catalyzed by metallacyclic iridium-phosphoramidite complexes, in combination with studies on the deactivation of these catalysts in the presence of heterocyclic nucleophiles, provide insight into the effects of the structure of the phosphoramidite ligands on the stability of the metallacyclic catalysts. The data obtained from these studies has led to the development of N-allylations of benzimidazoles and imidazoles in the absence of an exogenous base. PMID:19480431

  9. Application of 7-azaisatins in enantioselective Morita–Baylis–Hillman reaction

    Directory of Open Access Journals (Sweden)

    Qing He

    2016-02-01

    Full Text Available 7-Azaisatin and 7-azaoxindole skeletons are valuable building blocks in diverse biologically active substances. Here 7-azaisatins turned out to be more efficient electrophiles than the analogous isatins in the enantioselective Morita–Baylis–Hillman (MBH reactions with maleimides using a bifunctional tertiary amine, β-isocupreidine (β-ICD, as the catalyst. This route allows a convenient approach to access multifunctional 3-hydroxy-7-aza-2-oxindoles with high enantiopurity (up to 94% ee. Other types of activated alkenes, such as acrylates and acrolein, could also be efficiently utilized.

  10. High Torque, Direct Drive Electric Motor, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — Bear Engineering proposes to advance the development of an innovative high torque, low speed, direct drive motor in order to meet NASA's requirements for such...

  11. High Torque, Direct Drive Electric Motor, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Bear Engineering proposes to develop an innovative high torque, low speed, direct drive motor in order to meet NASA's requirements for such devices. Fundamentally,...

  12. A Simple Primary Amine Catalyst for Enantioselective α-Hydroxylations and α-Fluorinations of Branched Aldehydes

    OpenAIRE

    Witten, Michael R.; Jacobsen, Eric N.

    2015-01-01

    A new primary amine catalyst for the asymmetric α-hydroxylation and α-fluorination of α-branched aldehydes is described. The products of the title transformations are generated in excellent yields and with high enantioselectivities. Both processes can be performed within short reaction times and on gram scale. The similarity in the results obtained in both reactions, combined with computational evidence, implies a common basis for stereoinduction and the possibility of a general catalytic mec...

  13. Sequential rhodium/palladium catalysis: enantioselective formation of dihydroquinolinones in the presence of achiral and chiral ligands.

    Science.gov (United States)

    Zhang, Lei; Qureshi, Zafar; Sonaglia, Lorenzo; Lautens, Mark

    2014-12-08

    Compatible combinations of achiral and chiral ligands can be used in rhodium/palladium catalysis to achieve highly enantioselective domino reactions. The difference in rates of catalysis and minimal effects of ligand interference confer control in the domino sequence. The "all-in-one" 1,4-conjugate arylation and C-N cross-coupling through sequential Rh/Pd catalysis provides access to enantioenriched dihydroquinolinone building blocks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Thermostable Alcohol Dehydrogenase from Thermococcus kodakarensis KOD1 for Enantioselective Bioconversion of Aromatic Secondary Alcohols

    Science.gov (United States)

    Wu, Xi; Zhang, Chong; Orita, Izumi; Imanaka, Tadayuki

    2013-01-01

    A novel thermostable alcohol dehydrogenase (ADH) showing activity toward aromatic secondary alcohols was identified from the hyperthermophilic archaeon Thermococcus kodakarensis KOD1 (TkADH). The gene, tk0845, which encodes an aldo-keto reductase, was heterologously expressed in Escherichia coli. The enzyme was found to be a monomer with a molecular mass of 31 kDa. It was highly thermostable with an optimal temperature of 90°C and a half-life of 4.5 h at 95°C. The apparent Km values for the cofactors NAD(P)+ and NADPH were similar within a range of 66 to 127 μM. TkADH preferred secondary alcohols and accepted various ketones and aldehydes as substrates. Interestingly, the enzyme could oxidize 1-phenylethanol and its derivatives having substituents at the meta and para positions with high enantioselectivity, yielding the corresponding (R)-alcohols with optical purities of greater than 99.8% enantiomeric excess (ee). TkADH could also reduce 2,2,2-trifluoroacetophenone to (R)-2,2,2-trifluoro-1-phenylethanol with high enantioselectivity (>99.6% ee). Furthermore, the enzyme showed high resistance to organic solvents and was particularly highly active in the presence of H2O–20% 2-propanol and H2O–50% n-hexane or n-octane. This ADH is expected to be a useful tool for the production of aromatic chiral alcohols. PMID:23354700

  15. Direct drive digital servo press with high parallel control

    Science.gov (United States)

    Murata, Chikara; Yabe, Jun; Endou, Junichi; Hasegawa, Kiyoshi

    2013-12-01

    Direct drive digital servo press has been developed as the university-industry joint research and development since 1998. On the basis of this result, 4-axes direct drive digital servo press has been developed and in the market on April of 2002. This servo press is composed of 1 slide supported by 4 ball screws and each axis has linearscale measuring the position of each axis with high accuracy less than μm order level. Each axis is controlled independently by servo motor and feedback system. This system can keep high level parallelism and high accuracy even with high eccentric load. Furthermore the 'full stroke full power' is obtained by using ball screws. Using these features, new various types of press forming and stamping have been obtained by development and production. The new stamping and forming methods are introduced and 'manufacturing' need strategy of press forming with high added value and also the future direction of press forming are also introduced.

  16. Enantioselective cycloadditions with alpha,beta-disubstituted acrylimides.

    Science.gov (United States)

    Sibi, Mukund P; Ma, Zhihua; Itoh, Kennosuke; Prabagaran, Narayanasamy; Jasperse, Craig P

    2005-06-09

    [reaction: see text] The use of N-H imide templates provides a solution to the problem of rotamer control in Lewis acid catalyzed reactions of alpha,beta-disubstituted acryloyl imides. Reactions proceed through the s-cis rotamer and with improved reactivity because A(1,3) strain is avoided. Enantioselective nitrone, nitrile oxide, and Diels-Alder cycloadditions demonstrate the principle.

  17. Lanthanide Lewis acid-mediated enantioselective conjugate radical additions.

    Science.gov (United States)

    Sibi, Mukund P; Manyem, Shankar

    2002-08-22

    [reaction: see text] Lanthanide triflates along with proline-derived ligands have been found to be efficient catalysts for enantioselective conjugate addition of nucleophilic radicals to enoates. N-Acyl oxazolidinones, when used as achiral additives, gave meaningful enhancements in the ees for the product.

  18. Enantioselective potential of polysaccharide-based chiral stationary phases in supercritical fluid chromatography.

    Science.gov (United States)

    Kucerova, Gabriela; Kalikova, Kveta; Tesarova, Eva

    2017-06-01

    The enantioselective potential of two polysaccharide-based chiral stationary phases for analysis of chiral structurally diverse biologically active compounds was evaluated in supercritical fluid chromatography using a set of 52 analytes. The chiral selectors immobilized on 2.5 μm silica particles were tris-(3,5-dimethylphenylcarmabate) derivatives of cellulose or amylose. The influence of the polysaccharide backbone, different organic modifiers, and different mobile phase additives on retention and enantioseparation was monitored. Conditions for fast baseline enantioseparation were found for the majority of the compounds. The success rate of baseline and partial enantioseparation with cellulose-based chiral stationary phase was 51.9% and 15.4%, respectively. Using amylose-based chiral stationary phase we obtained 76.9% of baseline enantioseparations and 9.6% of partial enantioseparations of the tested compounds. The best results on cellulose-based chiral stationary phase were achieved particularly with propane-2-ol and a mixture of isopropylamine and trifluoroacetic acid as organic modifier and additive to CO 2 , respectively. Methanol and basic additive isopropylamine were preferred on amylose-based chiral stationary phase. The complementary enantioselectivity of the cellulose- and amylose-based chiral stationary phases allows separation of the majority of the tested structurally different compounds. Separation systems were found to be directly applicable for analyses of biologically active compounds of interest. © 2017 Wiley Periodicals, Inc.

  19. Graphene-based hybrid for enantioselective sensing applications.

    Science.gov (United States)

    Zor, Erhan; Morales-Narváez, Eden; Alpaydin, Sabri; Bingol, Haluk; Ersoz, Mustafa; Merkoçi, Arben

    2017-01-15

    Chirality is a major field of research of chemical biology and is essential in pharmacology. Accordingly, approaches for distinguishing between different chiral forms of a compound are of great interest. We report on an efficient and generic enantioselective sensor that is achieved by coupling reduced graphene oxide with γ-cyclodextrin (rGO/γ-CD). The enantioselective sensing capability of the resulting structure was operated in both electrical and optical mode for of tryptophan enantiomers (D-/L-Trp). In this sense, voltammetric and photoluminescence measurements were conducted and the experimental results were compared to molecular docking method. We gain insight into the occurring recognition mechanism with selectivity toward D- and L-Trp as shown in voltammetric, photoluminescence and molecular docking responses. As an enantioselective solid phase on an electrochemical transducer, thanks to the different dimensional interaction of enantiomers with hybrid material, a discrepancy occurs in the Gibbs free energy leading to a difference in oxidation peak potential as observed in electrochemical measurements. The optical sensing principle is based on the energy transfer phenomenon that occurs between photoexcited D-/L-Trp enantiomers and rGO/γ-CD giving rise to an enantioselective photoluminescence quenching due to the tendency of chiral enantiomers to form complexes with γ-CD in different molecular orientations as demonstrated by molecular docking studies. The approach, which is the first demonstration of applicability of molecular docking to show both enantioselective electrochemical and photoluminescence quenching capabilities of a graphene-related hybrid material, is truly new and may have broad interest in combination of experimental and computational methods for enantiosensing of chiral molecules. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Asymmetric Construction of Benzindoloquinolizidine: Application of An Organocatalytic Enantioselective Conjugate Addition-Cyclization Cascade Reaction

    International Nuclear Information System (INIS)

    Kim, Cheolwoong; Seo, Seung Woo; Lee, Yona; Kim, Sunggon

    2014-01-01

    We have developed the synthetic methodology of enantioenriched benzindoloquinolizidines based on the organocatalytic enantioselective conjugate addition-cyclization cascade reaction of o-N-(3-indoleacetyl)amino-cinnamaldehydes with malonates followed by an acid-catalyzed intramolecular Pictet-Spengler type cyclization. The asymmetric reaction using diphenylprolinol TMS ether as an organocatalyst produces the desired products with good to excellent yields and high enantioselectivities (up to 98% ee). The evaluation of the applications of this synthetic methodology for generating enantioenriched benzindolo-quinolizidines and studies on the biological activity of these compounds against human prostate cancer in particular are now in progress. Results of these studies will be presented in due course. Many new types of chemical reactions have been developed to facilitate easier synthesis of complex compounds. Among the strategies, domino reactions, which have been utilized for the efficient and stereoselective construction of complex molecules from simple precursors in a single process, are widely used due to their high synthetic efficiency by reducing both the number of synthetic operation required and the quantities of chemicals and solvents used

  1. Bioaccumulation and enantioselectivity of type I and type II pyrethroid pesticides in earthworm.

    Science.gov (United States)

    Chang, Jing; Wang, Yinghuan; Wang, Huili; Li, Jianzhong; Xu, Peng

    2016-02-01

    In this study, the bioavailability and enantioselectivity differences between bifenthrin (BF, typeⅠpyrethroid) and lambad-cyhalothrin (LCT, type Ⅱ pyrethroid) in earthworm (Eisenia fetida) were investigated. The bio-soil accumulation factors (BSAFs) of BF was about 4 times greater than that of LCT. LCT was degraded faster than BF in soil while eliminated lower in earthworm samples. Compound sorption plays an important role on bioavailability in earthworm, and the soil-adsorption coefficient (K(oc)) of BF and LCT were 22 442 and 42 578, respectively. Metabolic capacity of earthworm to LCT was further studied as no significant difference in the accumulation of LCT between the high and low dose experiment was found. 3-phenoxybenzoic acid (PBCOOH), a metabolite of LCT produced by earthworm was detected in soil. The concentration of PBCOOH at high dose exposure was about 4.7 times greater than that of in low dose level at the fifth day. The bioaccumulation of BF and LCT were both enantioselective in earthworm. The enantiomer factors of BF and LCT in earthworm were approximately 0.12 and 0.65, respectively. The more toxic enantiomers ((+)-BF and (-)-LCT) had a preferential degradation in earthworm and leaded to less toxicity on earthworm for racemate exposure. In combination with other studies, a liner relationship between Log BSAF(S) and Log K(ow) was observed, and the Log BSAF(S) decreased with the increase of Log K(ow). Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Development of high temperature fasteners using directionally solidified eutectic alloys

    Science.gov (United States)

    George, F. D.

    1972-01-01

    The suitability of the eutectics for high temperature fasteners was investigated. Material properties were determined as a function of temperature, and included shear parallel and perpendicular to the growth direction and torsion parallel to it. Techniques for fabricating typical fastener shapes included grinding, creep forming, and direct casting. Both lamellar Ni3Al-Ni3Nb and fibrous (Co,Cr,Al)-(Cr,Co)7C3 alloys showed promise as candidate materials for high temperature fastener applications. A brief evaluation of the performance of the best fabricated fastener design was made.

  3. High Temperature 300°C Directional Drilling System

    Energy Technology Data Exchange (ETDEWEB)

    Chatterjee, Kamalesh [Baker Hughes Oilfield Operations, Houston, TX (United States); Aaron, Dick [Baker Hughes Oilfield Operations, Houston, TX (United States); Macpherson, John [Baker Hughes Oilfield Operations, Houston, TX (United States)

    2015-07-31

    Many countries around the world, including the USA, have untapped geothermal energy potential. Enhanced Geothermal Systems (EGS) technology is needed to economically utilize this resource. Temperatures in some EGS reservoirs can exceed 300°C. To effectively utilize EGS resources, an array of injector and production wells must be accurately placed in the formation fracture network. This requires a high temperature directional drilling system. Most commercial services for directional drilling systems are rated for 175°C while geothermal wells require operation at much higher temperatures. Two U.S. Department of Energy (DOE) Geothermal Technologies Program (GTP) projects have been initiated to develop a 300°C capable directional drilling system, the first developing a drill bit, directional motor, and drilling fluid, and the second adding navigation and telemetry systems. This report is for the first project, “High Temperature 300°C Directional Drilling System, including drill bit, directional motor and drilling fluid, for enhanced geothermal systems,” award number DE-EE0002782. The drilling system consists of a drill bit, a directional motor, and drilling fluid. The DOE deliverables are three prototype drilling systems. We have developed three drilling motors; we have developed four roller-cone and five Kymera® bits; and finally, we have developed a 300°C stable drilling fluid, along with a lubricant additive for the metal-to-metal motor. Metal-to-metal directional motors require coatings to the rotor and stator for wear and corrosion resistance, and this coating research has been a significant part of the project. The drill bits performed well in the drill bit simulator test, and the complete drilling system has been tested drilling granite at Baker Hughes’ Experimental Test Facility in Oklahoma. The metal-to-metal motor was additionally subjected to a flow loop test in Baker Hughes’ Celle Technology Center in Germany, where it ran for more than 100

  4. Enantioselective analysis of citalopram and escitalopram in postmortem blood together with genotyping for CYP2D6 and CYP2C19.

    Science.gov (United States)

    Carlsson, Björn; Holmgren, Anita; Ahlner, Johan; Bengtsson, Finn

    2009-03-01

    Citalopram is marketed as a racemate (50:50) mixture of the S(+)-enantiomer and R(-)-enantiomer and the active S(+)-enantiomer (escitalopram) that possess inhibitory effects. Citalopram was introduced in Sweden in 1992 and is the most frequently used antidepressant to date in Sweden. In 2002, escitalopram was introduced onto the Swedish market for treatment of depression and anxiety disorders. The main objective of this study was to investigate S(+)-citalopram [i.e., the racemic drug (citalopram) or the enantiomer (escitalopram)] present in forensic autopsy cases positive for the presence of citalopram in routine screening using a non-enantioselective bioanalytical method. Fifty out of the 270 samples found positive by gas chromatography-nitrogen-phosphorus detection were further analyzed using enantioselective high-performance liquid chromatography. The 50 cases were genotyped for CYP2D6 and CYP2C19, as these isoenzymes are implicated in the metabolism of citalopram and escitalopram. In samples positive for racemic citalopram using the screening method for forensic autopsy cases, up to 20% would have been misinterpreted in the absence of an enantioselective method. An enantioselective method is thus necessary for correct interpretation of autopsy cases, after the enantiomer has been introduced onto the market. The percentage of poor metabolizers was 6% for CYP2D6 and 8% for CYP2C19.

  5. Direct Electroplating on Highly Doped Patterned Silicon Wafers

    NARCIS (Netherlands)

    Vargas Llona, Laura Dolores; Jansen, Henricus V.; Elwenspoek, Michael Curt

    Nickel thin films have been electrodeposited directly on highly doped silicon wafers after removal of the native oxide layer. These substrates conduct sufficiently well to allow deposition using a periferical electrical contact on the wafer. Films 2 μm thick were deposited using a nickel sulfamate

  6. Direct unavailability computation of a maintained highly reliable system

    Czech Academy of Sciences Publication Activity Database

    Briš, R.; Byczanski, Petr

    2010-01-01

    Roč. 224, č. 3 (2010), s. 159-170 ISSN 1748-0078 Grant - others:GA Mšk(CZ) MSM6198910007 Institutional research plan: CEZ:AV0Z30860518 Keywords : high reliability * availability * directed acyclic graph Subject RIV: BA - General Mathematics http:// journals .pepublishing.com/content/rtp3178l17923m46/

  7. Poly(propylene carbonate): Insight into the Microstructure and Enantioselective Ring-Opening Mechanism

    KAUST Repository

    Salmeia, Khalifah A.

    2012-11-13

    Different poly(propylene carbonate) (PPC) microstructures have been synthesized from the alternating copolymerization of CO 2 with both racemic propylene oxide (PO) and various mixtures of PO enantiomers using chiral salen catalysts. The microstructures of the obtained copolymers as a function of polymerization time have been analyzed by a combination of chiral GC and high-resolution NMR spectroscopy. The 13C NMR spectra of selected poly(propylene carbonate) samples were recorded using a 900 MHz ( 1H) spectrometer, showing a previously unreported fine splitting of the carbonate resonances. This allowed a detailed assignment of signals for various copolymer microstructures taking into account the specifics in their stereo- and regioirregularities. For example, the enantioselectivity preference of the (R,R-salen)Co catalyst for (S)-PO at the beginning of the copolymerization leads predominantly to (S)-PO insertion, with any (R)-PO misinsertion being followed by incorporation of (S)-PO, so that the microstructure features isolated stereoerrors. K rel calculations for the copolymerization showed around 5-fold enantioselectivity for (S)-PO over (R)-PO at short reaction time. Analysis of the copolymer microstructures obtained under various reaction conditions appears to be an additional approach to differentiate the occurrence of bimetallic and bifunctional copolymerization mechanisms that are widely discussed in the literature. © 2012 American Chemical Society.

  8. A catalytic reactor for the organocatalyzed enantioselective continuous flow alkylation of aldehydes.

    Science.gov (United States)

    Porta, Riccardo; Benaglia, Maurizio; Puglisi, Alessandra; Mandoli, Alessandro; Gualandi, Andrea; Cozzi, Pier Giorgio

    2014-12-01

    The use of immobilized metal-free catalysts offers the unique possibility to develop sustainable processes in flow mode. The challenging intermolecular organocatalyzed enantioselective alkylation of aldehydes was performed for the first time under continuous flow conditions. By using a packed-bed reactor filled with readily available supported enantiopure imidazolidinone, different aldehydes were treated with three distinct cationic electrophiles. In the organocatalyzed α-alkylation of aldehydes with 1,3-benzodithiolylium tetrafluoroborate, excellent enantioselectivities, in some cases even better than those obtained in the flask process (up to 95% ee at 25 °C), and high productivity (more than 3800 h(-1) ) were obtained, which thus shows that a catalytic reactor may continuously produce enantiomerically enriched compounds. Treatment of the alkylated products with Raney-nickel furnished enantiomerically enriched α-methyl derivatives, key intermediates for active pharmaceutical ingredients and natural products. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Poly(propylene carbonate): Insight into the Microstructure and Enantioselective Ring-Opening Mechanism

    KAUST Repository

    Salmeia, Khalifah A.; Vagin, Sergei; Anderson, Carly E.; Rieger, Bernhard

    2012-01-01

    Different poly(propylene carbonate) (PPC) microstructures have been synthesized from the alternating copolymerization of CO 2 with both racemic propylene oxide (PO) and various mixtures of PO enantiomers using chiral salen catalysts. The microstructures of the obtained copolymers as a function of polymerization time have been analyzed by a combination of chiral GC and high-resolution NMR spectroscopy. The 13C NMR spectra of selected poly(propylene carbonate) samples were recorded using a 900 MHz ( 1H) spectrometer, showing a previously unreported fine splitting of the carbonate resonances. This allowed a detailed assignment of signals for various copolymer microstructures taking into account the specifics in their stereo- and regioirregularities. For example, the enantioselectivity preference of the (R,R-salen)Co catalyst for (S)-PO at the beginning of the copolymerization leads predominantly to (S)-PO insertion, with any (R)-PO misinsertion being followed by incorporation of (S)-PO, so that the microstructure features isolated stereoerrors. K rel calculations for the copolymerization showed around 5-fold enantioselectivity for (S)-PO over (R)-PO at short reaction time. Analysis of the copolymer microstructures obtained under various reaction conditions appears to be an additional approach to differentiate the occurrence of bimetallic and bifunctional copolymerization mechanisms that are widely discussed in the literature. © 2012 American Chemical Society.

  10. Enantioselective conjugate addition of diethylzinc to chalcone catalyzed by Co(acac)2 and chiral amino alcohols

    NARCIS (Netherlands)

    Vries, André H.M. de; Feringa, Bernard

    1997-01-01

    Co(acac)2 in the presence of chiral ligands has been employed as catalyst for the enantioselective conjugate addition of diethylzinc to chalcone. With chiral amino alcohols derived from (+)-camphor, enantioselectivities up to 83% were achieved.

  11. Effect of cavitation in high-pressure direct injection

    Science.gov (United States)

    Aboulhasanzadeh, Bahman; Johnsen, Eric

    2015-11-01

    As we move toward higher pressures for Gasoline Direct Injection and Diesel Direct Injection, cavitation has become an important issue. To better understand the effect of cavitation on the nozzle flow and primary atomization, we use a high-order accurate Discontinuous Galerkin approach using multi-GPU parallelism to simulate the compressible flow inside and outside the nozzle. Phase change is included using the six-equations model. We investigate the effect of nozzle geometry on cavitation inside the injector and on primary atomization outside the nozzle.

  12. A Direct DME High Temperature PEM Fuel Cell

    DEFF Research Database (Denmark)

    Vassiliev, Anton; Jensen, Jens Oluf; Li, Qingfeng

    2012-01-01

    Dimethyl ether (DME) has been identified as an alternative to methanol for use in direct fuel cells. It combines the advantages of hydrogen in terms of pumpless fuel delivery and high energy density like methanol, but without the toxicity of the latter. The performance of a direct dimethyl ether...... fuel cell suffers greatly from the very low DME-water miscibility. To cope with the problem polybenzimidazole (PBI) based membrane electrode assemblies (MEAs) have been made and tested in a vapor fed system. PtRu on carbon has been used as anode catalyst and air at ambient pressure was used as oxidant...

  13. Experimental investigation of a directionally enhanced DHX concept for high temperature Direct Reactor Auxiliary Cooling Systems

    International Nuclear Information System (INIS)

    Hughes, Joel T.; Blandford, Edward D.

    2016-01-01

    Highlights: • A novel directional heat exchanger design has been developed. • Hydrodynamic tests have been performed on the proposed design. • Heat transfer performance is inferred by hydrodynamic results. • Results are discussed and future work is suggested. - Abstract: The use of Direct Reactor Auxiliary Cooling Systems (DRACSs) as a safety-related decay heat removal system for advanced reactors has developed historically through the Sodium Fast Reactor (SFR) community. Beginning with the EBR-II, DRACSs have been utilized in a large number of past and current SFR designs. More recently, the DRACS has been adopted for Fluoride Salt-Cooled High-Temperature Reactors (FHRs) for similar decay heat removal functions. In this paper we introduce a novel directionally enhanced DRACS Heat Exchanger (DHX) concept. We present design options for optimizing such a heat exchanger so that shell-side heat transfer is enhanced in one primary coolant flow direction and degraded in the opposite coolant flow direction. A reduced-scale experiment investigating the hydrodynamics of a directionally enhanced DHX was built and the data collected is presented. The concept of thermal diodicity is expanded to heat exchanger technologies and used as performance criteria for evaluating design options. A heat exchanger that can perform as such would be advantageous for use in advanced reactor concepts where primary coolant flow reversal is expected during Loss-of-Forced-Circulation (LOFC) accidents where the ability to circulate coolant is compromised. The design could also find potential use in certain advanced Sodium Fast Reactor (SFR) designs utilizing fluidic diode concepts.

  14. Experimental investigation of a directionally enhanced DHX concept for high temperature Direct Reactor Auxiliary Cooling Systems

    Energy Technology Data Exchange (ETDEWEB)

    Hughes, Joel T.; Blandford, Edward D., E-mail: edb@unm.edu

    2016-07-15

    Highlights: • A novel directional heat exchanger design has been developed. • Hydrodynamic tests have been performed on the proposed design. • Heat transfer performance is inferred by hydrodynamic results. • Results are discussed and future work is suggested. - Abstract: The use of Direct Reactor Auxiliary Cooling Systems (DRACSs) as a safety-related decay heat removal system for advanced reactors has developed historically through the Sodium Fast Reactor (SFR) community. Beginning with the EBR-II, DRACSs have been utilized in a large number of past and current SFR designs. More recently, the DRACS has been adopted for Fluoride Salt-Cooled High-Temperature Reactors (FHRs) for similar decay heat removal functions. In this paper we introduce a novel directionally enhanced DRACS Heat Exchanger (DHX) concept. We present design options for optimizing such a heat exchanger so that shell-side heat transfer is enhanced in one primary coolant flow direction and degraded in the opposite coolant flow direction. A reduced-scale experiment investigating the hydrodynamics of a directionally enhanced DHX was built and the data collected is presented. The concept of thermal diodicity is expanded to heat exchanger technologies and used as performance criteria for evaluating design options. A heat exchanger that can perform as such would be advantageous for use in advanced reactor concepts where primary coolant flow reversal is expected during Loss-of-Forced-Circulation (LOFC) accidents where the ability to circulate coolant is compromised. The design could also find potential use in certain advanced Sodium Fast Reactor (SFR) designs utilizing fluidic diode concepts.

  15. High performance direct methanol fuel cell with thin electrolyte membrane

    Science.gov (United States)

    Wan, Nianfang

    2017-06-01

    A high performance direct methanol fuel cell is achieved with thin electrolyte membrane. 320 mW cm-2 of peak power density and over 260 mW cm-2 at 0.4 V are obtained when working at 90 °C with normal pressure air supply. It is revealed that the increased anode half-cell performance with temperature contributes primarily to the enhanced performance at elevated temperature. From the comparison of iR-compensated cathode potential of methanol/air with that of H2/air fuel cell, the impact of methanol crossover on cathode performance decreases with current density and becomes negligible at high current density. Current density is found to influence fuel efficiency and methanol crossover significantly from the measurement of fuel efficiency at different current density. At high current density, high fuel efficiency can be achieved even at high temperature, indicating decreased methanol crossover.

  16. High power density reactors based on direct cooled particle beds

    Science.gov (United States)

    Powell, J. R.; Horn, F. L.

    Reactors based on direct cooled High Temperature Gas Cooled Reactor (HTGR) type particle fuel are described. The small diameter particle fuel is packed between concentric porous cylinders to make annular fuel elements, with the inlet coolant gas flowing inwards. Hot exit gas flows out along the central channel of each element. Because of the very large heat transfer area in the packed beds, power densities in particle bed reactors (PBRs) are extremely high resulting in compact, lightweight systems. Coolant exit temperatures are high, because of the ceramic fuel temperature capabilities, and the reactors can be ramped to full power and temperature very rapidly. PBR systems can generate very high burst power levels using open cycle hydrogen coolant, or high continuous powers using closed cycle helium coolant. PBR technology is described and development requirements assessed.

  17. Enhancing the potential of enantioselective organocatalysis with light

    Science.gov (United States)

    Silvi, Mattia; Melchiorre, Paolo

    2018-02-01

    Organocatalysis—catalysis mediated by small chiral organic molecules—is a powerful technology for enantioselective synthesis, and has extensive applications in traditional ionic, two-electron-pair reactivity domains. Recently, organocatalysis has been successfully combined with photochemical reactivity to unlock previously inaccessible reaction pathways, thereby creating new synthetic opportunities. Here we describe the historical context, scientific reasoning and landmark discoveries that were essential in expanding the functions of organocatalysis to include one-electron-mediated chemistry and excited-state reactivity.

  18. Catalytic enantioselective alkene aminohalogenation/cyclization involving atom transfer.

    Science.gov (United States)

    Bovino, Michael T; Chemler, Sherry R

    2012-04-16

    Problem solved: the title reaction was used for the synthesis of chiral 2-bromo, chloro, and iodomethyl indolines and 2-iodomethyl pyrrolidines. Stereocenter formation is believed to occur by enantioselective cis aminocupration and C-X bond formation is believed to occur by atom transfer. The ultility of the products as versatile synthetic intermediates was demonstrated, as was a radical cascade cyclization sequence. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Directly patternable high refractive index ferroelectric sol–gel resist

    Energy Technology Data Exchange (ETDEWEB)

    Garoli, D., E-mail: denis.garoli@iit.it [Istituto Italiano di Tecnologia, Via Morego 16, 16136 Genova (Italy); Della Giustina, G. [Industrial Engineering Department, University of Padova and INSTM, Via Marzolo 9, 35131 Padova (Italy)

    2015-08-15

    The development of a ferroelectric negative tone sol–gel resist for Ultraviolet (UV) and Electron Beam (EB) lithography is presented. A new system based on Lead Zirconate Titanate (PZT, with formula PbZr{sub 0.52}Ti{sub 0.48}O{sub 3}) was synthesized by sol–gel method. The lithographic performances were investigated and several structures spanning from the micron range down to less than 50 nm have been achieved by UV and EB lithography. The system interaction with UV light and Electron beam was thoroughly characterized by FT-IT spectroscopy. The exposed PZT was annealed at high temperatures in order to study the crystalline phase evolution, the optical constants values and stability of patterned structures. After exposure and annealing, the refractive index of the material can vary from 1.68 up to 2.33 (@400 nm), while the ferroelectric behaviour seems to be maintained after high temperature annealing. These results suggest a possible application of PZT resist not only as ferroelectric but also as nanopatternable high refractive index material. Moreover, direct nanopatterning by means of Focused Ion Beam (FIB) lithography was verified and the potentiality for the preparation of high aspect ratio hollow nanostructures will be presented. - Highlights: • A new formula directly patternable PZT high refractive index resist is presented. • The gel is sensitive to both UV and electron beam exposure. • The refractive index can vary from 1.68 up to 2.33 (@400 nm). • Direct nanopatterning by means of Focused Ion Beam (FIB) lithography was verified. • High aspect ratio hollow nanostructures will be presented.

  20. High power density reactors based on direct cooled particle beds

    International Nuclear Information System (INIS)

    Powell, J.R.; Horn, F.L.

    1985-01-01

    Reactors based on direct cooled HTGR type particle fuel are described. The small diameter particle fuel is packed between concentric porous cylinders to make annular fuel elements, with the inlet coolant gas flowing inwards. Hot exit gas flows out long the central channel of each element. Because of the very large heat transfer area in the packed beds, power densities in particle bed reactors (PBR's) are extremely high resulting in compact, lightweight systems. Coolant exit temperatures are high, because of the ceramic fuel temperature capabilities, and the reactors can be ramped to full power and temperature very rapidly. PBR systems can generate very high burst power levels using open cycle hydrogen coolant, or high continuous powers using closed cycle helium coolant. PBR technology is described and development requirements assessed. 12 figs

  1. Application of enantioselective radical reactions: synthesis of (+)-ricciocarpins A and B.

    Science.gov (United States)

    Sibi, Mukund P; He, Liwen

    2004-05-27

    Enantioselective synthesis of (+)-ricciocarpins A and B has been achieved in 41 and 45% overall yields, respectively, starting from a beta-substituted oxazolidinone. The key steps in the strategy are an enantioselective conjugate radical addition and the addition of a furyl organometallic to a key aldehyde intermediate. [reaction--see text

  2. Enantioselective rhodium enolate protonations. A new methodology for the synthesis of beta2-amino acids.

    Science.gov (United States)

    Sibi, Mukund P; Tatamidani, Hiroto; Patil, Kalyani

    2005-06-23

    [reaction: see text] Rhodium-catalyzed conjugate addition of an aryl boronic acid to alpha-methylamino acrylates followed by enantioselective protonation of the oxa-pi-allylrhodium intermediate provides access to aryl-substituted beta(2)-amino acids. The impact of the different variables of the reaction on the levels of enantioselectivity has been assessed.

  3. Enantioselective H-atom transfer reaction: a strategy to synthesize formaldehyde aldol products.

    Science.gov (United States)

    Sibi, Mukund P; Patil, Kalyani

    2005-04-14

    [reaction: see text] Enantioselective radical alkylation of Baylis-Hillman adducts furnished aldol products in good yield and selectivity. The results illustrate that the selectivity in the hydrogen atom transfer is dependent on the size of the ester substituent, with smaller substituents providing better enantioselectivity.

  4. Enantioselective Rhodium Enolate Protonations. A New Methodology for the Synthesis of β2-Amino Acids

    Science.gov (United States)

    Sibi, Mukund P.; Tatamidani, Hiroto; Patil, Kalyani

    2008-01-01

    Rhodium catalyzed conjugate addition of an aryl boronic acid to α-methylamino acrylates followed by enantioselective protonation of the oxa-π-allylrhodium intermediate provides access to aryl substituted β2-amino acids. The impact of the different variables of the reaction on the levels of enantioselectivity has been assessed. PMID:15957893

  5. DNA-based catalytic enantioselective intermolecular oxa-Michael addition reactions

    NARCIS (Netherlands)

    Megens, Rik P.; Roelfes, Gerard

    2012-01-01

    Using the DNA-based catalysis concept, a novel Cu(II) catalyzed enantioselective oxa-Michael addition of alcohols to enones is reported. Enantioselectivities of up to 86% were obtained. The presence of water is important for the reactivity, possibly by reverting unwanted side reactions such as

  6. Enantioselective silver nanoclusters: Preparation, characterization and photoluminescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Farrag, Mostafa, E-mail: mostafafarrag@aun.edu.eg

    2016-09-01

    prepared silver nanoclusters were investigated using nitrogen adsorption-desorption at −196 °C. Specific surface area S{sub BET}, pore volume and average pore diameter were calculated. - Highlights: • New wet chemistry method to prepare mirror image small silver clusters protected by penicillamine. • Preparation enantioselective catalysts by easy wet chemistry method. • The synthesized silver clusters have photoluminescence properties. • The synthesized silver clusters show high Anisotropy factors up to 3 × 10{sup −4}. • The adsorption isotherms of all synthesized clusters are mainly of type II of Brunaue’s classification.

  7. Fluids with highly directional attractive forces. III. Multiple attraction sites

    International Nuclear Information System (INIS)

    Wertheim, M.S.

    1986-01-01

    The authors derive a reformulation of statistical thermodynamics for fluids of molecules which interact by highly directional attraction. The molecular model consists of a repulsive core and several sites of very short-ranged attraction. The authors explore the relationship between graph cancellation in the fugacity expansion and three types of steric incompatibility between repulsive and attractive interactions involving several molecules. The steric effects are used to best advantage in a limited regrouping of bonds. This controls the density parameters which appear when articulation points are eliminated in the graphical representation. Each density parameter is a singlet density for a species consisting of molecules with a specified set of sites bonded. The densities satisfy subsidiary conditions of internal consistency. These conditions are equivalent to a minimization of the Helmholtz free energy A. Graphical expressions for A and for the pressure are derived. Analogs of the s-particle direct correlation functions and of the Ornstein-Zernike equation are found

  8. Direct dimethyl ether high temperature polymer electrolyte membrane fuel cells

    DEFF Research Database (Denmark)

    Vassiliev, Anton; Jensen, Jens Oluf; Li, Qingfeng

    and suffers from low DME solubility in water. When the DME - water mixture is fed as vapour miscibility is no longer a problem. The increased temperature is more beneficial for the kinetics of the direct oxidation of DME than of methanol. The Open Circuit Voltage (OCV) with DME operation was 50 to 100 m......A high temperature polybenzimidazole (PBI) polymer fuel cell was fed with dimethyl ether (DME) and water vapour mixture on the anode at ambient pressure with air as oxidant. A peak power density of 79 mW/cm2 was achieved at 200°C. A conventional polymer based direct DME fuel cell is liquid fed......V higher than that of methanol, indicating less fuel crossover....

  9. High-temperature ultrasonic measurements applied to directly heated samples

    International Nuclear Information System (INIS)

    Moore, R.I.; Taylor, R.E.

    1984-01-01

    High-temperature ultrasonic measurements of Young's modulus were made of graphite samples heated directly. The samples were cylindrical rods of the same geometry as that used in the multiproperty apparatus for simultaneous/consecutive measurements of a number of thermophysical properties to high temperatures. The samples were resonated in simple longitudinal vibration modes. Measurements were performed up to 2000 K. Incorporation of ultrasonic measurements of Young's modulus in the capabilities of the multiproperty apparatus is valuable because (i) ultrasonic measurements can be related to normal destructive measurements of this property; (ii) they can be used for screening materials or acceptance testing of specimens; (iii) they can be used to increase the understanding of thermophysical properties and property correlations. (author)

  10. High-voltage direct-current circuit breakers

    International Nuclear Information System (INIS)

    Yoshioka, Y.; Hirasawa, K.

    1991-01-01

    This paper reports that in 1954 the first high-voltage direct-current (HVDC) transmission system was put into operation between Gotland and the mainland of Sweden. Its system voltage and capacity were 100 kV and 20 MW, respectively. Since then many HVDC transmission systems have been planned, constructed, or commissioned in more than 30 places worldwide, and their total capacity is close to 40 GW. Most systems commissioned to date are two-terminal schemes, and HVDC breakers are not yet used in the high-potential main circuit of those systems, because the system is expected to perform well using only converter/inverter control even at a fault stage of the transmission line. However, even in a two-terminal scheme there are not a few merits in using an HVDC breaker when the system has two parallel transmission lines, that is, when it is a double-circuit system

  11. Enantioselective changes in oxidative stress and toxin release in Microcystis aeruginosa exposed to chiral herbicide diclofop acid

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Jing [School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418 (China); MOE Key Lab of Environmental Remediation and Ecosystem Health, College of Natural Research and Environmental Sciences, Zhejiang University, Hangzhou 310058 (China); Zhang, Ying [Department of Environmental Science, East China Normal University, Shanghai 200241 (China); Chen, Shengwen [School of Urban Development and Environment Engineering, Shanghai Second Polytechnic University, Shanghai 201209 (China); Liu, Chaonan; Zhu, Yongqiang [School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418 (China); Liu, Weiping, E-mail: wliu@zju.edu.cn [MOE Key Lab of Environmental Remediation and Ecosystem Health, College of Natural Research and Environmental Sciences, Zhejiang University, Hangzhou 310058 (China)

    2014-01-15

    Highlights: •The first study on enantioselective oxidative stress and toxin release from Microcystis aeruginosa. •Provide information for the R-enantiomer poses more oxidative stress than the S-enantiomer. •Lifecycle analysis of chiral pollutants needs more attention in environmental assessment. -- Abstract: Enantioselective oxidative stress and toxin release from Microcystis aeruginosa after exposure to the chiral herbicide diclofop acid were investigated. Racemic diclofop acid, R-diclofop acid and S-diclofop acid induced reactive oxygen species (ROS) generation, increased the concentration of malondialdehyde (MDA), enhanced the activity of superoxide dismutase (SOD) and triggered toxin release in M. aeruginosa to varying degrees. The increase in MDA concentration and SOD activity in M. aeruginosa occurred sooner after exposure to diclofop acid than when the cyanobacteria was exposed to either the R- and the S-enantiomer. In addition, enantioselective toxicity of the enantiomers was observed. The R-enantiomer trigged more ROS generation, more SOD activity and more toxin synthesis and release in M. aeruginosa cells than the S-enantiomer. Diclofop acid and its R-enantiomer may collapse the transmembrane proton gradient and destroy the cell membrane through lipid peroxidation and free radical oxidation, whereas the S-enantiomer did not demonstrate such action. R-diclofop acid inhibits the growth of M. aeruginosa in the early stage, but ultimately induced greater toxin release, which has a deleterious effect on the water column. These results indicate that more comprehensive study is needed to determine the environmental safety of the enantiomers, and application of chiral pesticides requires more direct supervision and training. Additionally, lifecycle analysis of chiral pollutants in aquatic system needs more attention to aide in the environmental assessment of chiral pesticides.

  12. Enantioselective synthesis of no-carrier added (NCA) 6-[18F]Fluoro-L-Dopa

    International Nuclear Information System (INIS)

    Duanzhi Yin; Lan Zhang; Yongxian Wang; Ganghua Tang; First Military Medical Univ., Guangzhou; Xiaolan Tang

    2003-01-01

    6-[ 18 F]Fluoro-L-Dopa (6-FDOPA) is the analogue of L-Dopa, the biosynthesis precursor for dopamine. As a PET tracer, it was widely applied for the presynaptic dopamine function studies in human brain. The application of a chiral phase-transfer-catalyst (PTC) in enantioselective synthesis of N.C.A. 6-[ 18 F]Fluoro-L-Dopa has been developed recently. An improved procedure was described. The labeling precursor (6-Trimethylammoniumveratraldehyde Triflate) and PTC (O-Allyl-N-(9)-anthracenylcinchonidinium Bromide) were synthesized. A successful synthesis route was developed for the preparation of 6-[ 18 F]Fluoro-L-Dopa with high radiochemical yields (4-9%, decay uncorrected) and short synthesis time(80min). The radiochemical purity was over 99% and no D-isomer was detected by HPLC analysis using a chiral mobile phase. (author)

  13. Enantioselective rhodium/ruthenium photoredox catalysis en route to chiral 1,2-aminoalcohols.

    Science.gov (United States)

    Ma, Jiajia; Harms, Klaus; Meggers, Eric

    2016-08-09

    A rhodium-based chiral Lewis acid catalyst combined with [Ru(bpy)3](PF6)2 as a photoredox sensitizer allows for the visible-light-activated redox coupling of α-silylamines with 2-acyl imidazoles to afford, after desilylation, 1,2-amino-alcohols in yields of 69-88% and with high enantioselectivity (54-99% ee). The reaction is proposed to proceed via an electron exchange between the α-silylamine (electron donor) and the rhodium-chelated 2-acyl imidazole (electron acceptor), followed by a stereocontrolled radical-radical reaction. Substrate scope and control experiments reveal that the trimethylsilyl group plays a crucial role in this reductive umpolung of the carbonyl group.

  14. Nickel(0)-catalyzed enantioselective annulations of alkynes and arylenoates enabled by a chiral NHC ligand: efficient access to cyclopentenones.

    Science.gov (United States)

    Ahlin, Joachim S E; Donets, Pavel A; Cramer, Nicolai

    2014-11-24

    Cyclopentenones are versatile structural motifs of natural products as well as reactive synthetic intermediates. The nickel-catalyzed reductive [3+2] cycloaddition of α,β-unsaturated aromatic esters and alkynes constitutes an efficient method for their synthesis. Here, nickel(0) catalysts comprising a chiral bulky C1-symmetric N-heterocyclic carbene ligand were shown to enable an efficient asymmetric synthesis of cyclopentenones from mesityl enoates and internal alkynes under mild conditions. The bulky NHC ligand provided the cyclopentenone products in very high enantioselectivity and led to a regioselective incorporation of unsymmetrically substituted alkynes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Isoindolinones as Michael Donors under Phase Transfer Catalysis: Enantioselective Synthesis of Phthalimidines Containing a Tetrasubstituted Carbon Stereocenter

    Directory of Open Access Journals (Sweden)

    Francesco Scorzelli

    2015-05-01

    Full Text Available Readily available chiral ammonium salts derived from cinchona alkaloids have proven to be effective phase transfer catalysts in the asymmetric Michael reaction of 3-substituted isoindolinones. This protocol provides a convenient method for the construction of valuable asymmetric 3,3-disubstituted isoindolinones in high yields and  moderate to good enantioselectivity. Diastereoselectivity was also investigated in the construction of contiguous tertiary and quaternary stereocenters. The use of acrolein as Michael acceptor led to an interesting tricyclic derivative, a pyrroloisoindolinone analogue, via a tandem conjugated addition/cyclization reaction.

  16. High-quality cardiopulmonary resuscitation: current and future directions.

    Science.gov (United States)

    Abella, Benjamin S

    2016-06-01

    Cardiopulmonary resuscitation (CPR) represents the cornerstone of cardiac arrest resuscitation care. Prompt delivery of high-quality CPR can dramatically improve survival outcomes; however, the definitions of optimal CPR have evolved over several decades. The present review will discuss the metrics of CPR delivery, and the evidence supporting the importance of CPR quality to improve clinical outcomes. The introduction of new technologies to quantify metrics of CPR delivery has yielded important insights into CPR quality. Investigations using CPR recording devices have allowed the assessment of specific CPR performance parameters and their relative importance regarding return of spontaneous circulation and survival to hospital discharge. Additional work has suggested new opportunities to measure physiologic markers during CPR and potentially tailor CPR delivery to patient requirements. Through recent laboratory and clinical investigations, a more evidence-based definition of high-quality CPR continues to emerge. Exciting opportunities now exist to study quantitative metrics of CPR and potentially guide resuscitation care in a goal-directed fashion. Concepts of high-quality CPR have also informed new approaches to training and quality improvement efforts for cardiac arrest care.

  17. Fluids with highly directional attractive forces. IV. Equilibrium polymerization

    International Nuclear Information System (INIS)

    Wertheim, M.S.

    1986-01-01

    The author investigates approximation methods for systems of molecules interacting by core repulsion and highly directional attraction due to several attraction sites. The force model chosen imitates a chemical bond by providing for bond saturation when binding occurs. The dense fluid is an equilibrium mixture of s-mers with mutual repulsion. The author uses a previously derived reformulation of statistical thermodynamics in which the particle species are monomeric units with a specified set of attraction sites bonded. Thermodynamic perturbation theory (TPT) and integral equations of two types are derived. The use of TPT is illustrated by explicit calculation for a molecular model with two attraction sites capable of forming chain and ring polymers. Successes and defects of TPT are discussed. The integral equations for pair correlations between particles of specified bonding include calculation of self-consistent densities of species. Methods of calculating thermodynamic properties from the solutions of integral equations are given

  18. Development of Environment-Friendly Insecticides Based on Enantioselectivity: Bifenthrin as a Case.

    Science.gov (United States)

    Qian, Yi; Zhou, Peixue; Zhang, Quan

    2017-01-01

    Chiral insecticides significantly contribute to the environmental pollutions recently. As the development of industry and agriculture, increasing number of chiral insecticides are to be introduced into the market. However, their enantioselective toxicology to ecosystem still remains uncertain. In this review, we embarked on a structured search of bibliographic databases for peer-reviewed articles regarding the enantioselective effects of bifenthrin, a typical chiral insecticide, on both target and non-target species. With this enantioselective property of chiral insecticides, they often exhibit adverse effects on non-target species enantioselectively. Specifically, the enantioselective effects of bifenthrin on target and non-target organisms were discussed. In target species, R-bifenthrin exerts more significant activities in deinsectization, compared with S-bifenthrin. On the other hand, Sbifenthrin is more toxic to non-target species than R-bifenthrin, which suggests that the application of sole enantiomer is more efficient and environment-friendly than that of racemate. This review confirms the choice of environment-friendly insecticides from the perspective of the enantioselectivity of chiral insecticides. To make insecticides more efficient to target species and less toxic to non-target species, further research should be done to investigated the potential effects of targetactive enantiomers on non-target organisms as well as the enantioselective fate of enantiomers in multiple environmental matrix.

  19. Enantioselective Degradation and Chiral Stability of Metalaxyl-M in Tomato Fruits.

    Science.gov (United States)

    Jing, Xu; Yao, Guojun; Wang, Peng; Liu, Donghui; Qi, Yanli; Zhou, Zhiqiang

    2016-05-01

    Metalaxyl is an important chiral acetanilide fungicide, and the activity almost entirely originates from the R-enantiomer. Racemic metalaxyl has been gradually replaced by the enantiopure R-enantiomer (metalaxyl-M). In this study a chiral residue analysis method for metalaxyl and the metabolite metalaxyl acid was set up based on high-performance liquid chromatography tandem mass spectroscopy (HPLC-MS/MS). The enantioselective degradation and chiral stability of metalaxyl-M in tomato fruits in two geographically distinct regions of China (Heilongjiang and Hunan Province) were evaluated and the enantioselectivity of metalaxyl acid was also investigated. Tomato plants grew under field conditions with a one-time spray application of metalaxyl-M wettable powder. It was found that R-metalaxyl was not chirally stable and the inactive S-metalaxyl was detected in tomato fruits. At day 40, S-metalaxyl derived from R-metalaxyl accounted for 32% and 26% of the total amount of metalaxyl, respectively. The metabolites R-metalaxyl acid and S-metalaxyl acid were both observed in tomato, and the ratio of S-metalaxyl acid to the sum of S- and R-metalaxyl acid was 36% and 28% at day 40, respectively. For both metalaxyl and metalaxyl acid, the half-life of the S-enantiomer was longer than the R-enantiomer. The results indicated that the enantiomeric conversion should be considered in the bioactivity evaluation and environmental pollution assessment. Chirality 28:382-386, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  20. Enantioselective toxicities of chiral ionic liquids 1-alkyl-3-methyl imidazolium tartrate on Scenedesmus obliquus.

    Science.gov (United States)

    Liu, Huijun; Zhang, Xiaoqiang; Dong, Ying; Chen, Caidong; Zhu, Shimin; Ma, Xiangjuan

    2015-12-01

    Ionic liquids (ILs) are being used in various industries during the last few decades, while the good solubility and high stability of ILs may pose a potential threat to the aquatic environment. Effect of chiral ionic liquids (CILs) 1-alkyl-3-methyl imidazolium tartrate (RMIM T) on Scenedesmus obliquus (S.obliquus) was studied. The growth rate inhibition and cell membrane permeability increased with increasing RMIM T concentration and increasing alkyl chain lengths. The IC50 values of D-(-)-tartrate 1-hexyl-3-methyl imidazolium (D-(-)-HMIM T) were 28.30, 12.23,10.15 and 14.41 mg/L, respectively, at 24, 48, 72 and 96h. While that of L-(+)-tartrate 1-hexyl-3-methyl imidazolium (L-(+)-HMIM T) were 15.97, 7.91, 9.43 and 12.04 mg/L respectively. The concentration of chl a, chl b and chl (a+b) decreased with increasing RMIM T concentration. The chlorophyll fluorescence parameters (F0, Fv/Fm, Fv/F0, Y(II), ETR and NPQ) were affected by RMIM T, indicating that the RMIM T will damage the PSII, inhibit the transmission of excitation energy, decrease the efficiency of photosynthesis. The results showed that there were enantioselective toxicity of RMIM T to algae, and the toxicity of L-(+)-RMIM T was greater than that of D-(-)-RMIM T, but the enantioselective difference becomes smaller with increasing exposure time, and with the increasing carbon chain length of cation, indicating that cation properties may have a larger effect on toxicity than anion properties. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Enantioselective assay for therapeutic drug monitoring of eslicarbazepine acetate: no interference with carbamazepine and its metabolites.

    Science.gov (United States)

    Alves, Gilberto; Fortuna, Ana; Sousa, Joana; Direito, Rosa; Almeida, Anabela; Rocha, Marília; Falcão, Amílcar; Soares-da-Silva, Patrício

    2010-08-01

    As add-on therapy, phase III clinical trials of eslicarbazepine acetate (ESL) conducted in patients with refractory partial-onset seizures have shown good efficacy, safety, and tolerability, even in patients taking carbamazepine (CBZ) at baseline (approximately 60% of the enrolled patients). Thus, considering the pharmacological disadvantages of CBZ and the similar efficacy spectrum of CBZ and ESL, switching to ESL may be successful in many patients. As ESL is a prodrug almost instantaneously converted to S-licarbazepine (S-Lic; approximately 95%), an interest in therapeutic drug monitoring (TDM) of S-Lic is likely to develop in the future. This study investigated the plasma concentrations of S-Lic and R-licarbazepine (R-Lic) enantiomers in patients under CBZ long-term treatment to assess the potential interference of CBZ or its metabolites in the enantioselective TDM of ESL (using S-Lic concentrations). A chiral high-performance liquid chromatography assay with ultraviolet detection (HPLC-UV) previously developed and validated by our research group was used. Twenty-four patients admitted to the Coimbra University Hospital and supposedly receiving CBZ long-term treatment were identified. Blood samples were collected from patients and serum CBZ concentrations were measured by the usual TDM protocol. Aliquots of plasma from such patients were also submitted to a chiral HPLC-UV analysis. The bioanalytical data indicated that S-Lic and R-Lic were not present at detectable concentrations in plasma samples of the CBZ-treated patients. The chromatograms generated by the analysis of patient plasma samples, when compared with those obtained from blank plasma samples spiked with S-Lic and R-Lic, clearly showed the absence of interferences at the retention times of both Lic enantiomers. These data support the usefulness of the chiral HPLC-UV method used for the enantioselective TDM of ESL (using S-Lic) for programs in which switching from CBZ to ESL is implemented.

  2. Enantioselective accumulation, metabolism and phytoremediation of lactofen by aquatic macrophyte Lemna minor.

    Science.gov (United States)

    Wang, Fang; Yi, Xiaotong; Qu, Han; Chen, Li; Liu, Donghui; Wang, Peng; Zhou, Zhiqiang

    2017-09-01

    Pesticides are frequently detected in water bodies due to the agricultural application, which may pose impacts on aquatic organisms. The enantioselective bioaccumulation and metabolism of the herbicide lactofen in aquatic floating macrophyte Lemna minor (L. minor) were studied and the potential L. minor phytoremediation was investigated. Ultra-high performance liquid chromatography - tandem mass spectrometry (UHPLC-MS-MS) analysis for lactofen and its two known metabolites in L. minor was performed. The initial concentrations of racemic lactofen, R-lactofen and S-lactofen were all 30μgL -1 in the growth solution. The distribution of lactofen and its metabolites in growth solution and L. minor was determined throughout a 5-d laboratory trial. It was observed that S-lactofen was preferentially taken up and metabolized in L. minor. After rac-lactofen exposure, the accumulation amount of S-lactofen was approximately 3-fold more than that of R-lactofen in L. minor and the metabolism rate of S-lactofen (T 1/2 =0.92 d) was significantly faster than R-lactofen (T 1/2 =1.55 d). L. minor could only slightly accelerate the metabolism and removal of lactofen in the growth solution. As for the metabolites, desethyl lactofen was found to be the major metabolite in L. minor and the growth solution, whereas the metabolite acifluorfene was undetectable. No interconversion of the two enantiomers was observed after individual enantiomer exposure, indicating they were configurationally stable. The findings of this work represented that the accumulation and metabolism of lactofen in L. minor were enantioselective, and L. minor had limited capacity for the removal of lactofen and its metabolite in water. Copyright © 2017. Published by Elsevier Inc.

  3. Comparison of liquid and supercritical fluid chromatography mobile phases for enantioselective separations on polysaccharide stationary phases.

    Science.gov (United States)

    Khater, Syame; Lozac'h, Marie-Anne; Adam, Isabelle; Francotte, Eric; West, Caroline

    2016-10-07

    Analysis and production of enantiomerically pure compounds is a major topic of interest when active pharmaceutical ingredients are concerned. Enantioselective chromatography has become a favourite both at the analytical and preparative scales. High-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC) are dominating the scene and are often seen as complementary techniques. Nowadays, for economic and ecologic reasons, SFC may be preferred over normal-phase HPLC (NPLC) as it allows significant reductions in solvent consumption. However, the transfer of NPLC methods to SFC is not always straightforward. In this study, we compare the retention of achiral molecules and separation of enantiomers under supercritical fluid (carbon dioxide with ethanol or isopropanol) and liquid normal-phase (heptane with ethanol or isopropanol) elution modes with polysaccharide stationary phases in order to explore the differences between the retention and enantioseparation properties between the two modes. Chemometric methods (namely quantitative structure-retention relationships and discriminant analysis) are employed to compare the results obtained on a large set of analytes (171 achiral probes and 97 racemates) and gain some understanding on the retention and separation mechanisms. The results indicate that, contrary to popular belief, carbon dioxide - solvent SFC mobile phases are often weaker eluents than liquid mobile phases. It appears that SFC and NPLC elution modes provide different retention mechanisms. While some enantioseparations are unaffected, facilitating the transfer between the two elution modes, other enantioseparations may be drastically different due to different types and strength of interactions contributing to enantioselectivity. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Direct fuel cell - A high proficiency power generator for biofuels

    International Nuclear Information System (INIS)

    Patel, P.S.; Steinfeld, G.; Baker, B.S.

    1994-01-01

    Conversion of renewable bio-based resources into energy offers significant benefits for our environment and domestic economic activity. It also improves national security by displacing fossil fuels. However, in the current economic environment, it is difficult for biofuel systems to compete with other fossil fuels. The biomass-fired power plants are typically smaller than 50 MW, lower in electrical efficiencies (<25%) and experience greater costs for handling and transporting the biomass. When combined with fuel cells such as the Direct Fuel Cell (DFC), biofuels can produce power more efficiently with negligible environmental impact. Agricultural and other waste biomass can be converted to ethanol or methane-rich biofuels for power generation use in the DFC. These DFC power plants are modular and factory assembled. Due to their electrochemical (non-combustion) conversion process, these plants are environmentally friendly, highly efficient and potentially cost effective, even in sizes as small as a few meagawatts. They can be sited closer to the source of the biomass to minimize handling and transportation costs. The high-grade waste heat available from DFC power plants makes them attractive in cogeneration applications for farming and rural communities. The DFC potentially opens up new markets for biofuels derived from wood, grains and other biomass waste products

  5. Dual Enantioselective Control using D-phenylglycine-L-proline-derived Catalysts for the Enantioselective Addition of Diethylzinc to Aldehyde

    International Nuclear Information System (INIS)

    Kang, Seock Yong; Park, Yong Sun

    2016-01-01

    Dipeptide-derived catalysts are of great interest in various asymmetric transformations because of their short and simple preparation and easy modification of their modular structure by using different α-amino acids. We recently reported the first example of dipeptide-catalyzed enantioselective addition of dialkylzinc to aldehydes. We have developed a novel D-Phg-L-Pro dipeptide-derived catalyst for the addition of diethylzinc to aromatic aldehydes. We also disclosed an effective chiral switching by simply modifying nonchiral part of D-Phg-L-Pro dipeptide.

  6. Directed PCR-free engineering of highly repetitive DNA sequences

    Directory of Open Access Journals (Sweden)

    Preissler Steffen

    2011-09-01

    Full Text Available Abstract Background Highly repetitive nucleotide sequences are commonly found in nature e.g. in telomeres, microsatellite DNA, polyadenine (poly(A tails of eukaryotic messenger RNA as well as in several inherited human disorders linked to trinucleotide repeat expansions in the genome. Therefore, studying repetitive sequences is of biological, biotechnological and medical relevance. However, cloning of such repetitive DNA sequences is challenging because specific PCR-based amplification is hampered by the lack of unique primer binding sites resulting in unspecific products. Results For the PCR-free generation of repetitive DNA sequences we used antiparallel oligonucleotides flanked by restriction sites of Type IIS endonucleases. The arrangement of recognition sites allowed for stepwise and seamless elongation of repetitive sequences. This facilitated the assembly of repetitive DNA segments and open reading frames encoding polypeptides with periodic amino acid sequences of any desired length. By this strategy we cloned a series of polyglutamine encoding sequences as well as highly repetitive polyadenine tracts. Such repetitive sequences can be used for diverse biotechnological applications. As an example, the polyglutamine sequences were expressed as His6-SUMO fusion proteins in Escherichia coli cells to study their aggregation behavior in vitro. The His6-SUMO moiety enabled affinity purification of the polyglutamine proteins, increased their solubility, and allowed controlled induction of the aggregation process. We successfully purified the fusions proteins and provide an example for their applicability in filter retardation assays. Conclusion Our seamless cloning strategy is PCR-free and allows the directed and efficient generation of highly repetitive DNA sequences of defined lengths by simple standard cloning procedures.

  7. Enantioselective degradation and enantiomerization of indoxacarb in soil.

    Science.gov (United States)

    Sun, Dali; Pang, Junxiao; Qiu, Jing; Li, Li; Liu, Chenglan; Jiao, Bining

    2013-11-27

    In this study, the enantioselective degradation and enantiomerizaton of indoxacarb were investigated in two soils under nonsterilized and sterilized conditions using a chiral OD-RH column on a reversed-phase HPLC. Under nonsterilized conditions, the degradation of indoxacarb in two soils was enantioselective. In acidic soil, the half-lives of R-(-)- and S-(+)-indoxacarb were 10.43 and 14.00 days, respectively. Acidic soil was preferential to the degradation of R-(-)-indoxacarb. In alkaline soil, the half-lives of R-(-)- and S-(+)-indoxacarb were 12.14 and 4.88 days, respectively. S-(+)-Indoxacarb was preferentially degraded. Under sterilized conditions, approximately 5-10% of the initial concentration degraded after 75 days of incubation in acidic soil, whereas in alkaline soil, approximately half of the initial concentration degraded due to chemical hydrolysis under alkaline conditions. Enantiomerization was also discovered in acidic and alkaline soils. The results showed that mutual transformation existed between two enantiomers and that S-(+)-indoxacarb had a significantly higher inversion rate to R-(-)-indoxacarb than its antipode.

  8. The role of achiral pyrazolidinone templates in enantioselective Diels-Alder reactions: scope, limitations, and conformational insights.

    Science.gov (United States)

    Sibi, Mukund P; Stanley, Levi M; Nie, Xiaoping; Venkatraman, Lakshmanan; Liu, Mei; Jasperse, Craig P

    2007-01-17

    We have evaluated the role of achiral pyrazolidinone templates in conjunction with chiral Lewis acids in room temperature, enantioselective Diels-Alder cycloadditions. The role of the fluxional N(1) substituent was examined, with the bulky 1-naphthylmethyl group providing enantioselectivities up to 99% ee, while templates with smaller fluxional groups gave lower selectivities. High selectivities were also observed in reactions of 7d with chiral Lewis acids derived from relatively small chiral ligands, suggesting the pyrazolidinone templates are capable of relaying stereochemical information from the ligand to the reaction center. Lewis acids capable of adapting square planar geometries, such as Cu(OTf)2, Cu(ClO4)2, and Pd(ClO4)2, were found to be particularly effective at providing high selectivities. Additionally, substitution at the C-5 position of the pyrazolidinone templates has been shown to be critical for optimal selectivity. Reactions of the optimal pyrazolidinone appended with a number of common dienophiles and various dienes demonstrate the utility of this achiral template. Furthermore, catalytic loadings could be lowered to 2.5 mol % with essentially no loss in selectivity. Pi-Pi interactions were evaluated as a means to explain the unusually high selectivity observed at room temperature. Finally, non-C2-symmetric ligands were employed as a test to determine if chiral relay was operative.

  9. Boosting Chemical Stability, Catalytic Activity, and Enantioselectivity of Metal-Organic Frameworks for Batch and Flow Reactions.

    Science.gov (United States)

    Chen, Xu; Jiang, Hong; Hou, Bang; Gong, Wei; Liu, Yan; Cui, Yong

    2017-09-27

    A key challenge in heterogeneous catalysis is the design and synthesis of heterogeneous catalysts featuring high catalytic activity, selectivity, and recyclability. Here we demonstrate that high-performance heterogeneous asymmetric catalysts can be engineered from a metal-organic framework (MOF) platform by using a ligand design strategy. Three porous chiral MOFs with the framework formula [Mn 2 L(H 2 O) 2 ] are prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 3,5-bis(trifluoromethyl)-, bismethyl-, and bisfluoro-phenyl substituents at the 3,3'-position. For the first time, we show that not only chemical stability but also catalytic activity and stereoselectivity of the MOFs can be tuned by modifying the ligand structures. Particularly, the MOF incorporated with -CF 3 groups on the pore walls exhibits enhanced tolerance to water, weak acid, and base compared with the MOFs with -F and -Me groups. Under both batch and flow reaction systems, the CF 3 -containing MOF demonstrated excellent reactivity, selectivity, and recyclability, affording high yields and enantioselectivities for alkylations of indoles and pyrrole with a range of ketoesters or nitroalkenes. In contrast, the corresponding homogeneous catalysts gave low enantioselectivity in catalyzing the tested reactions.

  10. Investigation of high-alpha lateral-directional control power requirements for high-performance aircraft

    Science.gov (United States)

    Foster, John V.; Ross, Holly M.; Ashley, Patrick A.

    1993-01-01

    Designers of the next-generation fighter and attack airplanes are faced with the requirements of good high angle-of-attack maneuverability as well as efficient high speed cruise capability with low radar cross section (RCS) characteristics. As a result, they are challenged with the task of making critical design trades to achieve the desired levels of maneuverability and performance. This task has highlighted the need for comprehensive, flight-validated lateral-directional control power design guidelines for high angles of attack. A joint NASA/U.S. Navy study has been initiated to address this need and to investigate the complex flight dynamics characteristics and controls requirements for high angle-of-attack lateral-directional maneuvering. A multi-year research program is underway which includes groundbased piloted simulation and flight validation. This paper will give a status update of this program that will include a program overview, description of test methodology and preliminary results.

  11. Recent Advances in High-Performance Direct Methanol Fuel Cells

    Science.gov (United States)

    Narayanan, S. R.; Chun, W.; Valdez, T. I.; Jeffries-Nakamura, B.; Frank, H.; Surumpudi, S.; Halpert, G.; Kosek, J.; Cropley, C.; La Conti, A. B.; hide

    1996-01-01

    Direct methanol fuel cells for portable power applications have been advanced significantly under DARPA- and ARO-sponsored programs over the last five years. A liquid-feed, direct methanol fuel cell developed under these programs, employs a proton exchange membrane as electrolyte and operates on aqueous solutions of methanol with air or oxygen as the oxidant.

  12. Optimisation of stabilised carboxylesterase NP for enantioselective hydrolysis of naproxen methyl ester

    CSIR Research Space (South Africa)

    Steenkamp, Lucia H

    2008-12-01

    Full Text Available Although the enantioselective kinetic resolution of ester racemates of the non-steroidal antiinflammatory drug naproxen ([2-(6-methoxy-2-naphthyl) propionic acid]) is a common demonstration for biocatalysis, the enantiomeric excess of the reactions...

  13. Asymmetric Synthesis of Optically Active Spirocyclic Indoline Scaffolds through an Enantioselective Reduction of Indoles

    KAUST Repository

    Borrmann, Ruediger; Knop, Nils; Rueping, Magnus

    2016-01-01

    An enantioselective synthesis of spirocyclic indoline scaffolds was achieved by applying an asymmetric iridium-catalyzed hydrogenation of 3H-indoles. Low catalyst loadings and mild reaction conditions provide a broad range of differently substituted

  14. BIOACCUMULATION AND ENANTIOSELECTIVE BIOTRANSFORMATION OF FIPRONIL BY RAINBOW TROUT (ONCORHYNCHUS MYKISS)

    Science.gov (United States)

    Dietary accumulation and enantioselective biotransformation was determined for rainbow trout (Oncorhynchus mykiss) exposed to fipronil, a widely used chiral pesticide. Measurement of the fish carcass tissue (whole fish minus GI tract and liver) showed a rapid accumulation of fip...

  15. Purification and characterisation of a novel enantioselective epoxide hydrolase from Aspergillus niger M200

    Czech Academy of Sciences Publication Activity Database

    Kotík, Michael; Kyslík, Pavel

    2006-01-01

    Roč. 1760, - (2006), s. 245-252 ISSN 0006-3002 Institutional research plan: CEZ:AV0Z50200510 Keywords : epoxide hydrolase * enantioselectivity * aspergillus niger Subject RIV: EE - Microbiology, Virology

  16. Enantioselective synthesis of almorexant via iridium-catalysed intramolecular allylic amidation

    NARCIS (Netherlands)

    Fananas Mastral, Martin; Teichert, Johannes F.; Fernandez-Salas, Jose Antonio; Heijnen, Dorus; Feringa, Ben L.

    2013-01-01

    An enantioselective synthesis of almorexant, a potent antagonist of human orexin receptors, is presented. The chiral tetrahydroisoquinoline core structure was prepared via iridium-catalysed asymmetric intramolecular allylic amidation. Further key catalytic steps of the synthesis include an oxidative

  17. Enantioselective catalytic fluorinative aza-semipinacol rearrangement.

    Science.gov (United States)

    Romanov-Michailidis, Fedor; Pupier, Marion; Besnard, Céline; Bürgi, Thomas; Alexakis, Alexandre

    2014-10-03

    An efficient and highly stereoselective fluorinative aza-semipinacol rearrangement is described. The catalytic reaction requires use of Selectfluor in combination with the chiral, enantiopure phosphate anion derived from acid L3. Under optimized conditions, cyclopropylamines A were transformed into β-fluoro cyclobutylimines B in good yields and high levels of diastereo- and enantiocontrol. Furthermore, the optically active cyclobutylimines were reduced diastereoselectively with L-Selectride in the corresponding fluorinated amines C, compounds of significant interest in the pharmacological industry.

  18. Potencial de biocatálise enantiosseletiva de lipases microbianas Potential of enantioselective biocatalysis by microbial lipases

    Directory of Open Access Journals (Sweden)

    Patrícia de O. Carvalho

    2005-08-01

    Full Text Available Microbial lipases have a great potential for commercial applications due to their stability, selectivity and broad substrate specificity because many non-natural acids, alcohols or amines can be used as the substrate. Three microbial lipases isolated from Brazilian soil samples (Aspergillus niger; Geotrichum candidum; Penicillium solitum were compared in terms of their stability and as biocatalysts in the enantioselective esterification using racemic substrates in organic medium. The lipase from Aspergillus niger showed the highest activity (18.2 U/mL and was highly thermostable, retaining 90% and 60% activity at 50 ºC and 60 ºC after 1 hour, respectively. In organic medium, this lipase provided the best results in terms of enantiomeric excess of the (S-active acid (ee = 6.1% and conversion value (c = 20% in the esterification of (R,S-ibuprofen with 1-propanol in isooctane. The esterification reaction of the racemic mixture of (R,S-2-octanol with decanoic acid proceeded with high enantioselectivity when lipase from Aspergillus niger (E = 13.2 and commercial lipase from Candida antarctica (E = 20 were employed.

  19. Enantioselective column coupled electrophoresis employing large bore capillaries hyphenated with tandem mass spectrometry for ultra-trace determination of chiral compounds in complex real samples.

    Science.gov (United States)

    Piešťanský, Juraj; Maráková, Katarína; Kovaľ, Marián; Havránek, Emil; Mikuš, Peter

    2015-12-01

    A new multidimensional analytical approach for the ultra-trace determination of target chiral compounds in unpretreated complex real samples was developed in this work. The proposed analytical system provided high orthogonality due to on-line combination of three different methods (separation mechanisms), i.e. (1) isotachophoresis (ITP), (2) chiral capillary zone electrophoresis (chiral CZE), and (3) triple quadrupole mass spectrometry (QqQ MS). The ITP step, performed in a large bore capillary (800 μm), was utilized for the effective sample pretreatment (preconcentration and matrix clean-up) in a large injection volume (1-10 μL) enabling to obtain as low as ca. 80 pg/mL limits of detection for the target enantiomers in urine matrices. In the chiral CZE step, the different chiral selectors (neutral, ionizable, and permanently charged cyclodextrins) and buffer systems were tested in terms of enantioselectivity and influence on the MS detection response. The performance parameters of the optimized ITP - chiral CZE-QqQ MS method were evaluated according to the FDA guidance for bioanalytical method validation. Successful validation and application (enantioselective monitoring of renally eliminated pheniramine and its metabolite in human urine) highlighted great potential of this chiral approach in advanced enantioselective biomedical applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Asymmetric Synthesis of Optically Active Spirocyclic Indoline Scaffolds through an Enantioselective Reduction of Indoles

    KAUST Repository

    Borrmann, Ruediger

    2016-11-30

    An enantioselective synthesis of spirocyclic indoline scaffolds was achieved by applying an asymmetric iridium-catalyzed hydrogenation of 3H-indoles. Low catalyst loadings and mild reaction conditions provide a broad range of differently substituted products with excellent yields and enantioselectivities. The developed methodology allows an efficient synthesis of this important spirocyclic structural motif, which is present in numerous biologically active molecules and privileged structures in medicinal chemistry.

  1. A New Mn–Salen Micellar Nanoreactor for Enantioselective Epoxidation of Alkenes in Water

    Directory of Open Access Journals (Sweden)

    Francesco P. Ballistreri

    2018-03-01

    Full Text Available A new chiral Mn–salen catalyst, functionalized with a long aliphatic chain and a choline group, able to act as surfactant catalyst for green epoxidation in water, is here described. This catalyst was employed with a commercial surfactant (CTABr leading to a nanoreactor for the enantioselective epoxidation of some selected alkenes in water, using NaClO as oxidant. This is the first example of a nanoreactor for enantioselective epoxidation of non-functionalized alkenes in water.

  2. Formal total syntheses of classic natural product target molecules via palladium-catalyzed enantioselective alkylation

    Directory of Open Access Journals (Sweden)

    Yiyang Liu

    2014-10-01

    Full Text Available Pd-catalyzed enantioselective alkylation in conjunction with further synthetic elaboration enables the formal total syntheses of a number of “classic” natural product target molecules. This publication highlights recent methods for setting quaternary and tetrasubstituted tertiary carbon stereocenters to address the synthetic hurdles encountered over many decades across multiple compound classes spanning carbohydrate derivatives, terpenes, and alkaloids. These enantioselective methods will impact both academic and industrial settings, where the synthesis of stereogenic quaternary carbons is a continuing challenge.

  3. Enantioselective Addition of Allyltin Reagents to Amino Aldehydes Catalyzed with Bis(oxazolinylphenylrhodium(III Aqua Complexes

    Directory of Open Access Journals (Sweden)

    Hisao Nishiyama

    2011-06-01

    Full Text Available Bis(oxazolinylphenylrhodium(III aqua complexes, (PheboxRhX2(H2O [X = Cl, Br], were found to be efficient Lewis acid catalysts for the enantioselective addition of allyl- and methallyltributyltin reagents to amino aldehydes. The reactions proceed smoothly in the presence of 5–10 mol % of (PheboxRhX2(H2O complex at ambient temperature to give the corresponding amino alcohols with modest to good enantioselectivity (up to 94% ee.

  4. Enantioselective aminocatalysis: Michael addition of unactivated ...

    Indian Academy of Sciences (India)

    KHIANGTE VANLALDINPUIA

    2017-09-25

    Sep 25, 2017 ... the case of acetone) were stirred at room temperature for. 30 min. Nitroolefin (1 ..... Kaprzak A and Gawronski J 2001 Review on the use of cinchona ... 2006 Functionalized chiral ionic liquids as highly effi- cient asymmetric ...

  5. Flexible Enantioselectivity of Tryptophanase Attributable to Benzene Ring in Heterocyclic Moiety of D-Tryptophan

    Directory of Open Access Journals (Sweden)

    Akihiko Shimada

    2012-05-01

    Full Text Available The invariance principle of enzyme enantioselectivity must be absolute because it is absolutely essential to the homochiral biological world. Most enzymes are strictly enantioselective, and tryptophanase is one of the enzymes with extreme absolute enantioselectivity for L-tryptophan. Contrary to conventional knowledge about the principle, tryptophanase becomes flexible to catalyze D-tryptophan in the presence of diammonium hydrogenphosphate. Since D-amino acids are ordinarily inert or function as inhibitors even though they are bound to the active site, the inhibition behavior of D-tryptophan and several inhibitors involved in this process was examined in terms of kinetics to explain the reason for this flexible enantioselectivity in the presence of diammonium hydrogenphosphate. Diammonium hydrogenphosphate gave tryptophanase a small conformational change so that D-tryptophan could work as a substrate. As opposed to other D-amino acids, D-tryptophan is a very bulky amino acid with a benzene ring in its heterocyclic moiety, and so we suggest that this structural feature makes the catalysis of D-tryptophan degradation possible, consequently leading to the flexible enantioselectivity. The present results not only help to understand the mechanism of enzyme enantioselectivity, but also shed light on the origin of homochirality.

  6. High Gain and High Directive of Antenna Arrays Utilizing Dielectric Layer on Bismuth Titanate Ceramics

    Directory of Open Access Journals (Sweden)

    F. H. Wee

    2012-01-01

    Full Text Available A high gain and high directive microstrip patch array antenna formed from dielectric layer stacked on bismuth titanate (BiT ceramics have been investigated, fabricated, and measured. The antennas are designed and constructed with a combination of two-, four-, and six-BiT elements in an array form application on microwave substrate. For gain and directivity enhancement, a layer of dielectric was stacked on the BiT antenna array. We measured the gain and directivity of BiT array antennas with and without the dielectric layer and found that the gain of BiT array antenna with the dielectric layer was enhanced by about 1.4 dBi of directivity and 1.3 dB of gain over the one without the dielectric layer at 2.3 GHz. The impedance bandwidth of the BiT array antenna both with and without the dielectric layer is about 500 MHz and 350 MHz, respectively, which is suitable for the application of the WiMAX 2.3 GHz system. The utilization of BiT ceramics that covers about 90% of antenna led to high radiation efficiency, and small-size antennas were produced. In order to validate the proposed design, theoretical and measured results are provided and discussed.

  7. Enantioselective degradation of Bromocyclene in sewage plants

    Energy Technology Data Exchange (ETDEWEB)

    Bester, K [Duisburg-Essen Univ. (Germany). FG Siedlungswasser- und Abfallwirtschaft/Inst. fuer Umweltanalytik

    2004-09-15

    Bromocyclene has been utilised as insecticide against ectoparasites, however the production in Germany was stopped around 1995. Until that time it was used in pet care as well as in sheep farming. Due to its high bioaccumulation it was detected not only in sewage systems and sewage treatment plants, but also in fresh water fish. Enatioselective determination at that time was used to obtain results on the biodegradation of Bromocyclene in fish. Considering the long time period since the phase out of Bromocyclene it was surprising it was easily identified in sludge samples from 2002.

  8. Enantioselective behaviour of tetraconazole during strawberry wine-making process.

    Science.gov (United States)

    Liu, Na; Pan, Xinglu; Zhang, Shuang; Ji, Mingshan; Zhang, Zhihong

    2018-05-01

    The fate of tetraconazole enantiomers in strawberries during wine-making process was studied. The residues were determined by ultra-performance convergence chromatography tandem triple quadrupole mass spectrometry after each process steps. Results indicated that there was significant enantioselective dissipation of tetraconazole enantiomers during the fermentation process. And (-)-tetraconazole degraded faster than (+)-tetraconazole. The half-lives of (-)-tetraconazole and (+)-tetraconazole were 3.12, 3.76 days with washing procedure and 3.18, 4.05 days without washing procedure. The processing factors of strawberry wine samples after each step were generally less than 1. In particular, the processing factors of the fermentation process were the lowest. The results could help facilitate more accurate risk assessments of tetraconazole during wine-making process. © 2018 Wiley Periodicals, Inc.

  9. Chemo- and Enantioselective Intramolecular Silver-Catalyzed Aziridinations.

    Science.gov (United States)

    Ju, Minsoo; Weatherly, Cale D; Guzei, Ilia A; Schomaker, Jennifer M

    2017-08-07

    Asymmetric nitrene-transfer reactions are a powerful tool for the preparation of enantioenriched amine building blocks. Reported herein are chemo- and enantioselective silver-catalyzed aminations which transform di- and trisubstituted homoallylic carbamates into [4.1.0]-carbamate-tethered aziridines in good yields and with ee values of up to 92 %. The effects of the substrate, silver counteranion, ligand, solvent, and temperature on both the chemoselectivity and ee value were explored. Stereochemical models were proposed to rationalize the observed absolute stereochemistry of the aziridines, which undergo nucleophilic ring opening to yield enantioenriched amines with no erosion in stereochemical integrity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. High-psub(T) direct photon production in pp collisions

    International Nuclear Information System (INIS)

    Anassontzis, E.; Karabarbounis, A.; Kourkoumelis, C.; Resvanis, L.K.; Palmer, R.B.; Rahm, D.C.; Rehak, P.; Stumer, I.; Fabjan, C.W.; Lissauer, D.

    1982-01-01

    Direct photon and neutral-pion production have been measured in pp collisions at the CERN ISR for 30 < √s < 63 GeV and transverse momenta up to 12 GeV/c. The direct photon signal relative to neutral-pion production increases with psub(T) and shows little √s-dependence. Results are reported from a variety of running conditions, and details are given on the method of analysis and on the evaluation of systematic errors for the inclusive cross-section of single-photon and neutral-pion production. (orig.)

  11. High-$p_{T}$ direct photon production in pp collisions

    CERN Document Server

    Anassontzis, E; Ferbel, T; Karabarbounis, A; Kourkoumelis, C; Lissauer, D; Mannelli, I; Molzon, W; Mouzourakis, P; Nappi, A; Palmer, R B; Rahm, David Charles; Rehak, P; Resvanis, L K; Rosso, E; Stumer, I; Willis, W

    1982-01-01

    Direct photon and neutral-pion production have been measured in pp collisions at the CERN ISR for 30< \\sqrt{s}<63 GeV and transverse momenta up to 12 GeV/c. The direct photon signal relative to neutral- pion production increases with p/sub T/ and shows little \\sqrt{s}-dependence. Results are reported from a variety of running conditions, and details are given on the method of analysis and on the evaluation of systematic errors for the inclusive cross-section of single-photon and neutral-pion production.

  12. Method and apparatus for high-efficiency direct contact condensation

    Science.gov (United States)

    Bharathan, Desikan; Parent, Yves; Hassani, A. Vahab

    1999-01-01

    A direct contact condenser having a downward vapor flow chamber and an upward vapor flow chamber, wherein each of the vapor flow chambers includes a plurality of cooling liquid supplying pipes and a vapor-liquid contact medium disposed thereunder to facilitate contact and direct heat exchange between the vapor and cooling liquid. The contact medium includes a plurality of sheets arranged to form vertical interleaved channels or passageways for the vapor and cooling liquid streams. The upward vapor flow chamber also includes a second set of cooling liquid supplying pipes disposed beneath the vapor-liquid contact medium which operate intermittently in response to a pressure differential within the upward vapor flow chamber. The condenser further includes separate wells for collecting condensate and cooling liquid from each of the vapor flow chambers. In alternate embodiments, the condenser includes a cross-current flow chamber and an upward flow chamber, a plurality of upward flow chambers, or a single upward flow chamber. The method of use of the direct contact condenser of this invention includes passing a vapor stream sequentially through the downward and upward vapor flow chambers, where the vapor is condensed as a result of heat exchange with the cooling liquid in the contact medium. The concentration of noncondensable gases in the resulting condensate-liquid mixtures can be minimized by controlling the partial pressure of the vapor, which depends in part upon the geometry of the vapor-liquid contact medium. In another aspect of this invention, the physical and chemical performance of a direct contact condenser can be predicted based on the vapor and coolant compositions, the condensation conditions. and the geometric properties of the contact medium.

  13. The High Direct Medical Costs of Prader-Willi Syndrome.

    Science.gov (United States)

    Shoffstall, Andrew J; Gaebler, Julia A; Kreher, Nerissa C; Niecko, Timothy; Douglas, Diah; Strong, Theresa V; Miller, Jennifer L; Stafford, Diane E; Butler, Merlin G

    2016-08-01

    To assess medical resource utilization associated with Prader-Willi syndrome (PWS) in the US, hypothesized to be greater relative to a matched control group without PWS. We used a retrospective case-matched control design and longitudinal US administrative claims data (MarketScan) during a 5-year enrollment period (2009-2014). Patients with PWS were identified by Classification of Diseases, Ninth Revision, Clinical Modification diagnosis code 759.81. Controls were matched on age, sex, and payer type. Outcomes included total, outpatient, inpatient and prescription costs. After matching and application of inclusion/exclusion criteria, we identified 2030 patients with PWS (1161 commercial, 38 Medicare supplemental, and 831 Medicaid). Commercially insured patients with PWS (median age 10 years) had 8.8-times greater total annual direct medical costs than their counterparts without PWS (median age 10 years: median costs $14 907 vs $819; P < .0001; mean costs: $28 712 vs $3246). Outpatient care comprised the largest portion of medical resource utilization for enrollees with and without PWS (median $5605 vs $675; P < .0001; mean $11 032 vs $1804), followed by mean annual inpatient and medication costs, which were $10 879 vs $1015 (P < .001) and $6801 vs $428 (P < .001), respectively. Total annual direct medical costs were ∼42% greater for Medicaid-insured patients with PWS than their commercially insured counterparts, an increase partly explained by claims for Medicaid Waiver day and residential habilitation. Direct medical resource utilization was considerably greater among patients with PWS than members without the condition. This study provides a first step toward quantifying the financial burden of PWS posed to individuals, families, and society. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

  14. Novel Materials for High Efficiency Direct Methanol Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Carson, Stephen [Arkema Inc.; Mountz, David [Arkema Inc.; He, Wensheng [Arkema Inc.; Zhang, Tao [Arkema Inc.

    2013-12-31

    Direct methanol fuel cell membranes were developed using blends of different polyelectrolytes with PVDF. The membranes showed complex relationships between polyelectrolyte chemistry, morphology, and processing. Although the PVDF grade was found to have little effect on the membrane permselectivity, it does impact membrane conductivity and methanol permeation values. Other factors, such as varying the polyelectrolyte polarity, using varying crosslinking agents, and adjusting the equivalent weight of the membranes impacted methanol permeation, permselectivity, and areal resistance. We now understand, within the scope of the project work completed, how these inter-related performance properties can be tailored to achieve a balance of performance.

  15. Engineering an enantioselective amine oxidase for the synthesis of pharmaceutical building blocks and alkaloid natural products.

    Science.gov (United States)

    Ghislieri, Diego; Green, Anthony P; Pontini, Marta; Willies, Simon C; Rowles, Ian; Frank, Annika; Grogan, Gideon; Turner, Nicholas J

    2013-07-24

    The development of cost-effective and sustainable catalytic methods for the production of enantiomerically pure chiral amines is a key challenge facing the pharmaceutical and fine chemical industries. This challenge is highlighted by the estimate that 40-45% of drug candidates contain a chiral amine, fueling a demand for broadly applicable synthetic methods that deliver target structures in high yield and enantiomeric excess. Herein we describe the development and application of a "toolbox" of monoamine oxidase variants from Aspergillus niger (MAO-N) which display remarkable substrate scope and tolerance for sterically demanding motifs, including a new variant, which exhibits high activity and enantioselectivity toward substrates containing the aminodiphenylmethane (benzhydrylamine) template. By combining rational structure-guided engineering with high-throughput screening, it has been possible to expand the substrate scope of MAO-N to accommodate amine substrates containing bulky aryl substituents. These engineered MAO-N biocatalysts have been applied in deracemization reactions for the efficient asymmetric synthesis of the generic active pharmaceutical ingredients Solifenacin and Levocetirizine as well as the natural products (R)-coniine, (R)-eleagnine, and (R)-leptaflorine. We also report a novel MAO-N mediated asymmetric oxidative Pictet-Spengler approach to the synthesis of (R)-harmicine.

  16. Direct asymmetric vinylogous aldol reaction of allyl ketones with isatins: Divergent synthesis of 3-hydroxy-2-oxindole derivatives

    KAUST Repository

    Zhu, Bo; Zhang, Wen; Lee, Richmond; Han, Zhiqiang; Yang, Wenguo; Tan, Davin; Huang, Kuo-Wei; Jiang, Zhiyong

    2013-01-01

    6 in 1: The highly enantioselective title reaction is mediated by a bifunctional catalyst and leads to E-configured vinylogous aldol products (see scheme). These products are used as common intermediates in the synthesis of six biologically active 3

  17. Very short intracavity directional coupler for high-speed communication

    Science.gov (United States)

    Griffel, Giora

    1993-07-01

    We propose a novel intracavity modulator/switch that consists of a directional-coupler located inside a Fabry-Perot cavity. The back mirror of the cavity has a unit reflectivity so that both input and output signals are at the same side. In this way we obtain a two-port, single side element, with coupling length of 83.5 μm, which is the shortest modulation coupler proposed so far. The upper frequency limit due to photon lifetime is 275 GHz, which is well over the bandwidth constraints of microwave lumped structures. A unified approach for the analysis of this device and other similar structures is presented and discussed.

  18. Enantioselective conjugate addition of diethylzinc to chalcone catalyzed by Co(acac)(2) and chiral amino alcohols

    NARCIS (Netherlands)

    de Vries, A.H.M.; Feringa, B.L.

    1997-01-01

    Co(acac)(2) in the presence of chiral ligands has been employed as catalyst for the enantioselective conjugate addition of diethylzinc to chalcone. With chiral amino alcohols derived from (+)-camphor, enantioselectivities up to 83% were achieved. (C) 1997 Elsevier Science Ltd.

  19. Direct-radiator loudspeaker systems with high B1

    NARCIS (Netherlands)

    Vanderkooy, J.; Boers, P.M.; Aarts, R.M.

    2008-01-01

    In an extension of an earlier paper by the authors additional consequences of a dramatic increase in the motor strength Bl of a driver are shown. Not only is the efficiency of the loudspeaker and amplifier greatly increased, but high Bl values have a positive influence on other aspects of

  20. Directed evolution of a thermostable l-aminoacylase biocatalyst

    DEFF Research Database (Denmark)

    Parker, Brenda M.; Taylor, Ian N.; Woodley, John

    2011-01-01

    Enzymes from extreme environments possess highly desirable traits of activity and stability for application under process conditions. One such example is l-aminoacylase (E.C. 3.5.1.14) from Thermococcus litoralis (TliACY), which catalyzes the enantioselective amide hydrolysis of N-protected l......-amino acids, useful for resolving racemic mixtures in the preparation of chiral intermediates. Variants of this enzyme with improved activity and altered substrate preference are highly desirable. We have created a structural homology model of the enzyme and applied various two different directed evolution....... The substrate preference of wild type decreases with increasingly branched and sterically hindered substrates. However, the mutant S100T/M106K disrupted this simple trend by selectively improving the substrate preference for N-benzoyl valine, with a >30-fold shift in the ratio of kcat values for N...

  1. High performance coronagraphy for direct imaging of exoplanets

    Directory of Open Access Journals (Sweden)

    Guyon O.

    2011-07-01

    Full Text Available Coronagraphy has recently been an extremely active field of research, with several high performance concepts proposed, and several new coronagraphs tested in laboratories and telescopes. Coronagraph concepts can be grouped in a few broad categories: Lyot-type coronagraphs, pupil apodization and nulling interferometers. Among existing coronagraph concepts, several approach the fundamental performance limit imposed by the physical nature of light. To achieve their full potential, coronagraphs require exquisite wavefront control and calibration. This has been, and still is, the main bottleneck for the scientifically productive use of coronagraphs on ground-based telescopes. New and promising wavefront sensing techniques suitable for high contrast imaging have however been developed in the last few years and are started to be realized in laboratories. I will review some of these enabling technologies, and show that coronagraphs are now ready for “prime time” on existing and future telescopes.

  2. A High-Pressure Bi-Directional Cycloid Rotor Flowmeter

    Directory of Open Access Journals (Sweden)

    Shuo Liu

    2014-08-01

    Full Text Available The measurement of the flow rate of various liquids and gases is critical in industrial automation. Rotary positive displacement meters (rotary PD meters are highly accurate flowmeters that are widely employed in engineering applications, especially in custody transfer operations and hydraulic control systems. This paper presents a high pressure rotary PD meter containing a pair of internal cycloid rotors. It has the advantages of concise structure, low pressure loss, high accuracy and low noise. The curve of the internal rotor is designed as an equidistant curtate epicycloid curve with the external rotor curve as its conjugate. The calculation method used to determine the displacement of the cycloid rotor flowmeter is discussed. A prototype was fabricated, and experiments were performed to confirm measurements over a flow range of 1–100 L/min with relative errors of less than ±0.5%. The pressure loss through the flowmeter was about 3 bar at a flow rate of 100 L/min.

  3. A hybrid nanoantenna for highly enhanced directional spontaneous emission

    Energy Technology Data Exchange (ETDEWEB)

    Chou, R. Yuanying; Lu, Guowei, E-mail: guowei.lu@pku.edu.cn; Shen, Hongming; He, Yingbo; Cheng, Yuqing [State Key Laboratory for Mesoscopic Physics, Department of Physics, Peking University, Beijing 100871 (China); Perriat, Pascal [MATEIS, UMR 5510 CNRS, INSA-Lyon, Université de Lyon, Villeurbanne Cedex 69621 (France); Martini, Matteo; Tillement, Olivier [ILM, UMR 5306 CNRS, Université de Lyon, Villeurbanne Cedex 69622 (France); Gong, Qihuang [State Key Laboratory for Mesoscopic Physics, Department of Physics, Peking University, Beijing 100871 (China); Collaborative Innovation Center of Quantum Matter, Beijing 100871 (China)

    2014-06-28

    Spontaneous emission modulated by a hybrid plasmonic nanoantenna has been investigated by employing finite-difference time-domain method. The hybrid nanoantenna configurations constituted by a gap hot-spot and of a plasmonic corrugated grating and a metal reflector sandwiching a SiO{sub 2} thin layer which appears promising for high spontaneous emission enhancement devices. Simulation assays show that the coupling between the gap-antenna and plasmonic corrugations reaches an ultra-high near-field enhancement factor in the excitation process. Moreover, concerning the emission process, the corrugations concentrate the far-field radiated power within a tiny angular volume, offering unprecedented collection efficiency. In the past decades, many kinds of optical antennas have been proposed and optimized to enhance single molecule detection. However, the excitation enhancement effect for single individual or dimmer plasmonic nanostructure is limited due to intrinsic nonradiative decay of the nanoparticle plasmon and quantum tunneling effect. The proposed hybrid configuration overwhelms the enhancement limit of single individual plasmonic structure. The findings provide an insight into spontaneous emission high enhancement through integrating the functions of different metallic nanostructures.

  4. A hybrid nanoantenna for highly enhanced directional spontaneous emission

    International Nuclear Information System (INIS)

    Chou, R. Yuanying; Lu, Guowei; Shen, Hongming; He, Yingbo; Cheng, Yuqing; Perriat, Pascal; Martini, Matteo; Tillement, Olivier; Gong, Qihuang

    2014-01-01

    Spontaneous emission modulated by a hybrid plasmonic nanoantenna has been investigated by employing finite-difference time-domain method. The hybrid nanoantenna configurations constituted by a gap hot-spot and of a plasmonic corrugated grating and a metal reflector sandwiching a SiO 2 thin layer which appears promising for high spontaneous emission enhancement devices. Simulation assays show that the coupling between the gap-antenna and plasmonic corrugations reaches an ultra-high near-field enhancement factor in the excitation process. Moreover, concerning the emission process, the corrugations concentrate the far-field radiated power within a tiny angular volume, offering unprecedented collection efficiency. In the past decades, many kinds of optical antennas have been proposed and optimized to enhance single molecule detection. However, the excitation enhancement effect for single individual or dimmer plasmonic nanostructure is limited due to intrinsic nonradiative decay of the nanoparticle plasmon and quantum tunneling effect. The proposed hybrid configuration overwhelms the enhancement limit of single individual plasmonic structure. The findings provide an insight into spontaneous emission high enhancement through integrating the functions of different metallic nanostructures.

  5. Enantioselective Organocatalysis in Microreactors: Continuous Flow Synthesis of a (S-Pregabalin Precursor and (S-Warfarin

    Directory of Open Access Journals (Sweden)

    Riccardo Porta

    2015-08-01

    Full Text Available Continuous flow processes have recently emerged as a powerful technology for performing chemical transformations since they ensure some advantages over traditional batch procedures. In this work, the use of commercially available and affordable PEEK (Polyetheretherketone and PTFE (Polytetrafluoroethylene HPLC (High Performance Liquid Chromatography tubing as microreactors was exploited to perform organic reactions under continuous flow conditions, as an alternative to the commercial traditional glass microreactors. The wide availability of tubing with different sizes allowed quickly running small-scale preliminary screenings, in order to optimize the reaction parameters, and then to realize under the best experimental conditions a reaction scale up for preparative purposes. The gram production of some Active Pharmaceutical Ingredients (APIs such as (S-Pregabalin and (S-Warfarin was accomplished in short reaction time with high enantioselectivity, in an experimentally very simple procedure.

  6. Protein-directed modulation of high-LET hyperthermic radiosensitization

    International Nuclear Information System (INIS)

    Chang, P.Y.

    1991-01-01

    A pair of Chinese Hamster Ovary cell lines, the wild-type CHO-SC1, and its temperature-sensitive mutant (CHO-tsH1) was used to examine the importance of protein synthesis in the development of thermotolerance. The classical biphasic thermotolerant survival response to hyperthermia was observed in the SC1 cells after continuous heating at 41.5C to 42.5C, while tsH1 showed no thermotolerance. In separate experiments, each cell line was triggered and challenged at 45C. The heat doses were separated with graded incubaton periods at 35C or 40C for thermotolerance development. SC1 cells expressed thermoresistance, with the synthesis of heat shock proteins, under both incubation conditions. tsH1 cells expressed thermotolerance similar to that seen in the SC1 cells when incubated at 35C, but the survival response with the non-permissive 40C incubation was much reduced in the absence of protein synthesis. The combined effects of heavy-ion radiation and hyperthermia were examined using the same cell system. A mild heat dose of 41.5C was used in conjunction with Neon particle radiation of various high LET values. The cell killing effects were highly dependent on the sequence of application of heat and Neon radiation. Heat applied immediately after Neon irradiation was more cytotoxic to SC1 cells than when heat was applied prior to the irradiation. The ability of cells to synthesize new proteins plays a key role in this sequence-dependent thermal radiosensitization. In the absence of protein synthesis in the tsH1 cells, the high-LET thermal enhancement for cell-killing was unchanged regardless of the sequence. In the presence of protein synthetic activity in the SC1 cells, the thermal enhancement of radiation-induced cell killing was LET-dependent

  7. Electrohydrodynamics: a high-voltage direct energy conversion process

    International Nuclear Information System (INIS)

    Brun, S.

    1967-04-01

    This analysis consists of a theoretical and practical study of a high-tension electrical power generator based on the Van de Graaff generator principle, the main difference being that the charges produced are transported by a gas in motion and not by a belt. The electrical and thermal properties of such a generator are studied, as well as the difficult problem of the production of the ionised particles used in the conversion. A certain number of results already published on this process for converting kinetic energy into electrical energy is given, as well as some possible applications in the field of space technology. (author) [fr

  8. High Voltage Bi-directional Flyback Converter for Capacitive Actuator

    DEFF Research Database (Denmark)

    Thummala, Prasanth; Zhang, Zhe; Andersen, Michael A. E.

    2013-01-01

    in the converter, including the most dominating parameters of the high voltage transformer viz., self-capacitance and leakage inductance. The specific capacitive load for this converter is a dielectric electro active polymer (DEAP) actuator, which can be used as an effective replacement for conventional actuators...... in a number of applications. In this paper, the discharging energy efficiency definition is introduced. The proposed converter has been experimentally tested with the film capacitive load and the DEAP actuator, and the experimental results are shown together with the efficiency measurements....

  9. Premixed direct injection nozzle for highly reactive fuels

    Science.gov (United States)

    Ziminsky, Willy Steve; Johnson, Thomas Edward; Lacy, Benjamin Paul; York, William David; Uhm, Jong Ho; Zuo, Baifang

    2013-09-24

    A fuel/air mixing tube for use in a fuel/air mixing tube bundle is provided. The fuel/air mixing tube includes an outer tube wall extending axially along a tube axis between an inlet end and an exit end, the outer tube wall having a thickness extending between an inner tube surface having a inner diameter and an outer tube surface having an outer tube diameter. The tube further includes at least one fuel injection hole having a fuel injection hole diameter extending through the outer tube wall, the fuel injection hole having an injection angle relative to the tube axis. The invention provides good fuel air mixing with low combustion generated NOx and low flow pressure loss translating to a high gas turbine efficiency, that is durable, and resistant to flame holding and flash back.

  10. Novel strategy for protein exploration: high-throughput screening assisted with fuzzy neural network.

    Science.gov (United States)

    Kato, Ryuji; Nakano, Hideo; Konishi, Hiroyuki; Kato, Katsuya; Koga, Yuchi; Yamane, Tsuneo; Kobayashi, Takeshi; Honda, Hiroyuki

    2005-08-19

    To engineer proteins with desirable characteristics from a naturally occurring protein, high-throughput screening (HTS) combined with directed evolutional approach is the essential technology. However, most HTS techniques are simple positive screenings. The information obtained from the positive candidates is used only as results but rarely as clues for understanding the structural rules, which may explain the protein activity. In here, we have attempted to establish a novel strategy for exploring functional proteins associated with computational analysis. As a model case, we explored lipases with inverted enantioselectivity for a substrate p-nitrophenyl 3-phenylbutyrate from the wild-type lipase of Burkhorderia cepacia KWI-56, which is originally selective for (S)-configuration of the substrate. Data from our previous work on (R)-enantioselective lipase screening were applied to fuzzy neural network (FNN), bioinformatic algorithm, to extract guidelines for screening and engineering processes to be followed. FNN has an advantageous feature of extracting hidden rules that lie between sequences of variants and their enzyme activity to gain high prediction accuracy. Without any prior knowledge, FNN predicted a rule indicating that "size at position L167," among four positions (L17, F119, L167, and L266) in the substrate binding core region, is the most influential factor for obtaining lipase with inverted (R)-enantioselectivity. Based on the guidelines obtained, newly engineered novel variants, which were not found in the actual screening, were experimentally proven to gain high (R)-enantioselectivity by engineering the size at position L167. We also designed and assayed two novel variants, namely FIGV (L17F, F119I, L167G, and L266V) and FFGI (L17F, L167G, and L266I), which were compatible with the guideline obtained from FNN analysis, and confirmed that these designed lipases could acquire high inverted enantioselectivity. The results have shown that with the aid of

  11. The fate and enantioselective behavior of zoxamide during wine-making process.

    Science.gov (United States)

    Pan, Xinglu; Dong, Fengshou; Liu, Na; Cheng, Youpu; Xu, Jun; Liu, Xingang; Wu, Xiaohu; Chen, Zenglong; Zheng, Yongquan

    2018-05-15

    The fate of zoxamide and its enantiomers were evaluated in detail during wine-making process. The enantiomers of zoxamide were separated and determined by ultra-high-performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) after each processing procedure including washing, peeling, fermentation and clarification. Significant enantioselectivity was observed in all three treatments with the half-lives of R-zoxamide and S-zoxamide estimated to be 45.6 and 52.9 h in Group A, 45.0 and 52.1 h in Group B, 56.8 and 70.7 h in Group C, respectively. The results indicated that R-zoxamide degraded faster than S-zoxamide during the fermentation process. The processing factors (PFs) of each procedure were generally less than 1, and the PF of the overall process ranged from 0.019 to 0.051, which indicated that the whole process can reduce the zoxamide residue in red and white wine obviously. The results could help facilitate more accurate risk assessments of zoxamide during wine-making process. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. BCL::EMAS — Enantioselective Molecular Asymmetry Descriptor for 3D-QSAR

    Directory of Open Access Journals (Sweden)

    Mariusz Butkiewicz

    2012-08-01

    Full Text Available Stereochemistry is an important determinant of a molecule’s biological activity. Stereoisomers can have different degrees of efficacy or even opposing effects when interacting with a target protein. Stereochemistry is a molecular property difficult to represent in 2D-QSAR as it is an inherently three-dimensional phenomenon. A major drawback of most proposed descriptors for 3D-QSAR that encode stereochemistry is that they require a heuristic for defining all stereocenters and rank-ordering its substituents. Here we propose a novel 3D-QSAR descriptor termed Enantioselective Molecular ASymmetry (EMAS that is capable of distinguishing between enantiomers in the absence of such heuristics. The descriptor aims to measure the deviation from an overall symmetric shape of the molecule. A radial-distribution function (RDF determines a signed volume of tetrahedrons of all triplets of atoms and the molecule center. The descriptor can be enriched with atom-centric properties such as partial charge. This descriptor showed good predictability when tested with a dataset of thirty-one steroids commonly used to benchmark stereochemistry descriptors (r2 = 0.89, q2 = 0.78. Additionally, EMAS improved enrichment of 4.38 versus 3.94 without EMAS in a simulated virtual high-throughput screening (vHTS for inhibitors and substrates of cytochrome P450 (PUBCHEM AID891.

  13. Enantioselective HPLC determination of oxiracetam enantiomers and application to a pharmacokinetic study in beagle dogs.

    Science.gov (United States)

    Zhang, Qiuyang; Yang, Wei; Zhang, Qing; Yang, Yue; Li, Junxiu; Lu, Yang; Zheng, Yi; He, Jiake; Zhao, Di; Chen, Xijing

    2015-07-01

    An enantioselective high-performance liquid chromatography method was developed and validated for the determination of oxiracetam enantiomers, a cognition and memory enhancer, in beagle dog plasma. The plasma samples were prepared by methanol extraction from 200μL plasma, and then the baseline resolution was achieved on a Chiralpak ID column (250mm×4.6mm, 5μm) with mobile phase of hexane-ethanol-trifluoroacetic acid (78:22:0.1, v/v/v) at flow rate of 1.0mL/min. The column elute was monitored using ultraviolet detection at 214nm. The method was linear over concentration range 0.50-100μg/mL for both enantiomers. The relative standard deviation values for intra- and inter-day precision were 0.78-13.61 and 0.74-8.92% for (R)- and (S)-oxiracetam, respectively. The relative error values of accuracy ranged from -4.74 to 10.48% for (R)-oxiracetam and from -0.19 to 11.48% for (S)-oxiracetam. The method was successfully applied to a pharmacokinetic study of individual enantiomer and racemic oxiracetam in beagle dogs after oral administration. The disposition of the two enantiomers was not stereoselective and chiral inversion was not observed in beagle dogs. The pharmacokinetic profiles of (S)-oxiracetam were similar with racemic oxiracetam in beagle dogs. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Organocatalysts for enantioselective synthesis of fine chemicals: definitions, trends and developments

    Directory of Open Access Journals (Sweden)

    Chiara Palumbo

    2015-02-01

    Full Text Available Organocatalysis, that is the use of small organic molecules to catalyze organic transformations, has been included among the most successful concepts in asymmetric catalysis, and it has been used for the enantioselective construction of C–C, C–N, C–O, C–S, C–P and C–halide bonds. Since the seminal works in early 2000, the scientific community has been paying an ever-growing attention to the use of organocatalysts for the synthesis, with high yields and remarkable stereoselectivities, of optically active fine chemicals of interest for the pharmaceutical industry. A brief overview is here presented about the two main classes of substrate activation by the catalyst: covalent organocatalysis and non-covalent organocatalysis, with a more stringent focus on some recent outcomes in the field of the latter and of hydrogen bond-based catalysis. Finally, some successful examples of heterogenization of organocatalysts are also discussed, in the view of a potential industrial exploitation.

  15. Future directions in high-pressure neutron diffraction

    Science.gov (United States)

    Guthrie, M.

    2015-04-01

    The ability to manipulate structure and properties using pressure has been well known for many centuries. Diffraction provides the unique ability to observe these structural changes in fine detail on lengthscales spanning atomic to nanometre dimensions. Amongst the broad suite of diffraction tools available today, neutrons provide unique capabilities of fundamental importance. However, to date, the growth of neutron diffraction under extremes of pressure has been limited by the weakness of available sources. In recent years, substantial government investments have led to the construction of a new generation of neutron sources while existing facilities have been revitalized by upgrades. The timely convergence of these bright facilities with new pressure-cell technologies suggests that the field of high-pressure (HP) neutron science is on the cusp of substantial growth. Here, the history of HP neutron research is examined with the hope of gleaning an accurate prediction of where some of these revolutionary capabilities will lead in the near future. In particular, a dramatic expansion of current pressure-temperature range is likely, with corresponding increased scope for extreme-conditions science with neutron diffraction. This increase in coverage will be matched with improvements in data quality. Furthermore, we can also expect broad new capabilities beyond diffraction, including in neutron imaging, small angle scattering and inelastic spectroscopy.

  16. Direction discovery: A science enrichment program for high school students.

    Science.gov (United States)

    Sikes, Suzanne S; Schwartz-Bloom, Rochelle D

    2009-03-01

    Launch into education about pharmacology (LEAP) is an inquiry-based science enrichment program designed to enhance competence in biology and chemistry and foster interest in science careers especially among under-represented minorities. The study of how drugs work, how they enter cells, alter body chemistry, and exit the body engages students to conceptualize fundamental precepts in biology, chemistry, and math. Students complete an intensive three-week course in the fundamentals of pharmacology during the summer followed by a mentored research component during the school year. Following a 5E learning paradigm, the summer course captures student interest by introducing controversial topics in pharmacology and provides a framework that guides them to explore topics in greater detail. The 5E learning cycle is recapitulated as students extend their knowledge to design and to test an original research question in pharmacology. LEAP students demonstrated significant gains in biology and chemistry knowledge and interests in pursuing science. Several students earned honors for the presentation of their research in regional and state science fairs. Success of the LEAP model in its initial 2 years argues that coupling college-level coursework of interest to teens with an authentic research experience enhances high school student success in and enthusiasm for science. Copyright © 2009 International Union of Biochemistry and Molecular Biology, Inc.

  17. High-Precision Direct Mass Determination of Unstable Isotopes

    CERN Multimedia

    2002-01-01

    The extension of systematic high-precision measurements of the nuclear mass to nuclei far from the valley of $\\beta$ stability is of great interest in nuclear physics and astrophysics. The mass, or binding energy, is a fundamental gross property and a key input parameter for nuclear matter calculations. It is also a sensitive probe for collective and single-particle effects in nuclear structure. \\\\ \\\\ For such purposes, nuclear masses need to be known to an accuracy of about 10$^{-7}$ (i.e. $\\Delta$M~$\\leq$~10~keV for A~=~100). To resolve a particular mass from its nuclear isomers and isobars, resolving power of 10$^6$ are often required. To achieve this, the ions delivered by the on-line mass separator ISOLDE are confined in a Penning quadrupole trap. This trap is placed in the very homogeneous and stable magnetic field of a superconducting magnet. Here, the cyclotron frequency and hence the mass are determined. \\\\ \\\\ The first measurements using this new technique have been completed for a long chain of Cs ...

  18. Enantioselective Effect of Flurbiprofen on Lithium Disposition in Rats.

    Science.gov (United States)

    Uwai, Yuichi; Matsumoto, Masashi; Kawasaki, Tatsuya; Nabekura, Tomohiro

    2017-01-01

    Lithium is administered for treating bipolar disorders and is mainly excreted into urine. Nonsteroidal anti-inflammatory drugs inhibit this process. In this study, we examined the enantioselective effect of flurbiprofen on the disposition of lithium in rats. Pharmacokinetic experiments with lithium were performed. Until 60 min after the intravenous administration of lithium chloride at 30 mg/kg as a bolus, 17.8% of lithium injected was recovered into the urine. Its renal clearance was calculated to be 1.62 mL/min/kg. Neither creatinine clearance (Ccr) nor pharmacokinetics of lithium was affected by the simultaneous injection of (R)-flurbiprofen at 20 mg/kg. (S)-flurbiprofen impaired the renal function and interfered with the urinary excretion of lithium. The ratio of renal clearance of lithium to Ccr was decreased by the (S)-enantiomer. This study clarified that the (S)-flurbiprofen but not (R)-flurbiprofen inhibited the renal excretion of lithium in rats. © 2017 S. Karger AG, Basel.

  19. Enhanced catalysis and enantioselective resolution of racemic naproxen methyl ester by lipase encapsulated within iron oxide nanoparticles coated with calix[8]arene valeric acid complexes.

    Science.gov (United States)

    Sayin, Serkan; Akoz, Enise; Yilmaz, Mustafa

    2014-09-14

    In this study, two types of nanoparticles have been used as additives for the encapsulation of Candida rugosa lipase via the sol-gel method. In one case, the nanoparticles were covalently linked with a new synthesized calix[8]arene octa valeric acid derivative (C[8]-C4-COOH) to produce new calix[8]arene-adorned magnetite nanoparticles (NP-C[8]-C4-COOH), and then NP-C[8]-C4-COOH was used as an additive in the sol-gel encapsulation process. In the other case, iron oxide nanoparticles were directly added into the sol-gel encapsulation process in order to interact electrostatically with both C[8]-C4-COOH and Candida rugosa lipase. The catalytic activities and enantioselectivities of two novel encapsulated lipases (Enc-NP-C[8]-C4-COOH and Enc-C[8]-C4-COOH@Fe3O4) in the hydrolysis reaction of racemic naproxen methyl ester were evaluated. The results showed that the activity and enantioselectivity of the lipase were improved when the lipase was encapsulated in the presence of calixarene-based additives. Indeed, the encapsulated lipases have an excellent rate of enantioselectivity, with E = 371 and 265, respectively, as compared to the free enzyme (E = 137). The lipases encapsulated with C[8]-C4-COOH and iron oxide nanoparticles (Enc-C[8]-C4-COOH@Fe3O4) retained more than 86% of their initial activities after 5 repeated uses and 92% with NP-C[8]-C4-COOH.

  20. Ruthenium Catalyzed Diastereo- and Enantioselective Coupling of Propargyl Ethers with Alcohols: Siloxy-Crotylation via Hydride Shift Enabled Conversion of Alkynes to π-Allyls.

    Science.gov (United States)

    Liang, Tao; Zhang, Wandi; Chen, Te-Yu; Nguyen, Khoa D; Krische, Michael J

    2015-10-14

    The first enantioselective carbonyl crotylations through direct use of alkynes as chiral allylmetal equivalents are described. Chiral ruthenium(II) complexes modified by Josiphos (SL-J009-1) catalyze the C-C coupling of TIPS-protected propargyl ether 1a with primary alcohols 2a-2o to form products of carbonyl siloxy-crotylation 3a-3o, which upon silyl deprotection-reduction deliver 1,4-diols 5a-5o with excellent control of regio-, anti-diastereo-, and enantioselectivity. Structurally related propargyl ethers 1b and 1c bearing ethyl- and phenyl-substituents engage in diastereo- and enantioselective coupling, as illustrated in the formation of adducts 5p and 5q, respectively. Selective mono-tosylation of diols 5a, 5c, 5e, 5f, 5k, and 5m is accompanied by spontaneous cyclization to deliver the trans-2,3-disubstituted furans 6a, 6c, 6e, 6f, 6k, and 6m, respectively. Primary alcohols 2a, 2l, and 2p were converted to the siloxy-crotylation products 3a, 3l, and 3p, which upon silyl deprotection-lactol oxidation were transformed to the trans-4,5-disubstituted γ-butyrolactones 7a, 7l, and 7p. The formation of 7p represents a total synthesis of (+)-trans-whisky lactone. Unlike closely related ruthenium catalyzed alkyne-alcohol C-C couplings, deuterium labeling studies provide clear evidence of a novel 1,2-hydride shift mechanism that converts metal-bound alkynes to π-allyls in the absence of intervening allenes.

  1. Direct Utilization of Coal Syngas in High Temperature Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Celik, Ismail B. [West Virginia University, Morgantown, WV (United States)

    2014-10-30

    This EPSCoR project had two primary goals: (i) to build infrastructure and work force at WVU to support long-term research in the area of fuel cells and related sciences; (ii) study effects of various impurities found in coal-syngas on performance of Solid Oxide Fuel Cells (SOFC). As detailed in this report the WVU research team has made significant accomplishments in both of these areas. What follows is a brief summary of these accomplishments: State-of-the-art test facilities and diagnostic tools have been built and put into use. These include cell manufacturing, half-cell and full-cell test benches, XPS, XRD, TEM, Raman, EDAX, SEM, EIS, and ESEM equipment, unique in-situ measurement techniques and test benches (Environmental EM, Transient Mass-Spectrometer-MS, and IR Optical Temperature measurements). In addition, computational capabilities have been developed culminating in a multi-scale multi-physics fuel cell simulation code, DREAM-SOFC, as well as a Beowulf cluster with 64 CPU units. We have trained 16 graduate students, 10 postdoctoral fellows, and recruited 4 new young faculty members who have actively participated in the EPSCoR project. All four of these faculty members have already been promoted to the tenured associate professor level. With the help of these faculty and students, we were able to secure 14 research awards/contracts amounting to a total of circa $5.0 Million external funding in closely related areas of research. Using the facilities mentioned above, the effects of PH3, HCl, Cl2, and H2S on cell performance have been studied in detail, mechanisms have been identified, and also remedies have been proposed and demonstrated in the laboratory. For example, it has been determined that PH3 reacts rapidly with Ni to from secondary compounds which may become softer or even melt at high temperature and then induce Ni migration to the surface of the cell changing the material and micro-structural properties of the cell drastically. It is found that

  2. Theoretical study on the reaction mechanisms of Michael chirality addition between propionaldehyde and nitroalkene catalyzed by an enantioselective catalyst.

    Science.gov (United States)

    Zhou, Xinming; Li, Ling; Sun, Xuejun; Wang, Yajun; Du, Dongmei; Fu, Hui

    2018-06-01

    The asymmetric Michael addition between propionaldehyde and nitroalkene catalyzed by 8-(ethoxycarbonyl)-1,2,3,3a,8,8a-hexahydropyrrolo[2,3-b]indole-2-carboxylic acid has obtained relatively high yields and excellent enantioselectivities at room temperature. In this study, the molecular structures and optical activity of the most stable conformation I are optimized at B3LYP/6-311++ G(d,p) level. We find that levorotatory conformation I catalyzing the same Michael addition can produce laevo-product A and dextrorotatory conformation I' can obtain the dextral-product A'. These results have guiding significance for further studying on the new chemzymes and the mechanism of the obtained different chiral products. © 2018 Wiley Periodicals, Inc.

  3. Lithium Enolates in the Enantioselective Construction of Tetrasubstituted Carbon Centers with Chiral Lithium Amides as Noncovalent Stereodirecting Auxiliaries.

    Science.gov (United States)

    Yu, Kai; Lu, Ping; Jackson, Jeffrey J; Nguyen, Thuy-Ai D; Alvarado, Joseph; Stivala, Craig E; Ma, Yun; Mack, Kyle A; Hayton, Trevor W; Collum, David B; Zakarian, Armen

    2017-01-11

    Lithium enolates derived from carboxylic acids are ubiquitous intermediates in organic synthesis. Asymmetric transformations with these intermediates, a central goal of organic synthesis, are typically carried out with covalently attached chiral auxiliaries. An alternative approach is to utilize chiral reagents that form discrete, well-defined aggregates with lithium enolates, providing a chiral environment conducive of asymmetric bond formation. These reagents effectively act as noncovalent, or traceless, chiral auxiliaries. Lithium amides are an obvious choice for such reagents as they are known to form mixed aggregates with lithium enolates. We demonstrate here that mixed aggregates can effect highly enantioselective transformations of lithium enolates in several classes of reactions, most notably in transformations forming tetrasubstituted and quaternary carbon centers. Easy recovery of the chiral reagent by aqueous extraction is another practical advantage of this one-step protocol. Crystallographic, spectroscopic, and computational studies of the central reactive aggregate, which provide insight into the origins of selectivity, are also reported.

  4. Asymmetric Hydrogenation of Seven-Membered C=N-containing Heterocycles and Rationalization of the Enantioselectivity.

    Science.gov (United States)

    Balakrishna, Bugga; Bauzá, Antonio; Frontera, Antonio; Vidal-Ferran, Anton

    2016-07-18

    Iridium(I) complexes with phosphine-phosphite ligands efficiently catalyze the enantioselective hydrogenation of diverse seven-membered C=N-containing heterocyclic compounds (eleven examples; up to 97 % ee). The P-OP ligand L3, which incorporates an ortho-diphenyl substituted octahydrobinol phosphite fragment, provided the highest enantioselectivities in the hydrogenation of most of the heterocyclic compounds studied. The observed stereoselection was rationalized by means of DFT calculations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Percutaneous Direct Puncture Embolization with N-butyl-cyanoacrylate for High-flow Priapism

    Energy Technology Data Exchange (ETDEWEB)

    Tokue, Hiroyuki, E-mail: tokue@s2.dion.ne.jp; Shibuya, Kei [Gunma University Hospital, Department of Diagnostic and Interventional Radiology (Japan); Ueno, Hiroyuki [Isesaki Municipal Hospital, Department of Radiology (Japan); Tokue, Azusa; Tsushima, Yoshito [Gunma University Hospital, Department of Diagnostic and Interventional Radiology (Japan)

    2016-09-15

    There are many treatment options in high-flow priapism. Those mentioned most often are watchful waiting, Doppler-guided compression, endovascular highly selective embolization, and surgery. We present a case of high-flow priapism in a 57-year-old man treated by percutaneous direct puncture embolization of a post-traumatic left cavernosal arteriovenous fistula using N-butyl-cyanoacrylate. Erectile function was preserved during a 12-month follow-up. No patients with percutaneous direct puncture embolization for high-flow priapism have been reported previously. Percutaneous direct puncture embolization is a potentially useful and safe method for management of high-flow priapism.

  6. High pressure direct synthesis of adipic acid from cyclohexene and hydrogen peroxide via capillary microreactors

    NARCIS (Netherlands)

    Shang, M.; Noël, T.; Su, Y.; Hessel, V.

    2016-01-01

    The direct synthesis of adipic acid from hydrogen peroxide and cyclohexene was investigated in capillary microreactors at high temperature (up to 115°C ) and pressure (up to 70 bar). High temperature was already applied in micro-flow packed-bed reactors for the direct adipic acid synthesis. In our

  7. Chiral recognition with enantioselective ion exchangers based on carbamoylated cinchonan derivatives as chiral selectors for the HPLC enantioseparation

    International Nuclear Information System (INIS)

    Laemmerhofer, M.

    1996-11-01

    The high-performance liquid chromatographic (HPLC) separation of enantiomers is preferentially performed using chiral stationary phases (CSPs). If the chiral auxiliary (selector, SO) contains charged or ionizable groups one gets ion exchanger type CSPs which may bind and retain oppositely charged analytes (selectands, SAs). We prepared anion exchanger type CSPs with various quinine and quinidine carbarnates as chiral SOs immobilized either on porous or non-porous silica. These CSPs are able to resolve the enantiomers of a wide spectrum of chiral carboxylic, sulfonic, phosphonic, phosphoric acids and of many other chiral acidic solutes (e.g. N-derivatized alpha-, beta- , gamma-amino acids as 2,4-dinitrophenyl, 3,5-dinitrobenzoyl, benzoyl, acetyl, formyl, t.-butoxycarbonyl, benzyloxycarbonyl, 9-fluorenylmethoxycarbonyl, dansyl amino acids and peptides, alpha-arylalkylcarboxylic acids as profens, alpha-aryloxyalkylcarboxylic acids, alpha-arylthioalkylcarboxylic acids and acidic drugs like etodolac, proglumide, acenocournarol, leucovorin, omeprazole, pantoprazole) employing buffered aqueous mobile phases or non-aqueous mobile phases with buffer dissolved in the organic solvent. The influence of mobile phase parameters and other experimental conditions on retention and enantioselectivity has been evaluated for isocratic and gradient elution techniques, aided by the commercial method development computer software DryLab. Several 'Quantitative Structure-Retention Relationships' (QSRR) have been derived, which allowed prediction of enantioselectivity of new analytes and moreover the optimization of the SO-structure. Spectroscopic investigations as H-NMR, FTIR of certain SO-SA-complexes have been exerted to unveil the mechanism of chiral recognition. (author)

  8. Molecularly imprinted polymer-matrix nanocomposite for enantioselective electrochemical sensing of D- and L-aspartic acid

    International Nuclear Information System (INIS)

    Prasad, Bhim Bali; Srivastava, Amrita; Tiwari, Mahavir Prasad

    2013-01-01

    A new molecularly imprinted polymer-matrix (titanium dioxide nanoparticle/multiwalled carbon nanotubes) nanocomposite was developed for the modification of pencil graphite electrode as an enantioselective sensing probe for aspartic acid isomers, prevalent at ultra trace level in aqueous and real samples. The nanocomposite having many shape complementary cavities was synthesized adopting surface initiated-activators regenerated by electron transfer for atom transfer radical polymerization. The proposed sensor has high stability, nanocomposite uniformity, good reproducibility, and enhanced electrocatalytic activity to respond oxidative peak current of L-aspartic acid quantitatively by differential pulse anodic stripping voltammetry, without any cross-reactivity in real samples. Under the optimized operating conditions, the L-aspartic acid imprinted modified electrode showed a wide linear response for L-aspartic acid within the concentration range 9.98–532.72 ng mL −1 , with the minimum detection limit of 1.73–1.79 ng mL −1 (S/N = 3) in aqueous and real samples. Almost similar stringent limit (1.79 ng mL −1 ) was obtained with cerebrospinal fluid which is typical for the primitive diagnosis of neurological disorders, caused by an acute depletion of L-aspartic acid biomarker, in clinical settings. Highlights: • We have adopted surface initiated-activators regenerated by electron transfer for atom transfer radical polymerization. • This approach takes advantage of the nanostructured ultrathin imprinted film. • Successful enantioselective sensing and ultratrace analysis of D- and L-aspartic acid. • Stringent detection limit without any non-specific false-positive contribution

  9. Molecularly imprinted polymer-matrix nanocomposite for enantioselective electrochemical sensing of D- and L-aspartic acid

    Energy Technology Data Exchange (ETDEWEB)

    Prasad, Bhim Bali, E-mail: prof.bbpd@yahoo.com; Srivastava, Amrita; Tiwari, Mahavir Prasad

    2013-10-15

    A new molecularly imprinted polymer-matrix (titanium dioxide nanoparticle/multiwalled carbon nanotubes) nanocomposite was developed for the modification of pencil graphite electrode as an enantioselective sensing probe for aspartic acid isomers, prevalent at ultra trace level in aqueous and real samples. The nanocomposite having many shape complementary cavities was synthesized adopting surface initiated-activators regenerated by electron transfer for atom transfer radical polymerization. The proposed sensor has high stability, nanocomposite uniformity, good reproducibility, and enhanced electrocatalytic activity to respond oxidative peak current of L-aspartic acid quantitatively by differential pulse anodic stripping voltammetry, without any cross-reactivity in real samples. Under the optimized operating conditions, the L-aspartic acid imprinted modified electrode showed a wide linear response for L-aspartic acid within the concentration range 9.98–532.72 ng mL{sup −1}, with the minimum detection limit of 1.73–1.79 ng mL{sup −1} (S/N = 3) in aqueous and real samples. Almost similar stringent limit (1.79 ng mL{sup −1}) was obtained with cerebrospinal fluid which is typical for the primitive diagnosis of neurological disorders, caused by an acute depletion of L-aspartic acid biomarker, in clinical settings. Highlights: • We have adopted surface initiated-activators regenerated by electron transfer for atom transfer radical polymerization. • This approach takes advantage of the nanostructured ultrathin imprinted film. • Successful enantioselective sensing and ultratrace analysis of D- and L-aspartic acid. • Stringent detection limit without any non-specific false-positive contribution.

  10. In-silico driven engineering of enantioselectivity of a penicillin G acylase towards active pharmaceutical ingredients

    Czech Academy of Sciences Publication Activity Database

    Grulich, Michal; Brezovský, J.; Štěpánek, Václav; Palyzová, Andrea; Marešová, Helena; Zahradník, Jiří; Kyslíková, Eva; Kyslík, Pavel

    2016-01-01

    Roč. 133, Supplement 1 (2016), s. 53-59 ISSN 1381-1177 Institutional support: RVO:61388971 Keywords : Docking experiments * Enantioselectivity * Penicillin G acylase Subject RIV: EE - Microbiology, Virology OBOR OECD: Microbiology Impact factor: 2.269, year: 2016

  11. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

    KAUST Repository

    Ahmed, Syud M.; Poater, Albert; Childers, M. Ian; Widger, Peter C B; Lapointe, Anne M.; Lobkovsky, Emil B.; Coates, Geoffrey W.; Cavallo, Luigi

    2013-01-01

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

  12. Aziridino Alcohols as Catalysts for the Enantioselective Addition of Diethylzinc to Aldehydes

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Kornø, Hanne Tøfting; Guijarro, David

    1998-01-01

    The chiral aziridino alcohols 1 -3 have been prepared either from amino acids (1a from serine; 1b - 1i and 3 from threonine; 2a - 2e from allo-threonine) or via asymmetric synthesis (1j, 1k, 1l and 2f from methyl cinnamate). These easily available ligands act as catalysts for the enantioselective...

  13. Enantioselective radical reactions. Evaluation of nitrogen protecting groups in the synthesis of β2-amino acids

    Science.gov (United States)

    Sibi, Mukund P.; Patil, Kalyani

    2006-01-01

    We have investigated the effect of nitrogen protecting groups in radical addition trapping experiments leading to β2-amino acids. Of the three N-protecting groups examined, the phthalimido group was optimal with respect to both yields and enantioselectivity. Additionally, radical additions to more complex acrylates were also investigated, which provided access to functionalized β2-amino acids in modest selectivity. PMID:16799704

  14. Enantioselective radical reactions. Evaluation of nitrogen protecting groups in the synthesis of beta-amino acids.

    Science.gov (United States)

    Sibi, Mukund P; Patil, Kalyani

    2006-02-20

    We have investigated the effect of nitrogen protecting groups in radical addition trapping experiments leading to beta(2)-amino acids. Of the three N-protecting groups examined, the phthalimido group was optimal with respect to both yields and enantioselectivity. Additionally, radical additions to more complex acrylates were also investigated, which provided access to functionalized beta(2)-amino acids in modest selectivity.

  15. Exploiting the enantioselectivity of Baeyer-Villiger monooxygenases via boron oxidation

    NARCIS (Netherlands)

    Brondani, Patricia B.; Dudek, Hanna; Reis, Joel S.; Fraaije, Marco W.; Andrade, Leandro H.

    2012-01-01

    The enantioselective carbon-boron bond oxidation of several chiral boron-containing compounds by Baeyer-Villiger monooxygenases was evaluated. PAMO and M446G PAMO conveniently oxidized 1-phenylethyl boronate into the corresponding 1-(phenyl)ethanol (ee = 82-91%). Cyclopropyl boronic esters were also

  16. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

    KAUST Repository

    Ahmed, Syud M.

    2013-12-18

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

  17. Optimisation of the enantioselective biocatalytic hydrolysis of naproxen ethyl ester using ChiroCLEC-CR

    CSIR Research Space (South Africa)

    Brady, D

    2004-03-04

    Full Text Available In a biocatalytic reaction the immobilized lipase ChiroCLEC-CR enantioselectively hydrolysed a naproxen ethyl ester racemate, yielding (S)-naproxen with an enantiomeric excess of more than 98%, an enantiomeric ratio (E) of more than 100...

  18. DNA-based asymmetric catalysis : Sequence-dependent rate acceleration and enantioselectivity

    NARCIS (Netherlands)

    Boersma, Arnold J.; Klijn, Jaap E.; Feringa, Ben L.; Roelfes, Gerard

    2008-01-01

    This study shows that the role of DNA in the DNA-based enantioselective Diels-Alder reaction of azachalcone with cyclopentadiene is not limited to that of a chiral scaffold. DNA in combination with the copper complex of 4,4'-dimethyl-2,2'-bipyridine (Cu-L1) gives rise to a rate acceleration of up to

  19. Equilibrium Studies on Enantioselective Liquid-Liquid Amino Acid Extraction Using a Cinchona Alkaloid Extractant

    NARCIS (Netherlands)

    Schuur, Boelo; Winkelman, Jozef G. M.; Heeres, Hero J.

    2008-01-01

    The enantioselective extraction of aqueous 3,5-dinitrobenzoyl-R,S-leucine (A(R,S)) by a cinchona alkaloid extractant (C) in 1,2-dichloroethane was studied at room temperature (294 K) in a batch system for a range of intake concentrations (10(-4)-10(-3) mol/L) and pH values (3.8-6.6). The

  20. Improvement of enantioselectivity by immobilized imprinting of epoxide hydrolase from Rhodotorula glutinis

    NARCIS (Netherlands)

    Kronenburg, N.A.E.; Bont, de J.A.M.; Fischer, L.

    2001-01-01

    The yeast Rhodotorula glutinis contains an enantioselective, membrane-associated epoxide hydrolase (EH). Partially purified EH was immobilized in a two-step procedure. In the first step, the proteins were derivatized with itaconic anhydride. In the second step, the derivatized proteins were

  1. A DFT exploration of the enantioselective rearrangement of cyclohexene oxide to cyclohexenol

    DEFF Research Database (Denmark)

    Brandt, Peter; Norrby, Per-Ola; Andersson, Pher G.

    2003-01-01

    In this paper, we present computational results for the (1S,3R,4R)-3-(pyrrolidinyl)-methyl-2-azabicyclo[2.2.1]heptane mediated rearrangement of cyclohexene oxide. The results nicely explain the differences in enantioselectivities between catalytic and stoichiometric mode between different ligands...

  2. Uncovering Key Structural Features of an Enantioselective Peptide-Catalyzed Acylation Utilizing Advanced NMR Techniques

    Czech Academy of Sciences Publication Activity Database

    Procházková, Eliška; Kolmer, A.; Ilgen, J.; Schwab, M.; Kaltschnee, L.; Fredersdorf, M.; Schmidts, V.; Wende, R. C.; Schreiner, P. R.; Thiele, C. M.

    2016-01-01

    Roč. 55, č. 51 (2016), s. 15754-15759 ISSN 1433-7851 Institutional support: RVO:61388963 Keywords : conformational analysis * enantioselective acylations * NMR spectroscopy * pure shift NMR * RDCs Subject RIV: CC - Organic Chemistry Impact factor: 11.994, year: 2016

  3. Resolution of alpha/beta-amino acids by enantioselective penicillin G acylase from Achromobacter sp

    Czech Academy of Sciences Publication Activity Database

    Grulich, Michal; Brezovský, J.; Štěpánek, Václav; Palyzová, Andrea; Kyslíková, Eva; Kyslík, Pavel

    2015-01-01

    Roč. 122, DEC 2015 (2015), s. 240-247 ISSN 1381-1177 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0109 Institutional support: RVO:61388971 Keywords : Penicillin G acylase * Enantioselectivity * Homologous model Subject RIV: CE - Biochemistry Impact factor: 2.189, year: 2015

  4. Enantioselective analysis of proteinogenic amino acids in cerebrospinal fluid by capillary electrophoresis–mass spectrometry

    NARCIS (Netherlands)

    Prior, Amir; Sánchez-Hernández, Laura; Sastre-Toraño, Javier; Marina, Maria Luisa; de Jong, Gerhardus J.; Somsen, Govert W.

    2016-01-01

    d-Amino acids (AAs) are increasingly being recognized as essential molecules in biological systems. Enantioselective analysis of proteinogenic AAs in biological samples was accomplished by CE–MS employing β-CD as chiral selector and ESI via sheath-liquid (SL) interfacing. Prior to analysis, AAs were

  5. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui; Guo, Donghui; Munkerup, Kristin; Huang, Kuo-Wei; Li, Fangyi; Wang, Jian

    2018-01-01

    on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a

  6. The Enantioselectivity of Odor Sensation: Some Examples for Undergraduate Chemistry Courses

    Science.gov (United States)

    Kraft, Philip; Mannschreck, Albrecht

    2010-01-01

    This article discusses seven chiral odorants that demonstrate the enantioselectivity of odor sensation: carvone, Celery Ketone, camphor, Florhydral, 3-methyl-3-sulfanylhexan-1-ol, muscone, and methyl jasmonate. After a general introduction of the odorant-receptor interaction and the combinatorial code of olfaction, the olfactory properties of the…

  7. Simple Aziridino Alcohols as Chiral Ligands. Enantioselective Additions of Diethylzinc to N-Diphenylphosphinoylimines

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Andersson, Pher G.; Guijarro, David

    1996-01-01

    Simple chiral aziridino alcohols 2-5, easily available from L-serine, L-threonine or L-allo-threonine, have been used as ligands to promote the addition of Et(2)Zn to the diphenylphosphinoylimine 1 (Ar=Ph). Enantioselectivities of up to 94% could be obtained by proper choice of the substituents...

  8. Pd(II)-Catalyzed Enantioselective C-H Olefination of Diphenylacetic Acids

    Science.gov (United States)

    Shi, Bing-Feng; Zhang, Yang-Hui; Lam, Jonathan K.; Wang, Dong-Hui; Yu, Jin-Quan

    2009-01-01

    Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acid substrates has been achieved through the use of mono-protected chiral amino acid ligands. The absolute configuration of the resulting olefinated products is consistent with that of a proposed C-H insertion intermediate. PMID:20017549

  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. Metabolism of styrene in the human liver in vitro: interindividual variation and enantioselectivity

    NARCIS (Netherlands)

    Wenker, M. A.; Kezić, S.; Monster, A. C.; de Wolff, F. A.

    2001-01-01

    1. The interindividual variation and enantioselectivity of the in vitro styrene oxidation by cytochrome P450 have been investigated in 20 human microsomal liver samples. Liver samples were genotyped for the CYP2E1*6 and CYP2E1*5B alleles. 2. Kinetic analysis indicated the presence of at least two

  11. Echolocating bats emit a highly directional sonar sound beam in the field

    DEFF Research Database (Denmark)

    Surlykke, Annemarie; Boel Pedersen, Simon; Jakobsen, Lasse

    2009-01-01

    Bats use echolocation or biosonar to navigate and find prey at night. They emit short ultrasonic calls and listen for reflected echoes. The beam width of the calls is central to the function of the sonar, but directionality of echolocation calls has never been measured from bats flying in the wild....... We used a microphone array to record sounds and determine horizontal directionality for echolocation calls of the trawling Daubenton's bat, Myotis daubentonii, flying over a pond in its natural habitat. Myotis daubentonii emitted highly directional calls in the field. Directionality increased...... and directionality can be explained by the simple piston model. The model also suggests that the increase in the emitted intensity in the field is caused by the increased directionality, focusing sound energy in the forward direction. The bat may increase directionality by opening the mouth wider to emit a louder...

  12. High temperature high velocity direct power extraction using an open-cycle oxy-combustion system

    Energy Technology Data Exchange (ETDEWEB)

    Love, Norman [Univ. of Texas, El Paso, TX (United States)

    2017-09-29

    The implementation of oxy-fuel technology in fossil-fuel power plants may contribute to increased system efficiencies and a reduction of pollutant emissions. One technology that has potential to utilize the temperature of undiluted oxy-combustion flames is open-cycle magnetohydrodynamic (MHD) power generators. These systems can be configured as a topping cycle and provide high enthalpy, electrically conductive flows for direct conversion of electricity. This report presents the design and modeling strategies of a MHD combustor operating at temperatures exceeding 3000 K. Throughout the study, computational fluid dynamics (CFD) models were extensively used as a design and optimization tool. A lab-scale 60 kWth model was designed, manufactured and tested as part of this project. A fully-coupled numerical method was developed in ANSYS FLUENT to characterize the heat transfer in the system. This study revealed that nozzle heat transfer may be predicted through a 40% reduction of the semi-empirical Bartz correlation. Experimental results showed good agreement with the numerical evaluation, with the combustor exhibiting a favorable performance when tested during extended time periods. A transient numerical method was employed to analyze fuel injector geometries for the 60-kW combustor. The ANSYS FLUENT study revealed that counter-swirl inlets achieve a uniform pressure and velocity ratio when the ports of the injector length to diameter ratio (L/D) is 4. An angle of 115 degrees was found to increase distribution efficiency. The findings show that this oxy-combustion concept is capable of providing a high-enthalpy environment for seeding, in order to render the flow to be conductive. Based on previous findings, temperatures in the range of 2800-3000 K may enable magnetohydrodynamic power extraction. The heat loss fraction in this oxy-combustion system, based on CFD and analytical calculations, at optimal operating conditions, was estimated to be less than 10 percent

  13. Crystallization and preliminary X-ray analysis of an enantioselective halohydrin dehalogenase from Agrobacterium radiobacter AD1

    NARCIS (Netherlands)

    Jong, René M. de; Rozeboom, Henriëtte J.; Kalk, Kor H.; Tang, Lixia; Janssen, Dick B.; Dijkstra, Bauke W.

    2002-01-01

    Halohydrin dehalogenases are key enzymes in the bacterial degradation of vicinal halopropanols and structurally related nematocides. Crystals of the enantioselective halohydrin dehalogenase HheC from Agrobacterium radiobacter AD1 have been obtained at room temperature from hanging-drop

  14. Crystallization and preliminary X-ray analysis of an enantioselective halohydrin dehalogenase from Agrobacterium radiobacter AD1

    NARCIS (Netherlands)

    de Jong, RM; Rozeboom, HJ; Kalk, KH; Tang, Lixia; Janssen, DB; Dijkstra, BW

    Halohydrin dehalogenases are key enzymes in the bacterial degradation of vicinal halopropanols and structurally related nematocides. Crystals of the enantioselective halohydrin dehalogenase HheC from Agrobacterium radiobacter AD1 have been obtained at room temperature from hanging-drop

  15. Total syntheses of mitragynine, paynantheine and speciogynine via an enantioselective thiourea-catalysed Pictet-Spengler reaction

    NARCIS (Netherlands)

    Kerschgens, I. P.; Claveau, E.; Wanner, M.J.; Ingemann, S.; van Maarseveen, J.H.; Hiemstra, H.

    2012-01-01

    The pharmacologically interesting indole alkaloids (-)-mitragynine, (+)-paynantheine and (+)-speciogynine were synthesised in nine steps from 4-methoxytryptamine by a route featuring (i) an enantioselective thiourea-catalysed Pictet-Spengler reaction, providing the tetrahydro-β-carboline ring and

  16. One pot 'click' reactions : tandem enantioselective biocatalytic epoxide ring opening and [3+2] azide alkyne cycloaddition

    NARCIS (Netherlands)

    Campbell-Verduyn, Lachlan S.; Szymanski, Wiktor; Postema, Christiaan P.; Dierckx, Rudi A.; Elsinga, Philip H.; Janssen, Dick B.; Feringa, Ben L.

    2010-01-01

    Halohydrin dehalogenase (HheC) can perform enantioselective azidolysis of aromatic epoxides to 1,2-azido alcohols which are subsequently ligated to alkynes producing chiral hydroxy triazoles in a one-pot procedure with excellent enantiomeric excess.

  17. Tuning and Switching Enantioselectivity of Asymmetric Carboligation in an Enzyme through Mutational Analysis of a Single Hot Spot.

    Science.gov (United States)

    Wechsler, Cindy; Meyer, Danilo; Loschonsky, Sabrina; Funk, Lisa-Marie; Neumann, Piotr; Ficner, Ralf; Brodhun, Florian; Müller, Michael; Tittmann, Kai

    2015-12-01

    Enantioselective bond making and breaking is a hallmark of enzyme action, yet switching the enantioselectivity of the reaction is a difficult undertaking, and typically requires extensive screening of mutant libraries and multiple mutations. Here, we demonstrate that mutational diversification of a single catalytic hot spot in the enzyme pyruvate decarboxylase gives access to both enantiomers of acyloins acetoin and phenylacetylcarbinol, important pharmaceutical precursors, in the case of acetoin even starting from the unselective wild-type protein. Protein crystallography was used to rationalize these findings and to propose a mechanistic model of how enantioselectivity is controlled. In a broader context, our studies highlight the efficiency of mechanism-inspired and structure-guided rational protein design for enhancing and switching enantioselectivity of enzymatic reactions, by systematically exploring the biocatalytic potential of a single hot spot. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Quantum secure direct communication with high-dimension quantum superdense coding

    International Nuclear Information System (INIS)

    Wang Chuan; Li Yansong; Liu Xiaoshu; Deng Fuguo; Long Guilu

    2005-01-01

    A protocol for quantum secure direct communication with quantum superdense coding is proposed. It combines the ideas of block transmission, the ping-pong quantum secure direct communication protocol, and quantum superdense coding. It has the advantage of being secure and of high source capacity

  19. Enantioselective Construction of 3-Hydroxypiperidine Scaffolds by Sequential Action of Light and Rhodium upon N-Allylglyoxylamides.

    Science.gov (United States)

    Ishida, Naoki; Nečas, David; Masuda, Yusuke; Murakami, Masahiro

    2015-06-15

    3-Hydroxypiperidine scaffolds were enantioselectively constructed in an atom-economical way by sequential action of light and rhodium upon N-allylglyoxylamides. In a formal sense, the allylic C-H bond was selectively cleaved and enantioselectively added across the ketonic carbonyl group with migration of the double bond (carbonyl-ene-type reaction). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Study of In-Cylinder Reactions of High Power-Density Direct Injection Diesel Engines

    National Research Council Canada - National Science Library

    Jansons, M

    2004-01-01

    Direct-injection (DI) Diesel or compression-ignition (CI) engine combustion process is investigated when new design and operational strategies are employed in order to achieve a high power-density (HPD) engine...

  1. Directional enhancement of selected high-order-harmonics from intense laser irradiated blazed grating targets.

    Science.gov (United States)

    Zhang, Guobo; Chen, Min; Liu, Feng; Yuan, Xiaohui; Weng, Suming; Zheng, Jun; Ma, Yanyun; Shao, Fuqiu; Sheng, Zhengming; Zhang, Jie

    2017-10-02

    Relativistically intense laser solid target interaction has been proved to be a promising way to generate high-order harmonics, which can be used to diagnose ultrafast phenomena. However, their emission direction and spectra still lack tunability. Based upon two-dimensional particle-in-cell simulations, we show that directional enhancement of selected high-order-harmonics can be realized using blazed grating targets. Such targets can select harmonics with frequencies being integer times of the grating frequency. Meanwhile, the radiation intensity and emission area of the harmonics are increased. The emission direction is controlled by tailoring the local blazed structure. Theoretical and electron dynamics analysis for harmonics generation, selection and directional enhancement from the interaction between multi-cycle laser and grating target are carried out. These studies will benefit the generation and application of laser plasma-based high order harmonics.

  2. Enantioselective Analysis in instruments onboard ROSETTA/PHILAE and ExoMars

    Science.gov (United States)

    Hendrik Bredehöft, Jan; Thiemann, Wolfram; Meierhenrich, Uwe; Goesmann, Fred

    It has been suggested a number of times in the past, to look for chirality as a biomarker. So far, for lack of appropriate instrumentation, space missions have never included enantioselective analysis. The distinction between enantiomers is of crucial importance to the question of the origin of the very first (pre)biotic molecules. If molecules detected in situ on another celestial body were found to exhibit a chiral bias, this would mean that at least partial asymmetric synthesis could take place abiotically. If this chiral bias should be found to be near 100For the currently flying ESA mission ROSETTA an enantioselective instrument was built, to try for the first time to detect and separate chiral molecules in situ. This instrument is COSAC, the Cometary Sampling and Acquisition Experiment, an enantioselective GCMS device[1,2], which is included in the lander PHLIAE that will eventually in 2014 land on the nucleus of comet 67P/Churyumov-Gerasimenko. A similar but even more powerful type of enantioselective GC-MS is in preparation for ESA's ExoMars mission. This instrument is part of MOMA, the Mars Organic Molecules Analyser. It has the objective of identifying and quantifying chiral organic molecules in surface and subsurface samples of Mars. Currently ExoMars is scheduled for 2018. The newly developed enantioselective technique utilized by both COSAC and MOMA will be described, including sample acquisition, derivatization, and separation in space-resistant chiral stationary capillary columns with time-of-flight mass spectrometric detection. Results of enantioselective analyses of representative test samples with special emphasis on amino acids[3], the building blocks of protein polymers, will be presented and we will discuss potential results of space missions Rosetta and ExoMars. [1] Thiemann W.H.-P., Meierhenrich U.: ESA Mission ROSETTA Will Probe for Chirality of Cometary Amino Acids. Origins of Life and Evolution of Biospheres 31 (2001), 199-210. [2

  3. Statistical and direct decay of high-lying single-particle excitations

    International Nuclear Information System (INIS)

    Gales, S.

    1993-01-01

    Transfer reactions induced by hadronic probes at intermediate energies have revealed a rich spectrum of high-lying excitations embedded in the nuclear continuum. The investigation of their decay properties is believed to be a severe test of their microscopic structure as predicted by microscopic nuclear models. In addition the degree of damping of these simple modes in the nuclear continuum can be obtained by means of the measured particle (n,p) decay branching ratios. The neutron and proton decay studies of high-lying single-particle states in heavy nuclei are presented. (author). 13 refs., 9 figs

  4. 72-directional display having VGA resolution for high-appearance image generation

    Science.gov (United States)

    Takaki, Yasuhiro; Dairiki, Takeshi

    2006-02-01

    The high-density directional display, which was originally developed in order to realize a natural 3D display, is not only a 3D display but also a high-appearance display. The appearances of objects, such as glare and transparency, are the results of the reflection and the refraction of rays. The faithful reproduction of such appearances of objects is impossible using conventional 2D displays because rays diffuse on the display screen. The high-density directional display precisely controls the horizontal ray directions so that it can reproduce the appearances of objects. The fidelity of the reproduction of object appearances depends on the ray angle sampling pitch. The angle sampling pitch is determined by considering the human eye imaging system. In the present study the high-appearance display which has the resolution of 640×400 and emits rays in 72 different horizontal directions with the angle pitch of 0.38° was constructed. Two 72-directional displays were combined, each of which consisted of a high-resolution LCD panel (3,840×2,400) and a slanted lenticular sheet. Two images produced by two displays were superimposed by a half mirror. A slit array was placed at the focal plane of the lenticular sheet for each display to reduce the horizontal image crosstalk in the combined image. The impression analysis shows that the high-appearance display provides higher appearances and presence than the conventional 2D displays do.

  5. Evaluation of reversible interconversion in comprehensive two-dimensional gas chromatography using enantioselective columns in first and second dimensions.

    Science.gov (United States)

    Kröger, Sabrina; Wong, Yong Foo; Chin, Sung-Tong; Grant, Jacob; Lupton, David; Marriott, Philip J

    2015-07-24

    The reversible molecular interconversion behaviour of a synthesised oxime (2-phenylpropanaldehyde oxime; (C6H5)CH(CH3)CHN(OH)) was investigated by both, single dimensional gas chromatography (1D GC) and comprehensive two-dimensional gas chromatography (GC×GC). Previous studies on small molecular weight oximes were extended to this larger aromatic oxime (molar mass 149.19gmol(-1)) with interest in the extent of interconversion, enantioselective resolution, and retention time. On a polyethylene glycol (PEG; wax-type) column, a characteristic interconversion zone between two antipodes of E and Z isomers was formed by molecules which have undergone isomerisation on the column (E⇌Z). The extent of interconversion was investigated by varying chromatographic conditions (oven temperature and carrier flow rate) to understand the nature of the behaviour observed. The extent of interconversion was negligible in both enantioselective and methyl-phenylpolysiloxane phase-columns, correlating with the low polarity of the stationary phase. In order to obtain isomerisation along with enantio-resolution, a wax-type and an enantioselective column were coupled in either enantioselective-wax or wax-enantioselective order. The most appropriate column arrangement was selected for study by using a GC×GC experiment with either a wax-phase or phenyl-methylpolysiloxane phase as (2)D column. In addition to evaluation of these fast elution columns, a long narrow-bore enantioselective column (10m) was introduced as (2)D, providing an enantioselective-PEG (coupled-column ensemble: (1)D1+(1)D2)×enantioselective ((2)D) column combination. In this instance, the (1)D1 enantioselective column provides enantiomeric separation of the corresponding enantiomers ((R) and (S)) of (E)- and (Z)-2-phenylpropanaldehyde oxime, followed by E/Z isomerisation in the coupled (1)D2 PEG (reactor) column. The resulting chromatographic interconversion region was modulated and separated into either E/Z isomers

  6. High rate response of ultra-high-performance fiber-reinforced concretes under direct tension

    Energy Technology Data Exchange (ETDEWEB)

    Tran, Ngoc Thanh [Department of Civil and Environmental Engineering, Sejong University, 98 Gunja-Dong, Gwangjin-Gu, Seoul 143-747 (Korea, Republic of); Tran, Tuan Kiet [Department of Civil and Environmental Engineering, Sejong University, 98 Gunja-Dong, Gwangjin-Gu, Seoul 143-747 (Korea, Republic of); Department of Civil Engineering and Applied Mechanics, Ho Chi Minh City University of Technology and Education, 01 Vo Van Ngan, Thu Duc District, Ho Chi Minh City (Viet Nam); Kim, Dong Joo, E-mail: djkim75@sejong.ac.kr [Department of Civil and Environmental Engineering, Sejong University, 98 Gunja-Dong, Gwangjin-Gu, Seoul 143-747 (Korea, Republic of)

    2015-03-15

    The tensile response of ultra-high-performance fiber-reinforced concretes (UHPFRCs) at high strain rates (5–24 s{sup −} {sup 1}) was investigated. Three types of steel fibers, including twisted, long and short smooth steel fibers, were added by 1.5% volume content in an ultra high performance concrete (UHPC) with a compressive strength of 180 MPa. Two different cross sections, 25 × 25 and 25 × 50 mm{sup 2}, of tensile specimens were used to investigate the effect of the cross section area on the measured tensile response of UHPFRCs. Although all the three fibers generated strain hardening behavior even at high strain rates, long smooth fibers produced the highest tensile resistance at high rates whereas twisted fiber did at static rate. The breakages of twisted fibers were observed from the specimens tested at high strain rates unlike smooth steel fibers. The tensile behavior of UHPFRCs at high strain rates was clearly influenced by the specimen size, especially in post-cracking strength.

  7. Enantioselective recognition of an isomeric ligand by a biomolecule: mechanistic insights into static and dynamic enantiomeric behavior and structural flexibility.

    Science.gov (United States)

    Peng, Wei; Ding, Fei

    2017-10-24

    Chirality is a ubiquitous basic attribute of nature, which inseparably relates to the life activity of living organisms. However, enantiomeric differences have still failed to arouse enough attention during the biological evaluation and practical application of chiral substances, and this poses a large threat to human health. In the current study, we explore the enantioselective biorecognition of a chiral compound by an asymmetric biomolecule, and then decipher the molecular basis of such a biological phenomenon on the static and, in particular, the dynamic scale. In light of the wet experiments, in silico docking results revealed that the orientation of the latter part of the optical isomer structures in the recognition domain can be greatly affected by the chiral carbon center in a model ligand molecule, and this event may induce large disparities between the static chiral bioreaction modes and noncovalent interactions (especially hydrogen bonding). Dynamic stereoselective biorecognition assays indicated that the conformational stability of the protein-(S)-diclofop system is clearly greater than the protein-(R)-diclofop adduct; and moreover, the conformational alterations of the diclofop enantiomers in the dynamic process will directly influence the conformational flexibility of the key residues found in the biorecognition region. These points enable the changing trends of biopolymer structural flexibility and free energy to exhibit significant distinctions when proteins sterically recognize the (R)-/(S)-stereoisomers. The outcomes of the energy decomposition further showed that the van der Waals' energy has roughly the same contribution to the chiral recognition biosystems, whereas the contribution of electrostatic energy to the protein-(R)-diclofop complex is notably smaller than to the protein-(S)-diclofop bioconjugate. This proves that differences in the noncovalent bonds would have a serious impact on the stereoselective biorecognition between a

  8. Enantioselective apoptosis induced by individual isomers of bifenthrin in Hep G2 cells.

    Science.gov (United States)

    Liu, Huigang; Li, Juan

    2015-03-01

    Bifenthrin (BF) has been used in racemate for agricultural purposes against soil insects, leading to increased inputs into soil environments. However, most of the studies about the toxicology research on BF were performed in its racemic form. The aim of the present study was to evaluate the enantiomer-specific cis-BF-induced apoptosis and intracellular reactive oxygen species (ROS) generation on human hepatocarcinoma cells (Hep G2). The results of cell viability assay and cytoflow assay indicated an obvious enantioselective hepatocyte toxicity of 1S-cis-BF in Hep G2 cells. 1S-cis-BF also induced ROS production, up-regulated Bax protein expression and down-regulated Bcl-2 expression levels. The present study suggested that enantioselective toxicity should be evaluated on currently used chiral pesticides, such as synthetic pyrethroids. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Ultrasound-Assisted Enantioselective Esterification of Ibuprofen Catalyzed by a Flower-Like Nanobioreactor

    Directory of Open Access Journals (Sweden)

    Baiyi An

    2016-04-01

    Full Text Available A flower-like nanobioreactor was prepared for resolution of ibuprofen in organic solvents. Ultrasound irradiation has been used to improve the enzyme performance of APE1547 (a thermophilic esterase from the archaeon Aeropyrum pernix K1 in the enantioselective esterification. Under optimum reaction conditions (ultrasound power, 225 W; temperature, 45 °C; water activity, 0.21, the immobilized APE1547 showed an excellent catalytic performance (enzyme activity, 13.26 μmol/h/mg; E value, 147.1. After ten repeated reaction batches, the nanobioreactor retained almost 100% of its initial enzyme activity and enantioselectivity. These results indicated that the combination of the immobilization method and ultrasound irradiation can enhance the enzyme performance dramatically.

  10. Effects of metals on enantioselective toxicity and biotransformation of cis-bifenthrin in zebrafish.

    Science.gov (United States)

    Yang, Ye; Ji, Dapeng; Huang, Xin; Zhang, Jianyun; Liu, Jing

    2017-08-01

    Co-occurrence of pyrethroids and metals in watersheds previously has been reported to pose great risk to aquatic species. Pyrethroids are a class of chiral insecticides that have been shown to have enantioselective toxicity and biotransformation. However, the influence of metals on enantioselectivity of pyrethroids has not yet been evaluated. In the present study, the effects of cadmium (Cd), copper (Cu), and lead (Pb) on the enantioselective toxicity and metabolism of cis-bifenthrin (cis-BF) were investigated in zebrafish at environmentally relevant concentrations. The addition of Cd, Cu, or Pb significantly increased the mortality of zebrafish in racemate and R-enantiomer of cis-BF-treated groups. In rac-cis-BF- or 1R-cis-BF-treated groups, the addition of Cd, Cu, or Pb caused a decrease in enantiomeric fraction (EF) and an increased ratio of R-enantiomer residues in zebrafish. In 1S-cis-BF-treated groups, coexposure to Cd led to a lower EF and decreased residue levels of S-enantiomer. In addition, coexposure to the 3 metals resulted in different biodegradation characteristics of each enantiomer accompanied with differential changes in the expression of cytochrome P450 (CYP)1, CYP2, and CYP3 genes, which might be responsible for the enantioselective biodegradation of cis-BF in zebrafish. These results suggest that the influence of coexistent metals should be considered in the ecological risk assessment of chiral pyrethroids in aquatic environments. Environ Toxicol Chem 2017;36:2139-2146. © 2017 SETAC. © 2017 SETAC.

  11. A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines

    Directory of Open Access Journals (Sweden)

    Erli Sugiono

    2013-11-01

    Full Text Available A continuous-flow asymmetric organocatalytic photocyclization–transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Brønsted acid catalysis. The photocylization and subsequent reduction was performed with catalytic amount of chiral BINOL derived phosphoric acid diester and Hantzsch dihydropyridine as hydrogen source providing the desired products in good yields and with excellent enantioselectivities.

  12. Copper(II)/amine synergistically catalyzed enantioselective alkylation of cyclic N-acyl hemiaminals with aldehydes.

    Science.gov (United States)

    Sun, Shutao; Mao, Ying; Lou, Hongxiang; Liu, Lei

    2015-07-07

    The first catalytic asymmetric alkylation of N-acyl quinoliniums with aldehydes has been described. A copper/amine synergistic catalytic system has been developed, allowing the addition of functionalized aldehydes to a wide range of electronically varied N-acyl quinoliniums in good yields with excellent enantiocontrol. The synergistic catalytic system was also effective for N-acyl dihydroisoquinoliniums and β-caboliniums, demonstrating the general applicability of the protocol in the enantioselective alkylation of diverse cyclic N-acyl hemiaminals.

  13. Rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes.

    Science.gov (United States)

    Li, Changkun; Kähny, Matthias; Breit, Bernhard

    2014-12-08

    A rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes to give branched N-allyl 2-pyridones is reported. Preliminary mechanistic studies support the hypothesis that the reaction was initiated from the more acidic 2-hydroxypyridine form, and the initial kinetic O-allylation product was finally converted into the thermodynamically more stable N-allyl 2-pyridones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. An iron/amine-catalyzed cascade process for the enantioselective functionalization of allylic alcohols.

    Science.gov (United States)

    Quintard, Adrien; Constantieux, Thierry; Rodriguez, Jean

    2013-12-02

    Three is a lucky number: An enantioselective transformation of allylic alcohols into β-chiral saturated alcohols has been developed by combining two distinct metal- and organocatalyzed catalytic cycles. This waste-free triple cascade process merges an iron-catalyzed borrowing-hydrogen step with an aminocatalyzed nucleophilic addition reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. A dual Lewis base activation strategy for enantioselective carbene-catalyzed annulations.

    Science.gov (United States)

    Izquierdo, Javier; Orue, Ane; Scheidt, Karl A

    2013-07-24

    A dual activation strategy integrating N-heterocyclic carbene (NHC) catalysis and a second Lewis base has been developed. NHC-bound homoenolate equivalents derived from α,β-unsaturated aldehydes combine with transient reactive o-quinone methides in an enantioselective formal [4 + 3] fashion to access 2-benzoxopinones. The overall approach provides a general blueprint for the integration of carbene catalysis with additional Lewis base activation modes.

  16. Modelling substrate specificity and enantioselectivity for lipases and esterases by substrate-imprinted docking

    Directory of Open Access Journals (Sweden)

    Tyagi Sadhna

    2009-06-01

    Full Text Available Abstract Background Previously, ways to adapt docking programs that were developed for modelling inhibitor-receptor interaction have been explored. Two main issues were discussed. First, when trying to model catalysis a reaction intermediate of the substrate is expected to provide more valid information than the ground state of the substrate. Second, the incorporation of protein flexibility is essential for reliable predictions. Results Here we present a predictive and robust method to model substrate specificity and enantioselectivity of lipases and esterases that uses reaction intermediates and incorporates protein flexibility. Substrate-imprinted docking starts with covalent docking of reaction intermediates, followed by geometry optimisation of the resulting enzyme-substrate complex. After a second round of docking the same substrate into the geometry-optimised structures, productive poses are identified by geometric filter criteria and ranked by their docking scores. Substrate-imprinted docking was applied in order to model (i enantioselectivity of Candida antarctica lipase B and a W104A mutant, (ii enantioselectivity and substrate specificity of Candida rugosa lipase and Burkholderia cepacia lipase, and (iii substrate specificity of an acetyl- and a butyrylcholine esterase toward the substrates acetyl- and butyrylcholine. Conclusion The experimentally observed differences in selectivity and specificity of the enzymes were reproduced with an accuracy of 81%. The method was robust toward small differences in initial structures (different crystallisation conditions or a co-crystallised ligand, although large displacements of catalytic residues often resulted in substrate poses that did not pass the geometric filter criteria.

  17. Performance enhancement of direct ethanol fuel cell using Nafion composites with high volume fraction of titania

    Science.gov (United States)

    Matos, B. R.; Isidoro, R. A.; Santiago, E. I.; Fonseca, F. C.

    2014-12-01

    The present study reports on the performance enhancement of direct ethanol fuel cell (DEFC) at 130 °C with Nafion-titania composite electrolytes prepared by sol-gel technique and containing high volume fractions of the ceramic phase. It is found that for high volume fractions of titania (>10 vol%) the ethanol uptake of composites is largely reduced while the proton conductivity at high-temperatures is weakly dependent on the titania content. Such tradeoff between alcohol uptake and conductivity resulted in a boost of DEFC performance at high temperatures using Nafion-titania composites with high fraction of the inorganic phase.

  18. Early Left Parietal Activity Elicited by Direct Gaze: A High-Density EEG Study

    Science.gov (United States)

    Burra, Nicolas; Kerzel, Dirk; George, Nathalie

    2016-01-01

    Gaze is one of the most important cues for human communication and social interaction. In particular, gaze contact is the most primary form of social contact and it is thought to capture attention. A very early-differentiated brain response to direct versus averted gaze has been hypothesized. Here, we used high-density electroencephalography to test this hypothesis. Topographical analysis allowed us to uncover a very early topographic modulation (40–80 ms) of event-related responses to faces with direct as compared to averted gaze. This modulation was obtained only in the condition where intact broadband faces–as opposed to high-pass or low-pas filtered faces–were presented. Source estimation indicated that this early modulation involved the posterior parietal region, encompassing the left precuneus and inferior parietal lobule. This supports the idea that it reflected an early orienting response to direct versus averted gaze. Accordingly, in a follow-up behavioural experiment, we found faster response times to the direct gaze than to the averted gaze broadband faces. In addition, classical evoked potential analysis showed that the N170 peak amplitude was larger for averted gaze than for direct gaze. Taken together, these results suggest that direct gaze may be detected at a very early processing stage, involving a parallel route to the ventral occipito-temporal route of face perceptual analysis. PMID:27880776

  19. An Annotated Bibliography of High-Voltage Direct-Current Transmission and Flexible AC Transmission (FACTS) Devices, 1991-1993.

    Energy Technology Data Exchange (ETDEWEB)

    Litzenberger, Wayne; Lava, Val

    1994-08-01

    References are contained for HVDC systems, converter stations and components, overhead transmission lines, cable transmission, system design and operations, simulation of high voltage direct current systems, high-voltage direct current installations, and flexible AC transmission system (FACTS).

  20. Direct synthesis of highly porous interconnected carbon nanosheets and their application as high-performance supercapacitors.

    Science.gov (United States)

    Sevilla, Marta; Fuertes, Antonio B

    2014-05-27

    An easy, one-step procedure is proposed for the synthesis of highly porous carbon nanosheets with an excellent performance as supercapacitor electrodes. The procedure is based on the carbonization of an organic salt, i.e., potassium citrate, at a temperature in the 750-900 °C range. In this way, carbon particles made up of interconnected carbon nanosheets with a thickness of <80 nm are obtained. The porosity of the carbon nanosheets consists essentially of micropores distributed in two pore systems of 0.7-0.85 nm and 0.95-1.6 nm. Importantly, the micropore sizes of both systems can be enlarged by simply increasing the carbonization temperature. Furthermore, the carbon nanosheets possess BET surface areas in the ∼1400-2200 m(2) g(-1) range and electronic conductivities in the range of 1.7-7.4 S cm(-1) (measured at 7.1 MPa). These materials behave as high-performance supercapacitor electrodes in organic electrolyte and exhibit an excellent power handling ability and a superb robustness over long-term cycling. Excellent results were obtained with the supercapacitor fabricated from the material synthesized at 850 °C in terms of both gravimetric and volumetric energy and power densities. This device was able to deliver ∼13 Wh kg(-1) (5.2 Wh L(-1)) at an extremely high power density of 78 kW kg(-1) (31 kW L(-1)) and ∼30 Wh kg(-1) (12 Wh L(-1)) at a power density of 13 kW kg(-1) (5.2 kW L(-1)) (voltage range of 2.7 V).

  1. Bicyclic Guanidine Catalyzed Asymmetric Tandem Isomerization Intramolecular-Diels-Alder Reaction: The First Catalytic Enantioselective Total Synthesis of (+)-alpha-Yohimbine.

    Science.gov (United States)

    Feng, Wei; Jiang, Danfeng; Kee, Choon-Wee; Liu, Hongjun; Tan, Choon-Hong

    2016-02-04

    Hydroisoquinoline derivatives were prepared in moderate to good enantioselectivities via a bicyclic guanidine-catalyzed tandem isomerization intramolecular-Diels-Alder (IMDA) reaction of alkynes. With this synthetic method, the first enantioselective synthesis of (+)-alpha-yohimbine was completed in 9 steps from the IMDA products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. High stability and high activity Pd/ITO-CNTs electrocatalyst for direct formic acid fuel cell

    International Nuclear Information System (INIS)

    Qu, Wei-Li; Gu, Da-Ming; Wang, Zhen-Bo; Zhang, Jing-Jia

    2014-01-01

    Graphical abstract: The addition of ITO in Pd/CNTs catalyst significantly improves the activity and stability of catalyst for formic acid electrooxidation due to excellent stability and high electrical conductivity of ITO, and metal-support interaction between Pd nanoparticles and ITO. - Highlights: • Pd catalyst with ITO and CNTs as a mixture support for DFAFC was first prepared by microwave-assisted polyol process. • The activity and stability of Pd/ITO-CNTs catalyst is significantly higher than those of Pd/CNTs. • When ITO content is 50% of ITO/CNTs support mass, Pd/ITO-CNTs exhibits the best performance. - Abstract: Indium tin oxide (ITO) and carbon nanotube hybrid has been explored as a support for Pd catalyst. Pd/ITO-CNTs catalysts with different ITO contents were prepared by the microwave-assisted polyol process. The as-prepared Pd/ITO-CNTs catalysts were characterized by X-ray diffraction (XRD), energy dispersive analysis of X-ray (EDAX), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), and electrochemical measurements in this work. The TEM results show that Pd particle size distribution in the Pd/ITO-CNTs catalyst is more uniform than that in Pd/CNTs, indicating that the ITO can promote the dispersion of Pd nanoparticles. It is found that there is metal-support interaction between Pd nanoparticles and ITO in the Pd/ITO-CNTs catalyst through XPS test. The results of electrochemical tests prove that the Pd/ITO-CNTs catalysts exhibit higher electro-catalytic activity and stability than Pd/CNTs toward formic acid electrooxidation. When the ITO content is 50% of ITO-CNTs support mass, the Pd/ITO-CNTs catalyst has the best catalytic performance for formic acid electrooxidation. The peak current density of formic acid electrooxidation on the Pd/ITO-CNTs50% electrode is 1.53 times as high as that on Pd/CNTs, 2.31 times higher than that on Pd/ITO. The results of aging

  3. Investigation into the dissolution and direct assay of high-fired plutonium dioxide

    International Nuclear Information System (INIS)

    Patterson, J.K.

    1976-01-01

    A fusion-melt and dissolution assay method has been developed and tested for the quantitative analysis of high-fired plutonium dioxide. The method employs fusion of the plutonium dioxide at temperatures greater than the melting point of an eutectic mixture of potassium pyrosulfate plus sodium peroxide. The resultant melt is then titrated directly by either controlled potential coulometry or a gravimetric titration, using standardized ceric sulfate as the titrant. It has been concluded from these investigations that by using the techniques described, high-fired plutonium dioxide (stochiometric) can be quantitatively dissolved and assayed to a degree heretofore beyond the state-of-the-art, while showing direct traceability to the Federal standards. After fusion, the dissolution and direct assay is applicable to existing routine analytical procedures. The method was designed so as to minimize physical handling, simplify the chemical operations, and maximize the personal safety of the analyst at an appreciable cost savings per analysis

  4. Main Directions in Ensuring Business Continuity for Information and Telecommunication Systems of High Availability

    Directory of Open Access Journals (Sweden)

    Boris Mikhailovich Egorov

    2014-12-01

    Full Text Available Enterprise Continuity Program, Information and Telecommunication System of Bank of Russia The results of the analysis of the main directions to ensure business continuity for the information and telecommunication systems of high availability in relation to expansion of the problems range, their intellectualization and the modern IT implementation are given.

  5. High-Priority Directions of Modernization of University Education in Innovational Society

    Science.gov (United States)

    Sergeev, Nikolai

    2017-01-01

    Purpose: The purpose of this paper is to verify the offered hypothesis and to determine high-priority directions of modernization of university education in an innovational society by the example of modern Russia. Design/methodology/approach: During the empirical study of connection between university education and innovational development of…

  6. Direct measurements of air layer profiles under impacting droplets using high-speed color interferometry

    NARCIS (Netherlands)

    van der Veen, Roeland; Tran, Tuan; Lohse, Detlef; Sun, Chao

    2012-01-01

    A drop impacting on a solid surface deforms before the liquid makes contact with the surface. We directly measure the time evolution of the air layer profile under the droplet using high-speed color interferometry, obtaining the air layer thickness before and during the wetting process. Based on the

  7. Hydroxide Self-Feeding High-Temperature Alkaline Direct Formate Fuel Cells.

    Science.gov (United States)

    Li, Yinshi; Sun, Xianda; Feng, Ying

    2017-05-22

    Conventionally, both the thermal degradation of the anion-exchange membrane and the requirement of additional hydroxide for fuel oxidation reaction hinder the development of the high-temperature alkaline direct liquid fuel cells. The present work addresses these two issues by reporting a polybenzimidazole-membrane-based direct formate fuel cell (DFFC). Theoretically, the cell voltage of the high-temperature alkaline DFFC can be as high as 1.45 V at 90 °C. It has been demonstrated that a proof-of-concept alkaline DFFC without adding additional hydroxide yields a peak power density of 20.9 mW cm -2 , an order of magnitude higher than both alkaline direct ethanol fuel cells and alkaline direct methanol fuel cells, mainly because the hydrolysis of formate provides enough OH - ions for formate oxidation reaction. It was also found that this hydroxide self-feeding high-temperature alkaline DFFC shows a stable 100 min constant-current discharge at 90 °C, proving the conceptual feasibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Dynamic effects of social influence and direct marketing on the adoption of high-technology products

    NARCIS (Netherlands)

    Risselada, H.; Verhoef, P.C.; Bijmolt, T.H.A.

    Many firms capitalize on their customers' social networks to improve the success rate of their new products. In this article, the authors analyze the dynamic effects of social influence and direct marketing on the adoption of a new high-technology product. Social influence is likely to play a role

  9. FoCal – A high granularity electromagnetic calorimeter for forward direct photon measurements

    NARCIS (Netherlands)

    Zhang, C.

    2017-01-01

    The measurement of direct photon production at forward rapidity (y∼3−5) at the LHC provides access to the structure of protons and nuclei at very small values of fractional momentum (x∼10−5). FoCal, an extremely-high-granularity Forward Calorimeter covering 3.3<η<5.3 is proposed as a detector

  10. Optimization Tool for Direct Water Cooling System of High Power IGBT Modules

    DEFF Research Database (Denmark)

    Bahman, Amir Sajjad; Blaabjerg, Frede

    2016-01-01

    important issue for thermal design engineers. This paper aims to present a user friendly optimization tool for direct water cooling system of a high power module which enables the cooling system designer to identify the optimized solution depending on customer load profiles and available pump power. CFD...

  11. Enantioselective ProPhenol-catalyzed addition of 1,3-diynes to aldehydes to generate synthetically versatile building blocks and diyne natural products.

    Science.gov (United States)

    Trost, Barry M; Chan, Vincent S; Yamamoto, Daisuke

    2010-04-14

    A highly enantioselective method for the catalytic addition of terminal 1,3-diynes to aldehydes was developed using our dinuclear zinc ProPhenol (1) system. Furthermore, triphenylphosphine oxide was found to interact synergistically with the catalyst to substantially enhance the chiral recognition. The generality of this catalytic transformation was demonstrated with aryl, alpha,beta-unsaturated and saturated aldehydes, of which the latter were previously limited in alkynyl zinc additions. The chiral diynol products are also versatile building blocks that can be readily elaborated; this was illustrated through highly selective trans-hydrosilylations, which enabled the synthesis of a beta-hydroxyketone and enyne. Additionally, the development of this method allowed for the rapid total syntheses of several biologically important diynol-containing natural products.

  12. High-performance, polymer-based direct cellular interfaces for electrical stimulation and recording

    Science.gov (United States)

    Kim, Seong-Min; Kim, Nara; Kim, Youngseok; Baik, Min-Seo; Yoo, Minsu; Kim, Dongyoon; Lee, Won-June; Kang, Dong-Hee; Kim, Sohee; Lee, Kwanghee; Yoon, Myung-Han

    2018-04-01

    Due to the trade-off between their electrical/electrochemical performance and underwater stability, realizing polymer-based, high-performance direct cellular interfaces for electrical stimulation and recording has been very challenging. Herein, we developed transparent and conductive direct cellular interfaces based on a water-stable, high-performance poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) film via solvent-assisted crystallization. The crystallized PEDOT:PSS on a polyethylene terephthalate (PET) substrate exhibited excellent electrical/electrochemical/optical characteristics, long-term underwater stability without film dissolution/delamination, and good viability for primarily cultured cardiomyocytes and neurons over several weeks. Furthermore, the highly crystallized, nanofibrillar PEDOT:PSS networks enabled dramatically enlarged surface areas and electrochemical activities, which were successfully employed to modulate cardiomyocyte beating via direct electrical stimulation. Finally, the high-performance PEDOT:PSS layer was seamlessly incorporated into transparent microelectrode arrays for efficient, real-time recording of cardiomyocyte action potentials with a high signal fidelity. All these results demonstrate the strong potential of crystallized PEDOT:PSS as a crucial component for a variety of versatile bioelectronic interfaces.

  13. Small numbers are sensed directly, high numbers constructed from size and density.

    Science.gov (United States)

    Zimmermann, Eckart

    2018-04-01

    Two theories compete to explain how we estimate the numerosity of visual object sets. The first suggests that the apparent numerosity is derived from an analysis of more low-level features like size and density of the set. The second theory suggests that numbers are sensed directly. Consistent with the latter claim is the existence of neurons in parietal cortex which are specialized for processing the numerosity of elements in the visual scene. However, recent evidence suggests that only low numbers can be sensed directly whereas the perception of high numbers is supported by the analysis of low-level features. Processing of low and high numbers, being located at different levels of the neural hierarchy should involve different receptive field sizes. Here, I tested this idea with visual adaptation. I measured the spatial spread of number adaptation for low and high numerosities. A focused adaptation spread of high numerosities suggested the involvement of early neural levels where receptive fields are comparably small and the broad spread for low numerosities was consistent with processing of number neurons which have larger receptive fields. These results provide evidence for the claim that different mechanism exist generating the perception of visual numerosity. Whereas low numbers are sensed directly as a primary visual attribute, the estimation of high numbers however likely depends on the area size over which the objects are spread. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Properties of Laser-Produced Highly Charged Heavy Ions for Direct Injection Scheme

    CERN Document Server

    Sakakibara, Kazuhiko; Hayashizaki, Noriyosu; Ito, Taku; Kashiwagi, Hirotsugu; Okamura, Masahiro

    2005-01-01

    To accelerate highly charged intense ion beam, we have developed the Direct Plasma Injection Scheme (DPIS) with laser ion source. In this scheme an ion beam from a laser ion source is injected directly to a RFQ linac without a low energy beam transport (LEBT) and the beam loss in the LEBT can be avoided. We achieved high current acceleration of carbon ions (60mA) by DPIS with the high current optimized RFQ. As the next setp we will use heavier elements like Ag, Pb, Al and Cu as target in LIS (using CO2, Nd-YAG or other laser) for DPIS and will examine properties of laser-produced plasma (the relationship of between charge state and laser power density, the current dependence of the distance from the target, etc).

  15. Compact high order schemes with gradient-direction derivatives for absorbing boundary conditions

    Science.gov (United States)

    Gordon, Dan; Gordon, Rachel; Turkel, Eli

    2015-09-01

    We consider several compact high order absorbing boundary conditions (ABCs) for the Helmholtz equation in three dimensions. A technique called "the gradient method" (GM) for ABCs is also introduced and combined with the high order ABCs. GM is based on the principle of using directional derivatives in the direction of the wavefront propagation. The new ABCs are used together with the recently introduced compact sixth order finite difference scheme for variable wave numbers. Experiments on problems with known analytic solutions produced very accurate results, demonstrating the efficacy of the high order schemes, particularly when combined with GM. The new ABCs are then applied to the SEG/EAGE Salt model, showing the advantages of the new schemes.

  16. Advancements in high-power high-brightness laser bars and single emitters for pumping and direct diode application

    Science.gov (United States)

    An, Haiyan; Jiang, Ching-Long J.; Xiong, Yihan; Zhang, Qiang; Inyang, Aloysius; Felder, Jason; Lewin, Alexander; Roff, Robert; Heinemann, Stefan; Schmidt, Berthold; Treusch, Georg

    2015-03-01

    We have continuously optimized high fill factor bar and packaging design to increase power and efficiency for thin disc laser system pump application. On the other hand, low fill factor bars packaged on the same direct copper bonded (DCB) cooling platform are used to build multi-kilowatt direct diode laser systems. We have also optimized the single emitter designs for fiber laser pump applications. In this paper, we will give an overview of our recent advances in high power high brightness laser bars and single emitters for pumping and direct diode application. We will present 300W bar development results for our next generation thin disk laser pump source. We will also show recent improvements on slow axis beam quality of low fill factor bar and its application on performance improvement of 4-5 kW TruDiode laser system with BPP of 30 mm*mrad from a 600 μm fiber. Performance and reliability results of single emitter for multiemitter fiber laser pump source will be presented as well.

  17. Microstructure of directionally solidified Ti-Fe eutectic alloy with low interstitial and high mechanical strength

    Science.gov (United States)

    Contieri, R. J.; Lopes, E. S. N.; Taquire de La Cruz, M.; Costa, A. M.; Afonso, C. R. M.; Caram, R.

    2011-10-01

    The performance of Ti alloys can be considerably enhanced by combining Ti and other elements, causing an eutectic transformation and thereby producing composites in situ from the liquid phase. This paper reports on the processing and characterization of a directionally solidified Ti-Fe eutectic alloy. Directional solidification at different growth rates was carried out in a setup that employs a water-cooled copper crucible combined with a voltaic electric arc moving through the sample. The results obtained show that a regular fiber-like eutectic structure was produced and the interphase spacing was found to be a function of the growth rate. Mechanical properties were measured using compression, microindentation and nanoindentation tests to determine the Vickers hardness, compressive strength and elastic modulus. Directionally solidified eutectic samples presented high values of compressive strength in the range of 1844-3000 MPa and ductility between 21.6 and 25.2%.

  18. Molecularly imprinted polymer-matrix nanocomposite for enantioselective electrochemical sensing of D- and L-aspartic acid.

    Science.gov (United States)

    Prasad, Bhim Bali; Srivastava, Amrita; Tiwari, Mahavir Prasad

    2013-10-01

    A new molecularly imprinted polymer-matrix (titanium dioxide nanoparticle/multiwalled carbon nanotubes) nanocomposite was developed for the modification of pencil graphite electrode as an enantioselective sensing probe for aspartic acid isomers, prevalent at ultra trace level in aqueous and real samples. The nanocomposite having many shape complementary cavities was synthesized adopting surface initiated-activators regenerated by electron transfer for atom transfer radical polymerization. The proposed sensor has high stability, nanocomposite uniformity, good reproducibility, and enhanced electrocatalytic activity to respond oxidative peak current of L-aspartic acid quantitatively by differential pulse anodic stripping voltammetry, without any cross-reactivity in real samples. Under the optimized operating conditions, the L-aspartic acid imprinted modified electrode showed a wide linear response for L-aspartic acid within the concentration range 9.98-532.72 ng mL(-1), with the minimum detection limit of 1.73-1.79 ng mL(-1) (S/N=3) in aqueous and real samples. Almost similar stringent limit (1.79 ng mL(-1)) was obtained with cerebrospinal fluid which is typical for the primitive diagnosis of neurological disorders, caused by an acute depletion of L-aspartic acid biomarker, in clinical settings. Copyright © 2013 Elsevier B.V. All rights reserved.

  19. Direct writing of sub-wavelength ripples on silicon using femtosecond laser at high repetition rate

    International Nuclear Information System (INIS)

    Xie, Changxin; Li, Xiaohong; Liu, Kaijun; Zhu, Min; Qiu, Rong; Zhou, Qiang

    2016-01-01

    Graphical abstract: - Highlights: • The NSRs and DSRs are obtained on silicon surface. • With increasing direct writing speed, the NSRs suddenly changes and becomes the DSRs. • We develop a Sipe–Drude interference theory by considering the thermal excitation. - Abstract: The near sub-wavelength and deep sub-wavelength ripples on monocrystalline silicon were formed in air by using linearly polarized and high repetition rate femtosecond laser pulses (f = 76 MHz, λ = 800 nm, τ = 50 fs). The effects of laser pulse energy, direct writing speed and laser polarization on silicon surface morphology are studied. When the laser pulse energy is 2 nJ/pulse and the direct writing speed varies from 10 to 25 mm/s, the near sub-wavelength ripples (NSRs) with orientation perpendicular to the laser polarization are generated. While the direct writing speed reaches 30 mm/s, the direction of the obtained deep sub-wavelength ripples (DSRs) suddenly changes and becomes parallel to the laser polarization, rarely reported so far for femtosecond laser irradiation of silicon. Meanwhile, we extend the Sipe–Drude interference theory by considering the thermal excitation, and numerically calculate the efficacy factor for silicon irradiated by femtosecond laser pulses. The revised Sipe–Drude interference theoretical results show good agreement with the periods and orientations of sub-wavelength ripples.

  20. High Dietary Fructose: Direct or Indirect Dangerous Factors Disturbing Tissue and Organ Functions.

    Science.gov (United States)

    Zhang, Dong-Mei; Jiao, Rui-Qing; Kong, Ling-Dong

    2017-03-29

    High dietary fructose is a major contributor to insulin resistance and metabolic syndrome, disturbing tissue and organ functions. Fructose is mainly absorbed into systemic circulation by glucose transporter 2 (GLUT2) and GLUT5, and metabolized in liver to produce glucose, lactate, triglyceride (TG), free fatty acid (FFA), uric acid (UA) and methylglyoxal (MG). Its extrahepatic absorption and metabolism also take place. High levels of these metabolites are the direct dangerous factors. During fructose metabolism, ATP depletion occurs and induces oxidative stress and inflammatory response, disturbing functions of local tissues and organs to overproduce inflammatory cytokine, adiponectin, leptin and endotoxin, which act as indirect dangerous factors. Fructose and its metabolites directly and/or indirectly cause oxidative stress, chronic inflammation, endothelial dysfunction, autophagy and increased intestinal permeability, and then further aggravate the metabolic syndrome with tissue and organ dysfunctions. Therefore, this review addresses fructose-induced metabolic syndrome, and the disturbance effects of direct and/or indirect dangerous factors on the functions of liver, adipose, pancreas islet, skeletal muscle, kidney, heart, brain and small intestine. It is important to find the potential correlations between direct and/or indirect risk factors and healthy problems under excess dietary fructose consumption.

  1. High Dietary Fructose: Direct or Indirect Dangerous Factors Disturbing Tissue and Organ Functions

    Directory of Open Access Journals (Sweden)

    Dong-Mei Zhang

    2017-03-01

    Full Text Available High dietary fructose is a major contributor to insulin resistance and metabolic syndrome, disturbing tissue and organ functions. Fructose is mainly absorbed into systemic circulation by glucose transporter 2 (GLUT2 and GLUT5, and metabolized in liver to produce glucose, lactate, triglyceride (TG, free fatty acid (FFA, uric acid (UA and methylglyoxal (MG. Its extrahepatic absorption and metabolism also take place. High levels of these metabolites are the direct dangerous factors. During fructose metabolism, ATP depletion occurs and induces oxidative stress and inflammatory response, disturbing functions of local tissues and organs to overproduce inflammatory cytokine, adiponectin, leptin and endotoxin, which act as indirect dangerous factors. Fructose and its metabolites directly and/or indirectly cause oxidative stress, chronic inflammation, endothelial dysfunction, autophagy and increased intestinal permeability, and then further aggravate the metabolic syndrome with tissue and organ dysfunctions. Therefore, this review addresses fructose-induced metabolic syndrome, and the disturbance effects of direct and/or indirect dangerous factors on the functions of liver, adipose, pancreas islet, skeletal muscle, kidney, heart, brain and small intestine. It is important to find the potential correlations between direct and/or indirect risk factors and healthy problems under excess dietary fructose consumption.

  2. Direct Calculation of Permeability by High-Accurate Finite Difference and Numerical Integration Methods

    KAUST Repository

    Wang, Yi

    2016-07-21

    Velocity of fluid flow in underground porous media is 6~12 orders of magnitudes lower than that in pipelines. If numerical errors are not carefully controlled in this kind of simulations, high distortion of the final results may occur [1-4]. To fit the high accuracy demands of fluid flow simulations in porous media, traditional finite difference methods and numerical integration methods are discussed and corresponding high-accurate methods are developed. When applied to the direct calculation of full-tensor permeability for underground flow, the high-accurate finite difference method is confirmed to have numerical error as low as 10-5% while the high-accurate numerical integration method has numerical error around 0%. Thus, the approach combining the high-accurate finite difference and numerical integration methods is a reliable way to efficiently determine the characteristics of general full-tensor permeability such as maximum and minimum permeability components, principal direction and anisotropic ratio. Copyright © Global-Science Press 2016.

  3. Direct electrical stimulation of human cortex evokes high gamma activity that predicts conscious somatosensory perception

    Science.gov (United States)

    Muller, Leah; Rolston, John D.; Fox, Neal P.; Knowlton, Robert; Rao, Vikram R.; Chang, Edward F.

    2018-04-01

    Objective. Direct electrical stimulation (DES) is a clinical gold standard for human brain mapping and readily evokes conscious percepts, yet the neurophysiological changes underlying these percepts are not well understood. Approach. To determine the neural correlates of DES, we stimulated the somatosensory cortex of ten human participants at frequency-amplitude combinations that both elicited and failed to elicit conscious percepts, meanwhile recording neural activity directly surrounding the stimulation site. We then compared the neural activity of perceived trials to that of non-perceived trials. Main results. We found that stimulation evokes distributed high gamma activity, which correlates with conscious perception better than stimulation parameters themselves. Significance. Our findings suggest that high gamma activity is a reliable biomarker for perception evoked by both natural and electrical stimuli.

  4. Insight into the stereospecificity of short-chain thermus thermophilus alcohol dehydrogenase showing pro-S hydride transfer and prelog enantioselectivity.

    Science.gov (United States)

    Pennacchio, Angela; Giordano, Assunta; Esposito, Luciana; Langella, Emma; Rossi, Mosè; Raia, Carlo A

    2010-04-01

    The stereochemistry of the hydride transfer in reactions catalyzed by NAD(H)-dependent alcohol dehydrogenase from Thermus thermophilus HB27 was determined by means of (1)H-NMR spectroscopy. The enzyme transfers the pro-S hydrogen of [4R-(2)H]NADH and exhibits Prelog specificity. Enzyme-substrate docking calculations provided structural details about the enantioselectivity of this thermophilic enzyme. These results give additional insights into the diverse active site architectures of the largely versatile short-chain dehydrogenase superfamily enzymes. A feasible protocol for the synthesis of [4R-(2)H]NADH with high yield was also set up by enzymatic oxidation of 2-propanol-d(8) catalyzed by Bacillus stearothermophilus alcohol dehydrogenase.

  5. Highly integrated CO2 capture and conversion: Direct synthesis of cyclic carbonates from industrial flue gas

    KAUST Repository

    Barthel, Alexander; Saih, Youssef; Gimenez, Michel; Pelletier, Jeremie; Kü hn, Fritz Elmar; D´ Elia, Valerio; Basset, Jean-Marie

    2016-01-01

    Robust and selective catalytic systems based on early transition metal halides (Y, Sc, Zr) and organic nucleophiles were found able to quantitatively capture CO2 from diluted streams via formation of hemicarbonate species and to convert it to cyclic organic carbonates under ambient conditions. This observation was exploited in the direct and selective chemical fixation of flue gas CO2 collected from an industrial exhaust, affording high degrees of CO2 capture and conversion.

  6. Development of an intelligent high-voltage direct-current power supply for nuclear detectors

    International Nuclear Information System (INIS)

    Zhao Xiuliang

    1997-01-01

    The operation and performances of a new type direct-current high-voltage power supply are described. The power supply with intelligent feature is controlled by a single-chip microcomputer (8031), and various kinds of output voltage can be preset. The output-voltage is monitored and regulated by the single-chip microcomputer and displayed by LED. The output voltage is stable when the load current is within the allowable limits

  7. Highly integrated CO2 capture and conversion: Direct synthesis of cyclic carbonates from industrial flue gas

    KAUST Repository

    Barthel, Alexander

    2016-02-08

    Robust and selective catalytic systems based on early transition metal halides (Y, Sc, Zr) and organic nucleophiles were found able to quantitatively capture CO2 from diluted streams via formation of hemicarbonate species and to convert it to cyclic organic carbonates under ambient conditions. This observation was exploited in the direct and selective chemical fixation of flue gas CO2 collected from an industrial exhaust, affording high degrees of CO2 capture and conversion.

  8. Highly ordered Pd nanowire arrays as effective electrocatalysts for ethanol oxidation in direct alcohol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Xu, C.W. [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Wang, H. [Departement of Applied Chemistry, Dongguan University of Technology, Dongguan 523106 (China); Shen, P.K. [School of Physics and Engineering, Sun Yet-Sen University, Guangzhou 510275 (China); Jiang, S.P.

    2007-12-03

    Pd nanowire arrays (NWAs) with high electrochemically active surface area are successfully fabricated using anodized aluminum oxide electrodeposition. The electrocatalytic activity and stability of the Pd NWAs for ethanol electrooxidation are not only significantly higher that of conventional Pd film electrodes, but also higher than that of well-established commercial PtRu/C electrocatalysts. The Pd NWAs show great potential as electrocatalysts for ethanol electrooxidation in alkaline media in direct ethanol fuel cells. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  9. Enantioselective small molecule synthesis by carbon dioxide fixation using a dual Brønsted acid/base organocatalyst.

    Science.gov (United States)

    Vara, Brandon A; Struble, Thomas J; Wang, Weiwei; Dobish, Mark C; Johnston, Jeffrey N

    2015-06-17

    Carbon dioxide exhibits many of the qualities of an ideal reagent: it is nontoxic, plentiful, and inexpensive. Unlike other gaseous reagents, however, it has found limited use in enantioselective synthesis. Moreover, unprecedented is a tool that merges one of the simplest biological approaches to catalysis-Brønsted acid/base activation-with this abundant reagent. We describe a metal-free small molecule catalyst that achieves the three component reaction between a homoallylic alcohol, carbon dioxide, and an electrophilic source of iodine. Cyclic carbonates are formed enantioselectively.

  10. Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

    KAUST Repository

    Widger, Peter C. B.; Ahmed, Syud M.; Coates, Geoffrey W.

    2011-01-01

    Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

  11. Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

    KAUST Repository

    Widger, Peter C. B.

    2011-07-26

    Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

  12. Design, Synthesis and Biological Activity of Novel Reversible Peptidyl FVIIa Inhibitors Rh-Catalyzed Enantioselective Synthesis of Diaryl Amines

    DEFF Research Database (Denmark)

    Storgaard, Morten

    functional group tolerance. Unfortunately, these -aryl tetramic acids were too unreactive and ring opening toward the synthesis of the building block did not succeed. However, -aryl tetramic acids are still interesting compounds due to their potential biological activity. The building block 3.15 (P1......-catalyzed enantioselective synthesis of diaryl amines, which is an important class of compounds (Chapter 4). For example it is found in the third generation anti-histaminic agent levocetirizine. Development of efficient synthetic routes is therefore of considerably interest. The rhodium-catalyzed enantioselective synthesis...

  13. Rhodium-catalyzed enantioselective intramolecular C-H silylation for the syntheses of planar-chiral metallocene siloles.

    Science.gov (United States)

    Zhang, Qing-Wei; An, Kun; Liu, Li-Chuan; Yue, Yuan; He, Wei

    2015-06-01

    Reported herein is the rhodium-catalyzed enantioselective C-H bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of (S)-TMS-Segphos, the reactions took place under very mild conditions to afford metallocene-fused siloles in good to excellent yields and with ee values of up to 97%. During this study it was observed that the steric hindrance of chiral ligands had a profound influence on the reactivity and enantioselectivity of the reaction, and might hold the key to accomplishing conventionally challenging asymmetric C-H silylations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. An enantioselective approach toward 3,4-dihydroisocoumarin through the bromocyclization of styrene-type carboxylic acids.

    Science.gov (United States)

    Chen, Jie; Zhou, Ling; Tan, Chong Kiat; Yeung, Ying-Yeung

    2012-01-20

    A facile and enantioselective approach toward 3,4-dihydroisocoumarin was developed. The method involved an amino-thiocarbamate catalyzed enantioselective bromocyclization of styrene-type carboxylic acids, yielding 3-bromo-3,4-dihydroisocoumarins with good yields and ee's. 3-Bromo-3,4-dihydroisocoumarins are versatile building blocks for various dihydroisocoumarin derivatives in which the Br group can readily be modified to achieve biologically important 4-O-type and 4-N-type 3,4-dihydroisocoumarin systems. In addition, studies indicated that, by refining some parameters, the synthetically useful 5-exo phthalide products could be achieved with good yields and ee's.

  15. Experiences with High-Level Programming Directives for Porting Applications to GPUs

    International Nuclear Information System (INIS)

    Ding, Wei; Chapman, Barbara; Sankaran, Ramanan; Graham, Richard L.

    2012-01-01

    HPC systems now exploit GPUs within their compute nodes to accelerate program performance. As a result, high-end application development has become extremely complex at the node level. In addition to restructuring the node code to exploit the cores and specialized devices, the programmer may need to choose a programming model such as OpenMP or CPU threads in conjunction with an accelerator programming model to share and manage the difference node resources. This comes at a time when programmer productivity and the ability to produce portable code has been recognized as a major concern. In order to offset the high development cost of creating CUDA or OpenCL kernels, directives have been proposed for programming accelerator devices, but their implications are not well known. In this paper, we evaluate the state of the art accelerator directives to program several applications kernels, explore transformations to achieve good performance, and examine the expressiveness and performance penalty of using high-level directives versus CUDA. We also compare our results to OpenMP implementations to understand the benefits of running the kernels in the accelerator versus CPU cores.

  16. Direct synthesis of highly textured Ge on flexible polyimide films by metal-induced crystallization

    Energy Technology Data Exchange (ETDEWEB)

    Oya, N.; Toko, K., E-mail: toko@bk.tsukuba.ac.jp; Suemasu, T. [Institute of Applied Physics, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573 (Japan); Saitoh, N.; Yoshizawa, N. [Electron Microscope Facility, TIA, AIST, 16-1 Onogawa, Tsukuba 305-8569 (Japan)

    2014-06-30

    The highly (111)-textured Ge thin film (50-nm thickness) is demonstrated on a flexible polyimide film via the low-temperature crystallization (325 °C) of amorphous Ge using Al as a catalyst. Covering the polyimide with insulators significantly improved the crystal quality of the resulting Ge layer. In particular, SiN covering led to 97% (111)-oriented Ge with grains 200 μm in size, two orders larger than the grain size of polycrystalline Ge directly formed on the polyimide film. This achievement will give a way to realize advanced electronic and optical devices simultaneously allowing for high performance, inexpensiveness, and flexibility.

  17. Microwave testing of high-Tc based direct current to a single flux quantum converter

    DEFF Research Database (Denmark)

    Kaplunenko, V. K.; Fischer, Gerd Michael; Ivanov, Z. G.

    1994-01-01

    Design, simulation, and experimental investigations of a direct current to a single flux quantum converter loaded with a Josephson transmission line and driven by an external 70 GHz microwave oscillator are reported. The test circuit includes nine YBaCuO Josephson junctions aligned on the grain...... boundary of a 0°–32° asymmetric Y-ZrO2 bicrystal substrate. The performance of such converters is important for the development of the fast Josephson samplers required for testing of high-Tc rapid single flux quantum circuits in high-speed digital superconducting electronics. Journal of Applied Physics...

  18. Automated work-flow for processing high-resolution direct infusion electrospray ionization mass spectral fingerprints

    DEFF Research Database (Denmark)

    Hansen, Michael Adsetts Edberg; Smedsgaard, Jørn

    2007-01-01

    an automated data processing pipeline to compare large numbers of fingerprint spectra from direct infusion experiments analyzed by high resolution MS. We describe some of the intriguing problems that have to be addressed. starting with the conversion and pre-processing of the raw data to the final data......The use of mass spectrometry (MS) is pivotal in analyses of the metabolome and presents a major challenge for subsequent data processing. While the last few years have given new high performance instruments, there has not been a comparable development in data processing. In this paper we discuss...

  19. Opportunities and challenges in green house gases reduction using high pressure direct injection of natural gas

    International Nuclear Information System (INIS)

    Ouellette, P.

    2001-01-01

    In an effort to reduce Greenhouse Gases, Westport Innovations is developing a high pressure direct injection (HPDI) technology for gaseous fuels. This technology adapts the diesel cycle for gaseous fuels, since the diesel cycle provides high efficiency, high low-speed torque, fast transient capabilities and reliability. Because of their high efficiency, diesels are very favorable from a Greenhouse Gas (GHG) point of view, however they remain challenged by high nitrogen oxides (NOx) and particulate matter (PM) emissions. When directly injecting natural gas, NOx and PM emissions can be reduced by approximately 50% while maintaining the performance of the diesel engine. This allows the use of abundant and historically cheaper natural gas. Because of its lower carbon content per unit energy, natural gas also offers further GHG reduction over the diesel if the efficiency is preserved and if methane emissions are low. This paper discusses development efforts at Westport for several applications including on-highway trucks, light-duty delivery trucks and power generation

  20. Molecular Design of a Chiral Brønsted Acid with Two Different Acidic Sites: Regio-, Diastereo-, and Enantioselective Hetero-Diels-Alder Reaction of Azopyridinecarboxylate with Amidodienes Catalyzed by Chiral Carboxylic Acid-Monophosphoric Acid.

    Science.gov (United States)

    Momiyama, Norie; Tabuse, Hideaki; Noda, Hirofumi; Yamanaka, Masahiro; Fujinami, Takeshi; Yamanishi, Katsunori; Izumiseki, Atsuto; Funayama, Kosuke; Egawa, Fuyuki; Okada, Shino; Adachi, Hiroaki; Terada, Masahiro

    2016-09-07

    A chiral Brønsted acid containing two different acidic sites, chiral carboxylic acid-monophosphoric acid 1a, was designed to be a new and effective concept in catalytic asymmetric hetero-Diels-Alder reactions of azopyridinecarboxylate with amidodienes. The multipoint hydrogen-bonding interactions among the carboxylic acid, monophosphoric acid, azopyridinecarboxylate, and amidodiene achieved high catalytic and chiral efficiency, producing substituted 1,2,3,6-tetrahydropyridazines with excellent stereocontrol in a single step. This constitutes the first example of regio-, diastereo-, and enantioselective azo-hetero-Diels-Alder reactions by chiral Brønsted acid catalysis.

  1. A new enantioselective CE method for determination of oxcarbazepine and licarbazepine after fungal biotransformation.

    Science.gov (United States)

    Bocato, Mariana Zuccherato; Bortoleto, Marcela Armelim; Pupo, Mônica Tallarico; de Oliveira, Anderson Rodrigo Moraes

    2014-10-01

    The present work describes, for the first time, the simultaneous separation of oxcarbazepine (OXC) and its active metabolite 10-hydroxy-10,11-dihydrocarbamazepine (licarbazepine, Lic) by chiral CE. The developed method was employed to monitor the enantioselective biotransformation of OXC into its active metabolite by fungi. The electrophoretic separations were performed using 10 mmol/L of a Tris-phosphate buffer solution (pH 2.5) containing 1% w/v of β-CD phosphate sodium salt (P-β-CD) as running electrolyte, -20 kV of applied voltage and a 15°C capillary temperature. The method was linear over the concentration range of 1000-30 000 ng/mL for OXC and 75-900 ng/mL for each Lic enantiomer (r ≥ 0.9952). Within-day precision and accuracy evaluated by RSD and relative errors, respectively, were lower than 15% for all analytes. The validated method was used to evaluate the enantioselective biotransformation of OXC, mediated by fungi, into its active metabolite Lic. This study showed that the fungi Glomerella cingulata (VA1) and Beuveria bassiana were able to enantioselectively metabolize the OXC into Lic after 360 h of incubation. Biotransformation by the fungus Beuveria bassiana showed 79% enantiomeric excess for (S)-(+)-Lic, while VA1 gave an enantiomeric excess of 100% for (S)-(+)-Lic. This study opens a new route to the drug (S)-(+)-licarbazepine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Method for exciting inductive-resistive loads with high and controllable direct current

    International Nuclear Information System (INIS)

    Hill, H.M. Jr.

    1976-01-01

    The apparatus and method for transmitting dc power to a load circuit by applying a dc voltage from a standard waveform synthesizer to duration modulate a bipolar rectangular wave generator are described. As the amplitude of the dc voltage increases, the widths of the rectangular wave generator output pulses increase, and as the amplitude of the dc voltage decreases, the widths of the rectangular wave generator output pulses decrease. Thus, the waveform synthesizer selectively changes the durations of the rectangular wave generator bipolar output pulses so as to produce a rectangular wave ac carrier that is duration modulated in accordance with and in direct proportion to the voltage amplitude from the synthesizer. Thereupon, by transferring the carrier to the load circuit through an amplifier and a rectifier, the load current also corresponds directly to the voltage amplitude from the synthesizer. To this end, the rectified wave at less than 100 percent duty factor amounts to a doubled frequency direct voltage pulse train for applying a direct current to the load, while the current ripple is minimized by a high L/R in the load circuit. In one embodiment, a power transmitting power amplifier means having a dc power supply is matched to the load circuit through a transformer for current magnification without sacrificing load current duration capability, while negative voltage and current feedback are provided in order to insure good output fidelity. 4 Claims, 18 Drawing Figures

  3. Development of High Efficiency and Low Emission Low Temperature Combustion Diesel Engine with Direct EGR Injection

    Science.gov (United States)

    Ho, R. J.; Kumaran, P.; Yusoff, M. Z.

    2016-03-01

    Focus on energy and environmental sustainability policy has put automotive research & development directed to developing high efficiency and low pollutant power train. Diffused flame controlled diesel combustion has reach its limitation and has driven R&D to explore other modes of combustions. Known effective mode of combustion to reduce emission are Low temperature combustion (LTC) and homogeneous charge combustion ignition by suppressing Nitrogen Oxide(NOx) and Particulate Matter (PM) formation. The key control to meet this requirement are chemical composition and distribution of fuel and gas during a combustion process. Most research to accomplish this goal is done by manipulating injected mass flow rate and varying indirect EGR through intake manifold. This research paper shows viable alternative direct combustion control via co-axial direct EGR injection with fuel injection process. A simulation study with OpenFOAM is conducted by varying EGR injection velocity and direct EGR injector diameter performed with under two conditions with non-combustion and combustion. n-heptane (C7H16) is used as surrogate fuel together with 57 species 290 semi-detailed chemical kinetic model developed by Chalmers University is used for combustion simulation. Simulation result indicates viability of co-axial EGR injection as a method for low temperature combustion control.

  4. Directional Change Mediates the Physiological Response to High-Intensity Shuttle Running in Professional Soccer Players

    Directory of Open Access Journals (Sweden)

    Remy Tang

    2018-04-01

    Full Text Available The purpose of this study was to investigate the influence that different frequencies of deceleration and acceleration actions had on the physiological demands in professional soccer players. Thirteen players were monitored via microelectromechanical devices during shuttle running protocols which involved one, three, or seven 180 degree directional changes. Heart rate exertion (HRE (1.1 ± 0.7 and rating of perceived exertion (RPE (5 ± 1 were significantly higher for the protocol which included seven directional changes when compared to the protocols which included one (HRE 0.5 ± 0.3, ES = 1.1, RPE 3 ± 0, ES = 2.7 or three (HRE 0.5 ± 0.2, ES = 1.1, RPE 3 ± 1, ES = 1.9 directional changes (p < 0.05. The gravitational force (g-force as measured through accelerometry (ACC also showed a similar trend when comparing the seven (8628.2 ± 1630.4 g to the one (5888.6 ± 1159.1 g, ES = 1.9 or three (6526.9 ± 1257.6 g, ES = 1.4 directional change protocols (p < 0.05. The results of this study suggest that increasing the frequency of decelerations and accelerations at a high intensity running (HIR speed alters the movement demands and elevates the physiological responses in professional players. This data has implications for the monitoring of physical performance and implementation of training drills.

  5. High-throughput STR analysis for DNA database using direct PCR.

    Science.gov (United States)

    Sim, Jeong Eun; Park, Su Jeong; Lee, Han Chul; Kim, Se-Yong; Kim, Jong Yeol; Lee, Seung Hwan

    2013-07-01

    Since the Korean criminal DNA database was launched in 2010, we have focused on establishing an automated DNA database profiling system that analyzes short tandem repeat loci in a high-throughput and cost-effective manner. We established a DNA database profiling system without DNA purification using a direct PCR buffer system. The quality of direct PCR procedures was compared with that of conventional PCR system under their respective optimized conditions. The results revealed not only perfect concordance but also an excellent PCR success rate, good electropherogram quality, and an optimal intra/inter-loci peak height ratio. In particular, the proportion of DNA extraction required due to direct PCR failure could be minimized to <3%. In conclusion, the newly developed direct PCR system can be adopted for automated DNA database profiling systems to replace or supplement conventional PCR system in a time- and cost-saving manner. © 2013 American Academy of Forensic Sciences Published 2013. This article is a U.S. Government work and is in the public domain in the U.S.A.

  6. Enantioselective Intramolecular CH-Insertions upon Cu-Catalyzed Decomposition of Phenyliodonium Ylides

    Directory of Open Access Journals (Sweden)

    Christelle Boléa

    2001-02-01

    Full Text Available The Cu-catalyzed intramolecular CH insertion of phenyliodonium ylide 5b has been investigated at 0° C in the presence of several chiral ligands. Enantioselectivities vary in the range of 38–72 %, and are higher than those resulting from reaction of the diazo compound 5c at 65° C. The results are consistent with a carbenoid mechanism for Cu-catalyzed decomposition of phenyliodonium ylides.

  7. Organocatalytic Michael and Friedel–Crafts reactions in enantioselective synthesis of biologically active compounds

    International Nuclear Information System (INIS)

    Maltsev, O V; Beletskaya, Irina P; Zlotin, Sergei G

    2011-01-01

    Recent applications of organocatalytic Michael and Friedel–Crafts reactions in enantioselective synthesis of biologically active compounds: natural products, pharmaceutical agents and plant protection agents are reviewed. The key mechanisms of stereoinduction, types of organocatalysts and reagents used in these reactions are considered. The material is classified according to the type of newly formed bonds incorporating the asymmetric carbon atom, and the information for the most numerous C–C coupling reactions is systematized according to the natures of the electrophile and the nucleophile. The bibliography includes 433 references.

  8. Enantioselective developmental toxicity and immunotoxicity of pyraclofos toward zebrafish (Danio rerio)

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang, Shulin, E-mail: shulin@zju.edu.cn [Institute of Environmental Science, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Hangzhou 310058 (China); Zhang, Zhisheng [Institute of Environmental Science, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhang, Wenjing; Bao, Lingling [Institute of Environmental Science, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Hangzhou 310058 (China); Xu, Chao, E-mail: chaoxu@zjut.edu.cn [Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Zhang, Hu [Institute of Quality and Standard for Agro-products, Zhejiang Academy of Agricultural Sciences, Hangzhou 210021 (China)

    2015-02-15

    Highlights: • Pyraclofos has significant enantioselective aquatic toxicities to zebrafish. • Pyraclofos induces time- and concentration-dependent developmental toxicity and immunotoxicity. • The mRNA level of IL-1β gene was significantly up-regulated by pyraclofos. • Pyraclofos binds potently to IL-1β, potentially affecting IL-1β-dependent proinflammatory signal transduction. • Our in vitro and in silico studies help to understand the molecular basis for aquatic toxicity of pyraclofos. - Abstract: Pyraclofos, a relatively new organophosphorus pesticide, has shown potential ecotoxicities, however, its aquatic toxicity, especially enantioselective aquatic toxicity, remains largely unknown. Using zebrafish (Danio rerio) as a preeminent vertebrate aquatic model, the enantioselective differences in the developmental toxicity and immunotoxicity of pyraclofos were evaluated. Following 96-h exposure, pyraclofos enantiomers exhibited acute toxicity and showed lethal concentration 50 of 2.23 and 3.99 mg/L for (R)-Pyraclofos and (S)-Pyraclofos, respectively. Exposure to pyraclofos caused time- and concentration-dependent malformations such as pericardial edema, yolk sac edema, crooked bodies and hatching during the embryonic development, with markedly higher percentages of malformation at higher concentrations. The concentration-dependent immunotoxicity to zebrafish embryo exposed to low level pyraclofos was induced with significant up-regulation of mRNA levels of immune-related interleukin-1β (IL-1β) gene. (R)-Pyraclofos was consistently more toxic than (S)-Pyraclofos for the acute toxicity, developmental toxicity and immunotoxicity to zebrafish. Molecular dynamics simulations revealed that at the atomic level, (R)-Pyraclofos binds more potently to IL-1β protein than (S)-Pyraclofos. This enantioselective binding is mainly contributed by the distinct binding mode of pyraclofos enantiomers and their electrostatic interactions with IL-1β, which potentially

  9. Enantioselective biotransformation of propranolol to the active metabolite 4-hydroxypropranolol by endophytic fungi

    Directory of Open Access Journals (Sweden)

    Keyller Bastos Borges

    2011-01-01

    Full Text Available The enantioselective biotransformation of propranolol (Prop by the endophytic fungi Phomopsis sp., Glomerella cingulata, Penicillium crustosum, Chaetomium globosum and Aspergillus fumigatus was investigated by studying the kinetics of the aromatic hydroxylation reaction with the formation of 4-hydroxypropranolol (4-OH-Prop. Both Prop enantiomers were consumed by the fungi in the biotransformation process, but the 4-hydroxylation reaction yielded preferentially (--(S-4-OH-Prop. The quantity of metabolites biosynthesized varied slightly among the evaluated endophytic fungi. These results show that all investigated endophytic fungi could be used as biosynthetic tools in biotransformation processes to obtain the enantiomers of 4-OH-Prop.

  10. Enzymatic Kinetic Resolution of 2-Piperidineethanol for the Enantioselective Targeted and Diversity Oriented Synthesis

    Directory of Open Access Journals (Sweden)

    Dario Perdicchia

    2015-12-01

    Full Text Available 2-Piperidineethanol (1 and its corresponding N-protected aldehyde (2 were used for the synthesis of several natural and synthetic compounds. The existence of a stereocenter at position 2 of the piperidine skeleton and the presence of an easily-functionalized group, such as the alcohol, set 1 as a valuable starting material for enantioselective synthesis. Herein, are presented both synthetic and enzymatic methods for the resolution of the racemic 1, as well as an overview of synthesized natural products starting from the enantiopure 1.

  11. Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

    Directory of Open Access Journals (Sweden)

    Katherine M. Byrd

    2015-04-01

    Full Text Available The conjugate addition reaction has been a useful tool in the formation of carbon–carbon bonds. The utility of this reaction has been demonstrated in the synthesis of many natural products, materials, and pharmacological agents. In the last three decades, there has been a significant increase in the development of asymmetric variants of this reaction. Unfortunately, conjugate addition reactions using α,β-unsaturated amides and lactams remain underdeveloped due to their inherently low reactivity. This review highlights the work that has been done on both diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams.

  12. Enantioselective developmental toxicity and immunotoxicity of pyraclofos toward zebrafish (Danio rerio)

    International Nuclear Information System (INIS)

    Zhuang, Shulin; Zhang, Zhisheng; Zhang, Wenjing; Bao, Lingling; Xu, Chao; Zhang, Hu

    2015-01-01

    Highlights: • Pyraclofos has significant enantioselective aquatic toxicities to zebrafish. • Pyraclofos induces time- and concentration-dependent developmental toxicity and immunotoxicity. • The mRNA level of IL-1β gene was significantly up-regulated by pyraclofos. • Pyraclofos binds potently to IL-1β, potentially affecting IL-1β-dependent proinflammatory signal transduction. • Our in vitro and in silico studies help to understand the molecular basis for aquatic toxicity of pyraclofos. - Abstract: Pyraclofos, a relatively new organophosphorus pesticide, has shown potential ecotoxicities, however, its aquatic toxicity, especially enantioselective aquatic toxicity, remains largely unknown. Using zebrafish (Danio rerio) as a preeminent vertebrate aquatic model, the enantioselective differences in the developmental toxicity and immunotoxicity of pyraclofos were evaluated. Following 96-h exposure, pyraclofos enantiomers exhibited acute toxicity and showed lethal concentration 50 of 2.23 and 3.99 mg/L for (R)-Pyraclofos and (S)-Pyraclofos, respectively. Exposure to pyraclofos caused time- and concentration-dependent malformations such as pericardial edema, yolk sac edema, crooked bodies and hatching during the embryonic development, with markedly higher percentages of malformation at higher concentrations. The concentration-dependent immunotoxicity to zebrafish embryo exposed to low level pyraclofos was induced with significant up-regulation of mRNA levels of immune-related interleukin-1β (IL-1β) gene. (R)-Pyraclofos was consistently more toxic than (S)-Pyraclofos for the acute toxicity, developmental toxicity and immunotoxicity to zebrafish. Molecular dynamics simulations revealed that at the atomic level, (R)-Pyraclofos binds more potently to IL-1β protein than (S)-Pyraclofos. This enantioselective binding is mainly contributed by the distinct binding mode of pyraclofos enantiomers and their electrostatic interactions with IL-1β, which potentially

  13. Activation of lipase from .I.Geotrichum candidum./I. and its enantioselectivity towards xenobiotic substrates

    Czech Academy of Sciences Publication Activity Database

    Kejík, Z.; Zarevúcka, Marie; Demnerová, K.

    2003-01-01

    Roč. 97, č. 5 (2003), s. 293-294 ISSN 0009-2770. [Sigma-Aldrich konference mladých chemiků, biochemiků a molekulárních biologů /3./. 04.06.2003-07.06.2003, Devět skal - Žďárské vrchy] R&D Projects: GA MŠk OC D13.10 Institutional research plan: CEZ:AV0Z4055905 Keywords : lipase * enantioselectivity Subject RIV: CC - Organic Chemistry

  14. Rapid directed evolution of stabilized proteins with cellular high-throughput encapsulation solubilization and screening (CHESS).

    Science.gov (United States)

    Yong, K J; Scott, D J

    2015-03-01

    Directed evolution is a powerful method for engineering proteins towards user-defined goals and has been used to generate novel proteins for industrial processes, biological research and drug discovery. Typical directed evolution techniques include cellular display, phage display, ribosome display and water-in-oil compartmentalization, all of which physically link individual members of diverse gene libraries to their translated proteins. This allows the screening or selection for a desired protein function and subsequent isolation of the encoding gene from diverse populations. For biotechnological and industrial applications there is a need to engineer proteins that are functional under conditions that are not compatible with these techniques, such as high temperatures and harsh detergents. Cellular High-throughput Encapsulation Solubilization and Screening (CHESS), is a directed evolution method originally developed to engineer detergent-stable G proteins-coupled receptors (GPCRs) for structural biology. With CHESS, library-transformed bacterial cells are encapsulated in detergent-resistant polymers to form capsules, which serve to contain mutant genes and their encoded proteins upon detergent mediated solubilization of cell membranes. Populations of capsules can be screened like single cells to enable rapid isolation of genes encoding detergent-stable protein mutants. To demonstrate the general applicability of CHESS to other proteins, we have characterized the stability and permeability of CHESS microcapsules and employed CHESS to generate thermostable, sodium dodecyl sulfate (SDS) resistant green fluorescent protein (GFP) mutants, the first soluble proteins to be engineered using CHESS. © 2014 Wiley Periodicals, Inc.

  15. High-content analysis of single cells directly assembled on CMOS sensor based on color imaging.

    Science.gov (United States)

    Tanaka, Tsuyoshi; Saeki, Tatsuya; Sunaga, Yoshihiko; Matsunaga, Tadashi

    2010-12-15

    A complementary metal oxide semiconductor (CMOS) image sensor was applied to high-content analysis of single cells which were assembled closely or directly onto the CMOS sensor surface. The direct assembling of cell groups on CMOS sensor surface allows large-field (6.66 mm×5.32 mm in entire active area of CMOS sensor) imaging within a second. Trypan blue-stained and non-stained cells in the same field area on the CMOS sensor were successfully distinguished as white- and blue-colored images under white LED light irradiation. Furthermore, the chemiluminescent signals of each cell were successfully visualized as blue-colored images on CMOS sensor only when HeLa cells were placed directly on the micro-lens array of the CMOS sensor. Our proposed approach will be a promising technique for real-time and high-content analysis of single cells in a large-field area based on color imaging. Copyright © 2010 Elsevier B.V. All rights reserved.

  16. High corrosion resistance of magnesium coated with hydroxyapatite directly synthesized in an aqueous solution

    International Nuclear Information System (INIS)

    Hiromoto, Sachiko; Yamamoto, Akiko

    2009-01-01

    Anticorrosion coatings are crucial for practical applications of magnesium alloys, which are used to reduce the weight of vehicles, aircraft, electronics enclosures etc. Hydroxyapatite (HAp) potentially offers high corrosion resistance and no environmental toxicity because its thermodynamic structural stability is high and it is a basic component of bone. However, direct synthesis of HAp on magnesium in aqueous solutions has been a scientific challenge because Mg ions prevent HAp crystallization. A new method of direct synthesis of HAp on magnesium was developed using a Ca chelate compound, which can maintain a sufficiently high concentration of Ca ions on the magnesium surface to overcome prevention of HAp crystallization with Mg ions. Highly crystallized HAp coatings were successfully formed on pure magnesium and AZ series alloys. Corrosion behavior of HAp-coated pure magnesium was examined by cyclic dry and wet tests with 1 g m -2 NaCl on the surface and polarization tests in a 3.5 wt% NaCl solution. A HAp-coated pure magnesium showed no noticeable corrosion pits after the dry and wet test. HAp-coated specimens showed 10 3 -10 4 times lower anodic current density than as-polished specimen in the polarization test. The results demonstrate the remarkable anticorrosion performance of HAp coatings on magnesium for the first time.

  17. High corrosion resistance of magnesium coated with hydroxyapatite directly synthesized in an aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Hiromoto, Sachiko [Biomaterials Center, National Institute for Materials Science, 1-1 Namiki, Tsukuba 305-0044 (Japan); International Center for Materials Nanoarchitectonics, National Institute for Materials Science, 1-1 Namiki, Tsukuba 305-0044 (Japan)], E-mail: hiromoto.sachiko@nims.go.jp; Yamamoto, Akiko [Biomaterials Center, National Institute for Materials Science, 1-1 Namiki, Tsukuba 305-0044 (Japan); International Center for Materials Nanoarchitectonics, National Institute for Materials Science, 1-1 Namiki, Tsukuba 305-0044 (Japan)

    2009-11-30

    Anticorrosion coatings are crucial for practical applications of magnesium alloys, which are used to reduce the weight of vehicles, aircraft, electronics enclosures etc. Hydroxyapatite (HAp) potentially offers high corrosion resistance and no environmental toxicity because its thermodynamic structural stability is high and it is a basic component of bone. However, direct synthesis of HAp on magnesium in aqueous solutions has been a scientific challenge because Mg ions prevent HAp crystallization. A new method of direct synthesis of HAp on magnesium was developed using a Ca chelate compound, which can maintain a sufficiently high concentration of Ca ions on the magnesium surface to overcome prevention of HAp crystallization with Mg ions. Highly crystallized HAp coatings were successfully formed on pure magnesium and AZ series alloys. Corrosion behavior of HAp-coated pure magnesium was examined by cyclic dry and wet tests with 1 g m{sup -2} NaCl on the surface and polarization tests in a 3.5 wt% NaCl solution. A HAp-coated pure magnesium showed no noticeable corrosion pits after the dry and wet test. HAp-coated specimens showed 10{sup 3}-10{sup 4} times lower anodic current density than as-polished specimen in the polarization test. The results demonstrate the remarkable anticorrosion performance of HAp coatings on magnesium for the first time.

  18. A new omni-directional multi-camera system for high resolution surveillance

    Science.gov (United States)

    Cogal, Omer; Akin, Abdulkadir; Seyid, Kerem; Popovic, Vladan; Schmid, Alexandre; Ott, Beat; Wellig, Peter; Leblebici, Yusuf

    2014-05-01

    Omni-directional high resolution surveillance has a wide application range in defense and security fields. Early systems used for this purpose are based on parabolic mirror or fisheye lens where distortion due to the nature of the optical elements cannot be avoided. Moreover, in such systems, the image resolution is limited to a single image sensor's image resolution. Recently, the Panoptic camera approach that mimics the eyes of flying insects using multiple imagers has been presented. This approach features a novel solution for constructing a spherically arranged wide FOV plenoptic imaging system where the omni-directional image quality is limited by low-end sensors. In this paper, an overview of current Panoptic camera designs is provided. New results for a very-high resolution visible spectrum imaging and recording system inspired from the Panoptic approach are presented. The GigaEye-1 system, with 44 single cameras and 22 FPGAs, is capable of recording omni-directional video in a 360°×100° FOV at 9.5 fps with a resolution over (17,700×4,650) pixels (82.3MP). Real-time video capturing capability is also verified at 30 fps for a resolution over (9,000×2,400) pixels (21.6MP). The next generation system with significantly higher resolution and real-time processing capacity, called GigaEye-2, is currently under development. The important capacity of GigaEye-1 opens the door to various post-processing techniques in surveillance domain such as large perimeter object tracking, very-high resolution depth map estimation and high dynamicrange imaging which are beyond standard stitching and panorama generation methods.

  19. Construction of a Direct Water-Injected Two-Stroke Engine for Phased Direct Fuel Injection-High Pressure Charging Investigations

    Science.gov (United States)

    Somsel, James P.

    1998-01-01

    The development of a water injected Orbital Combustion Process (OCP) engine was conducted to assess the viability of using the powerplant for high altitude NASA aircraft and General Aviation (GA) applications. An OCP direct fuel injected, 1.2 liter, three cylinder, two-stroke engine has been enhanced to independently inject water directly into the combustion chamber. The engine currently demonstrates low brake specific fuel consumption capability and an excellent power to weight ratio. With direct water injection, significant improvements can be made to engine power, to knock limits/ignition advance timing, and to engine NO(x) emissions. The principal aim of the testing was to validate a cyclic model developed by the Systems Analysis Branch at NASA Ames Research Center. The work is a continuation of Ames' investigations into a Phased Direct Fuel Injection Engine with High Pressure Charging (PDFI-ITPC).

  20. Ultra-high-throughput screening method for the directed evolution of glucose oxidase.

    Science.gov (United States)

    Ostafe, Raluca; Prodanovic, Radivoje; Nazor, Jovana; Fischer, Rainer

    2014-03-20

    Glucose oxidase (GOx) is used in many industrial processes that could benefit from improved versions of the enzyme. Some improvements like higher activity under physiological conditions and thermal stability could be useful for GOx applications in biosensors and biofuel cells. Directed evolution is one of the currently available methods to engineer improved GOx variants. Here, we describe an ultra-high-throughput screening system for sorting the best enzyme variants generated by directed evolution that incorporates several methodological refinements: flow cytometry, in vitro compartmentalization, yeast surface display, fluorescent labeling of the expressed enzyme, delivery of glucose substrate to the reaction mixture through the oil phase, and covalent labeling of the cells with fluorescein-tyramide. The method enables quantitative screening of gene libraries to identify clones with improved activity and it also allows cells to be selected based not only on the overall activity but also on the specific activity of the enzyme. Copyright © 2014 Elsevier Ltd. All rights reserved.

  1. Comparative studies of high-frequency and direct current molecular gas discharges

    International Nuclear Information System (INIS)

    Goichman, V.H.; Goldfarb, V.M.; Tendler, M.B.

    1975-01-01

    Electron gas parameters, gas temperatures, ionization and thermal instability are found to be markedly different in direct current glow discharges from capactive electrodless high frequency discharge even when equal net power input is provided. It is reasonable to expect that the combined discharge containing both types of discharges mentioned above may be expected to improve significantly both the steady-state and transient characteristics of the plasma. The characteristics of different discharges in air, nitrogen air-CO 2 -He mixture have been compared. Because of the lack of the direct electrical methods for measurements of the hf plasma, exphasis in this investigation has been laid on both theoretical) based on the analytical expression for electron energy distribution function received previously and experimental spectroscopic evaluations of the plasma parameters. (Auth.)

  2. Scaling model for high-aspect-ratio microballoon direct-drive implosions at short laser wavelengths

    International Nuclear Information System (INIS)

    Schirmann, D.; Juraszek, D.; Lane, S.M.; Campbell, E.M.

    1992-01-01

    A scaling model for hot spherical ablative implosions in direct-drive mode is presented. The model results have been compared with experiments from LLE, ILE, and LLNL. Reduction of the neutron yield due to illumination nonuniformities is taken into account by the assumption that the neutron emission is cut off when the gas shock wave reflected off the center meets the incoming pusher, i.e., at a time when the probability of shell breakup is greatly enhanced. The main advantage of this semiempirical scaling model is that it elucidates the principal features of these simple implosions and permits one to estimate very quickly the performance of a high-aspect-ratio direct-drive target illuminated by short-wavelength laser light. (Author)

  3. A highly directive graphene antenna embedded inside a Fabry-Perot cavity in terahertz regime

    Science.gov (United States)

    Roshanaei, Majid; Karami, Hamidreza; Dehkhoda, Parisa; Esfahani, Hamid; Dabir, Fatemeh

    2018-05-01

    In this paper, a highly directive nano-thickness graphene-based antenna is introduced in the terahertz frequency band. The antenna is a graphene patch dipole which is placed between two Bragg mirrors called Fabry-Perot cavity. Tunability of the graphene's conductivity makes it possible to excite the desired resonances of the cavity. Here, first, a single resonant antenna is introduced at 5 THz with an enhanced gain from 2.11 dBi to 12.8 dBi with a beamwidth of 22.7°. Then, a triple resonant antenna at 4.7, 5 and 5.3 THz is presented with respective gains of 7.97, 11.9 and 8.52 dBi. Finally, the effect of dimensions and number of the dielectric layers of the cavity are studied in order to further increase in directivity.

  4. Influence of rolling direction and carbide precipitation on IGSCC susceptibility in hydrogenated high temperature water

    International Nuclear Information System (INIS)

    Arioka, Koji; Yamada, Takuyo; Terachi, Takumi; Chiba, Goro

    2005-01-01

    IGSCC growth behaviors of austenitic stainless steels in hydrogenated high temperature water were studied using compact type specimens (0.5T for cold worked materials). The effect of cold rolling direction, alloy composition and carbide precipitation on crack growth behaviors was studied in hydrogenated high temperature water. Then, to examine the effect of cold work and carbide precipitation on IGSCC behaviors, the role of grain boundary sliding studied in high temperature air using CT specimens. The similar dependences of carbide precipitation and cold work on IGSCC and creep behaviors suggest that grain boundary sliding might play an important role by itself or in conjunction with other reactions such as crack tip dissolution etc. (author)

  5. High-resolution direct 3D printed PLGA scaffolds: print and shrink

    International Nuclear Information System (INIS)

    Chia, Helena N; Wu, Benjamin M

    2015-01-01

    Direct three-dimensional printing (3DP) produces the final part composed of the powder and binder used in fabrication. An advantage of direct 3DP is control over both the microarchitecture and macroarchitecture. Prints which use porogen incorporated in the powder result in high pore interconnectivity, uniform porosity, and defined pore size after leaching. The main limitations of direct 3DP for synthetic polymers are the use of organic solvents which can dissolve polymers used in most printheads and limited resolution due to unavoidable spreading of the binder droplet after contact with the powder. This study describes a materials processing strategy to eliminate the use of organic solvent during the printing process and to improve 3DP resolution by shrinking with a non-solvent plasticizer. Briefly, poly(lactic-co-glycolic acid) (PLGA) powder was prepared by emulsion solvent evaporation to form polymer microparticles. The printing powder was composed of polymer microparticles dry mixed with sucrose particles. After printing with a water-based liquid binder, the polymer microparticles were fused together to form a network by solvent vapor in an enclosed vessel. The sucrose is removed by leaching and the resulting scaffold is placed in a solution of methanol. The methanol acts as a non-solvent plasticizer and allows for polymer chain rearrangement and efficient packing of polymer chains. The resulting volumetric shrinkage is ∼80% at 90% methanol. A complex shape (honey-comb) was designed, printed, and shrunken to demonstrate isotropic shrinking with the ability to reach a final resolution of ∼400 μm. The effect of type of alcohol (i.e. methanol or ethanol), concentration of alcohol, and temperature on volumetric shrinking was studied. This study presents a novel materials processing strategy to overcome the main limitations of direct 3DP to produce high resolution PLGA scaffolds. (paper)

  6. High-resolution direct 3D printed PLGA scaffolds: print and shrink.

    Science.gov (United States)

    Chia, Helena N; Wu, Benjamin M

    2014-12-17

    Direct three-dimensional printing (3DP) produces the final part composed of the powder and binder used in fabrication. An advantage of direct 3DP is control over both the microarchitecture and macroarchitecture. Prints which use porogen incorporated in the powder result in high pore interconnectivity, uniform porosity, and defined pore size after leaching. The main limitations of direct 3DP for synthetic polymers are the use of organic solvents which can dissolve polymers used in most printheads and limited resolution due to unavoidable spreading of the binder droplet after contact with the powder. This study describes a materials processing strategy to eliminate the use of organic solvent during the printing process and to improve 3DP resolution by shrinking with a non-solvent plasticizer. Briefly, poly(lactic-co-glycolic acid) (PLGA) powder was prepared by emulsion solvent evaporation to form polymer microparticles. The printing powder was composed of polymer microparticles dry mixed with sucrose particles. After printing with a water-based liquid binder, the polymer microparticles were fused together to form a network by solvent vapor in an enclosed vessel. The sucrose is removed by leaching and the resulting scaffold is placed in a solution of methanol. The methanol acts as a non-solvent plasticizer and allows for polymer chain rearrangement and efficient packing of polymer chains. The resulting volumetric shrinkage is ∼80% at 90% methanol. A complex shape (honey-comb) was designed, printed, and shrunken to demonstrate isotropic shrinking with the ability to reach a final resolution of ∼400 μm. The effect of type of alcohol (i.e. methanol or ethanol), concentration of alcohol, and temperature on volumetric shrinking was studied. This study presents a novel materials processing strategy to overcome the main limitations of direct 3DP to produce high resolution PLGA scaffolds.

  7. High slope efficiency and high refractive index change in direct-written Yb-doped waveguide lasers with depressed claddings.

    Science.gov (United States)

    Palmer, Guido; Gross, Simon; Fuerbach, Alexander; Lancaster, David G; Withford, Michael J

    2013-07-15

    We report the first Yb:ZBLAN and Yb:IOG10 waveguide lasers fabricated by the fs-laser direct-writing technique. Pulses from a Titanium-Sapphire laser oscillator with 5.1 MHz repetition rate were utilized to generate negative refractive index modifications in both glasses. Multiple modifications were aligned in a depressed cladding geometry to create a waveguide. For Yb:ZBLAN we demonstrate high laser slope efficiency of 84% with a maximum output power of 170 mW. By using Yb:IOG10 a laser performance of 25% slope efficiency and 72 mW output power was achieved and we measured a remarkably high refractive index change exceeding Δn = 2.3 × 10(-2).

  8. Data-driven directions for effective footwear provision for the high-risk diabetic foot.

    Science.gov (United States)

    Arts, M L J; de Haart, M; Waaijman, R; Dahmen, R; Berendsen, H; Nollet, F; Bus, S A

    2015-06-01

    Custom-made footwear is used to offload the diabetic foot to prevent plantar foot ulcers. This prospective study evaluates the offloading effects of modifying custom-made footwear and aims to provide data-driven directions for the provision of effectively offloading footwear in clinical practice. Eighty-five people with diabetic neuropathy and a recently healed plantar foot ulcer, who participated in a clinical trial on footwear effectiveness, had their custom-made footwear evaluated with in-shoe plantar pressure measurements at three-monthly intervals. Footwear was modified when peak pressure was ≥ 200 kPa. The effect of single and combined footwear modifications on in-shoe peak pressure at these high-pressure target locations was assessed. All footwear modifications significantly reduced peak pressure at the target locations compared with pre-modification levels (range -6.7% to -24.0%, P diabetic neuropathy and a recently healed plantar foot ulcer, significant offloading can be achieved at high-risk foot regions by modifying custom-made footwear. These results provide data-driven directions for the design and evaluation of custom-made footwear for high-risk people with diabetes, and essentially mean that each shoe prescribed should incorporate those design features that effectively offload the foot. © 2015 The Authors. Diabetic Medicine © 2015 Diabetes UK.

  9. High electrical conductivity in out of plane direction of electrodeposited Bi2Te3 films

    Directory of Open Access Journals (Sweden)

    Miguel Muñoz Rojo

    2015-08-01

    Full Text Available The out of plane electrical conductivity of highly anisotropic Bi2Te3 films grown via electro-deposition process was determined using four probe current-voltage measurements performed on 4.6 - 7.2 μm thickness Bi2Te3 mesa structures with 80 - 120 μm diameters sandwiched between metallic film electrodes. A three-dimensional finite element model was used to predict the electric field distribution in the measured structures and take into account the non-uniform distribution of the current in the electrodes in the vicinity of the probes. The finite-element modeling shows that significant errors could arise in the measured film electrical conductivity if simpler one-dimensional models are employed. A high electrical conductivity of (3.2 ± 0.4 ⋅ 105 S/m is reported along the out of plane direction for Bi2Te3 films highly oriented in the [1 1 0] direction.

  10. Directional Growth of Ultralong CsPbBr3 Perovskite Nanowires for High-Performance Photodetectors.

    Science.gov (United States)

    Shoaib, Muhammad; Zhang, Xuehong; Wang, Xiaoxia; Zhou, Hong; Xu, Tao; Wang, Xiao; Hu, Xuelu; Liu, Huawei; Fan, Xiaopeng; Zheng, Weihao; Yang, Tiefeng; Yang, Shuzhen; Zhang, Qinglin; Zhu, Xiaoli; Sun, Litao; Pan, Anlian

    2017-11-08

    Directional growth of ultralong nanowires (NWs) is significant for practical application of large-scale optoelectronic integration. Here, we demonstrate the controlled growth of in-plane directional perovskite CsPbBr 3 NWs, induced by graphoepitaxial effect on annealed M-plane sapphire substrates. The wires have a diameter of several hundred nanometers, with lengths up to several millimeters. Microstructure characterization shows that CsPbBr 3 NWs are high-quality single crystals, with smooth surfaces and well-defined cross section. The NWs have very strong band-edge photoluminescence (PL) with a long PL lifetime of ∼25 ns and can realize high-quality optical waveguides. Photodetectors constructed on these individual NWs exhibit excellent photoresponse with an ultrahigh responsivity of 4400 A/W and a very fast response speed of 252 μs. This work presents an important step toward scalable growth of high-quality perovskite NWs, which will provide promising opportunities in constructing integrated nanophotonic and optoelectronic systems.

  11. Sub-100 fs high average power directly blue-diode-laser-pumped Ti:sapphire oscillator

    Science.gov (United States)

    Rohrbacher, Andreas; Markovic, Vesna; Pallmann, Wolfgang; Resan, Bojan

    2016-03-01

    Ti:sapphire oscillators are a proven technology to generate sub-100 fs (even sub-10 fs) pulses in the near infrared and are widely used in many high impact scientific fields. However, the need for a bulky, expensive and complex pump source, typically a frequency-doubled multi-watt neodymium or optically pumped semiconductor laser, represents the main obstacle to more widespread use. The recent development of blue diodes emitting over 1 W has opened up the possibility of directly diode-laser-pumped Ti:sapphire oscillators. Beside the lower cost and footprint, a direct diode pumping provides better reliability, higher efficiency and better pointing stability to name a few. The challenges that it poses are lower absorption of Ti:sapphire at available diode wavelengths and lower brightness compared to typical green pump lasers. For practical applications such as bio-medicine and nano-structuring, output powers in excess of 100 mW and sub-100 fs pulses are required. In this paper, we demonstrate a high average power directly blue-diode-laser-pumped Ti:sapphire oscillator without active cooling. The SESAM modelocking ensures reliable self-starting and robust operation. We will present two configurations emitting 460 mW in 82 fs pulses and 350 mW in 65 fs pulses, both operating at 92 MHz. The maximum obtained pulse energy reaches 5 nJ. A double-sided pumping scheme with two high power blue diode lasers was used for the output power scaling. The cavity design and the experimental results will be discussed in more details.

  12. High-speed fan-beam reconstruction using direct two-dimensional Fourier transform method

    International Nuclear Information System (INIS)

    Niki, Noboru; Mizutani, Toshio; Takahashi, Yoshizo; Inouye, Tamon.

    1984-01-01

    Since the first development of X-ray computer tomography (CT), various efforts have been made to obtain high quality of high-speed image. However, the development of high resolution CT and the ultra-high speed CT to be applied to hearts is still desired. The X-ray beam scanning method was already changed from the parallel beam system to the fan-beam system in order to greatly shorten the scanning time. Also, the filtered back projection (DFBP) method has been employed to directly processing fan-beam projection data as reconstruction method. Although the two-dimensional Fourier transform (TFT) method significantly faster than FBP method was proposed, it has not been sufficiently examined for fan-beam projection data. Thus, the ITFT method was investigated, which first executes rebinning algorithm to convert the fan-beam projection data to the parallel beam projection data, thereafter, uses two-dimensional Fourier transform. By this method, although high speed is expected, the reconstructed images might be degraded due to the adoption of rebinning algorithm. Therefore, the effect of the interpolation error of rebinning algorithm on the reconstructed images has been analyzed theoretically, and finally, the result of the employment of spline interpolation which allows the acquisition of high quality images with less errors has been shown by the numerical and visual evaluation based on simulation and actual data. Computation time was reduced to 1/15 for the image matrix of 512 and to 1/30 for doubled matrix. (Wakatsuki, Y.)

  13. Load Torque Compensator for Model Predictive Direct Current Control in High Power PMSM Drive Systems

    DEFF Research Database (Denmark)

    Preindl, Matthias; Schaltz, Erik

    2011-01-01

    The widely used cascade speed and torque controllers have a limited control performance in most high power applications due to the low switching frequency of power electronic converters and the convenience to avoid speed overshoots and oscillations for lifetime considerations. Model Predictive...... Direct Current Control (MPDCC) leads to an increase of torque control performance taking into account the discrete nature of inverters but temporary offsets and poor responses to load torque variations are still issues in speed control. A load torque estimator is proposed in this paper in order...

  14. Load Torque Compensator for Model Predictive Direct Current Control in High Power PMSM Drive Systems

    DEFF Research Database (Denmark)

    Preindl, Matthias; Schaltz, Erik

    2010-01-01

    In drive systems the most used control structure is the cascade control with an inner torque, i.e. current and an outer speed control loop. The fairly small converter switching frequency in high power applications, e.g. wind turbines lead to modest speed control performance. An improvement bring...... the use of a current controller which takes into account the discrete states of the inverter, e.g. DTC or a more modern approach: Model Predictive Direct Current Control (MPDCC). Moreover overshoots and oscillations in the speed are not desired in many applications, since they lead to mechanical stress...

  15. High-Capacity Quantum Secure Direct Communication Based on Quantum Hyperdense Coding with Hyperentanglement

    International Nuclear Information System (INIS)

    Wang Tie-Jun; Li Tao; Du Fang-Fang; Deng Fu-Guo

    2011-01-01

    We present a quantum hyperdense coding protocol with hyperentanglement in polarization and spatial-mode degrees of freedom of photons first and then give the details for a quantum secure direct communication (QSDC) protocol based on this quantum hyperdense coding protocol. This QSDC protocol has the advantage of having a higher capacity than the quantum communication protocols with a qubit system. Compared with the QSDC protocol based on superdense coding with d-dimensional systems, this QSDC protocol is more feasible as the preparation of a high-dimension quantum system is more difficult than that of a two-level quantum system at present. (general)

  16. Highly directive Fabry-Perot leaky-wave nanoantennas based on optical partially reflective surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lorente-Crespo, M.; Mateo-Segura, C., E-mail: C.Mateo-Segura@hw.ac.uk [Institute of Sensors, Signals and Systems, Heriot-Watt University, EH14 4AS Edinburgh (United Kingdom)

    2015-05-04

    Nanoantennas enhance the conversion between highly localized electromagnetic fields and far-field radiation. Here, we investigate the response of a nano-patch partially reflective surface backed with a silver mirror to an optical source embedded at the centre of the structure. Using full wave simulations, we demonstrate a two orders of magnitude increased directivity compared to the isotropic radiator, 50% power confinement to a 13.8° width beam and a ±16 nm bandwidth. Our antenna does not rely on plasmonic phenomena thus reducing non-radiative losses and conserving source coherence.

  17. Chiral separation of substituted phenylalanine analogues using chiral palladium phosphine complexes with enantioselective liquid-liquid extraction

    NARCIS (Netherlands)

    Verkuijl, B.J.V.; Schuur, B.; Minnaard, A.J.; Vries, de J.G.; Feringa, B.L.

    2010-01-01

    Chiral palladium phosphine complexes have been employed in the chiral separation of amino acids and phenylalanine analogues in particular. The use of (S)-xylyl-BINAP as a ligand for the palladium complex in enantioselective liquid–liquid extraction allowed the separation of the phenylalanine

  18. Enantioselective Effects of o,p'-DDT on Cell Invasion and Adhesion of Breast Cancer Cells: Chirality in Cancer Development.

    Science.gov (United States)

    He, Xiangming; Dong, Xiaowu; Zou, Dehong; Yu, Yang; Fang, Qunying; Zhang, Quan; Zhao, Meirong

    2015-08-18

    The o,p'-dichlorodiphenyltrichloroethane (DDT) with a chiral center possesses enantioselective estrogenic activity, in which R-(-)-o,p'-DDT exerts a more potent estrogenic effect than S-(+)-o,p'-DDT. Although concern regarding DDT exposure and breast cancer has increased in recent decades, the mode of enantioselective action of o,p'-DDT in breast cancer development is still unknown. Herein, we conducted a systematic study of the effect of o,p'-DDT on stereoselective breast tumor cell progression in a widely used in vitro breast tumor cell model, MCF-7 cells. We demonstrated that R-(-)-o,p'-DDT promoted more cancer cell invasion mediated by the human estrogen receptor (ER) by inducing invasion-promoted genes (matrix metalloproteinase-2 and -9 and human telomerase reverse transcriptase) and inhibiting invasion-inhibited genes (tissue inhibitor of metalloproteinase-1 and -4). Molecular docking verified that the binding affinity between R-(-)-o,p'-DDT and human ER was stronger than that of S-(+)-o,p'-DDT. The enantioselective-induced decrease in cell-to-cell adhesion may involve the downregulation of adhesion-promoted genes (E-cadherin and β-catenin). For the first time, these results reveal that estrogenic-like chiral compounds are of significant concern in the progression of human cancers and that human health risk assessment of chiral chemicals should consider enantioselectivity.

  19. Proof of concept for continuous enantioselective liquid-liquid extraction in capillary microreactors using 1-octanol as a sustainable solvent

    NARCIS (Netherlands)

    Susanti, S.; Meinds, Tim G.; Pinxterhuis, Erik B.; Schuur, Boelo; De Vries, Johannes G.; Feringa, Ben L.; Winkelman, Jozef G.M.; Yue, Jun; Heeres, Hero J.

    2017-01-01

    The use of capillary microreactors for enantioselective liquid-liquid extraction (ELLE) was successfully demonstrated using a model system consisting of a buffered aqueous amino acid derivative (3,5-dinitrobenzoyl-(R,S)-leucine) solution (phosphate buffer, pH 6.58) and a chiral cinchona alkaloid

  20. A Convergent Enantioselective Total Synthesis of (-)-Perhydrohistrionicotoxin with an Intramolecular Imino Ene-type Reaction as a Key Step

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Hagberg, Lars

    1998-01-01

    A convergent enantioselective total synthesis of the neurotoxic spirocyclic alkaloid (-)-perhydrohistrionicotoxin (2) is described. A Lewis acid-mediated intramolecular imine ene-type reaction was used for the key spirocyclisation step (14 to 3, with 3 being obtained as a single diastereoisomer...

  1. Organocatalytic Enantioselective Pictet-Spengler Approach to Biologically Relevant 1-Benzyl-1,2,3,4-Tetrahydroisoquinoline Alkaloids

    NARCIS (Netherlands)

    Ruiz-Olalla, A.; Würdemann, M.A.; Wanner, M.J.; Ingemann, S.; van Maarseveen, J.H.; Hiemstra, H.

    2015-01-01

    A general procedure for the synthesis of 1-benzyl-1,2,3,4-tetrahydroisoquinolines was developed, based on organocatalytic, regio- and enantioselective Pictet-Spengler reactions (86-92% ee) of N-(o-nitrophenylsulfenyl)-2-arylethyl-amines with arylacetaldehydes. The presence of the

  2. DNA-Accelerated Copper Catalysis of Friedel-Crafts Conjugate Addition/Enantioselective Protonation Reactions in Water

    NARCIS (Netherlands)

    García-Fernández, Almudena; Megens, Rik P.; Villarino, Lara; Roelfes, Gerard

    2016-01-01

    DNA-induced rate acceleration has been identified as one of the key elements for the success of the DNA-based catalysis concept. Here we report on a novel DNA-based catalytic Friedel-Crafts conjugate addition/enantioselective protonation reaction in water, which represents the first example of a

  3. Synthesis of l-threitol-based crown ethers and their application as enantioselective phase transfer catalyst in Michael additions.

    Science.gov (United States)

    Rapi, Zsolt; Nemcsok, Tamás; Pálvölgyi, Ádám; Keglevich, György; Grün, Alajos; Bakó, Péter

    2017-06-01

    A few new l-threitol-based lariat ethers incorporating a monoaza-15-crown-5 unit were synthesized starting from diethyl l-tartrate. These macrocycles were used as phase transfer catalysts in asymmetric Michael addition reactions under mild conditions to afford the adducts in a few cases in good to excellent enantioselectivities. The addition of 2-nitropropane to trans-chalcone, and the reaction of diethyl acetamidomalonate with β-nitrostyrene resulted in the chiral Michael adducts in good enantioselectivities (90% and 95%, respectively). The substituents of chalcone had a significant impact on the yield and enantioselectivity in the reaction of diethyl acetoxymalonate. The highest enantiomeric excess (ee) values (99% ee) were measured in the case of 4-chloro- and 4-methoxychalcone. The phase transfer catalyzed cyclopropanation reaction of chalcone and benzylidene-malononitriles using diethyl bromomalonate as the nucleophile (MIRC reaction) was also developed. The corresponding chiral cyclopropane diesters were obtained in moderate to good (up to 99%) enantioselectivities in the presence of the threitol-based crown ethers. © 2017 Wiley Periodicals, Inc.

  4. Enantioselective [2+2+2] cycloisomerisation of alkynes in the synthesis of helicenes: the search for effective chiral ligands

    Czech Academy of Sciences Publication Activity Database

    Stará, Irena G.; Andronova, Angelina; Kollárovič, Adrian; Vyskočil, Š.; Jugé, S.; Lloyd-Jones, G. C.; Guiry, P. J.; Starý, Ivo

    2011-01-01

    Roč. 76, č. 12 (2011), s. 2005-2022 ISSN 0010-0765 R&D Projects: GA ČR GA203/09/1766; GA MŠk LC512 Institutional research plan: CEZ:AV0Z40550506 Keywords : helicenes * enantioselectivity * cycloisomerisation Subject RIV: CC - Organic Chemistry Impact factor: 1.283, year: 2011

  5. Separation of racemic mixture by ultrafiltration of enantioselective micelles. 1 Effect of pH on separation and regeneration

    NARCIS (Netherlands)

    Overdevest, P.E.M.; Bruin, de T.J.M.; Riet, van 't K.; Keurentjes, J.T.F.; Padt, van der A.

    2001-01-01

    Many enantiomer separation systems are studied to meet the increasing demand for enantiopure compounds. One way to obtain pure enantiomers is to apply enantioselective micelles in ultrafiltration systems. We have studied the separation of phenylalanine (Phe) enantiomers by the ultrafiltration of

  6. High-Alpha Research Vehicle Lateral-Directional Control Law Description, Analyses, and Simulation Results

    Science.gov (United States)

    Davidson, John B.; Murphy, Patrick C.; Lallman, Frederick J.; Hoffler, Keith D.; Bacon, Barton J.

    1998-01-01

    This report contains a description of a lateral-directional control law designed for the NASA High-Alpha Research Vehicle (HARV). The HARV is a F/A-18 aircraft modified to include a research flight computer, spin chute, and thrust-vectoring in the pitch and yaw axes. Two separate design tools, CRAFT and Pseudo Controls, were integrated to synthesize the lateral-directional control law. This report contains a description of the lateral-directional control law, analyses, and nonlinear simulation (batch and piloted) results. Linear analysis results include closed-loop eigenvalues, stability margins, robustness to changes in various plant parameters, and servo-elastic frequency responses. Step time responses from nonlinear batch simulation are presented and compared to design guidelines. Piloted simulation task scenarios, task guidelines, and pilot subjective ratings for the various maneuvers are discussed. Linear analysis shows that the control law meets the stability margin guidelines and is robust to stability and control parameter changes. Nonlinear batch simulation analysis shows the control law exhibits good performance and meets most of the design guidelines over the entire range of angle-of-attack. This control law (designated NASA-1A) was flight tested during the Summer of 1994 at NASA Dryden Flight Research Center.

  7. Direct electron-pair production by high energy heavy charged particles

    Science.gov (United States)

    Takahashi, Y.; Gregory, J. C.; Hayashi, T.; Dong, B. L.

    1989-01-01

    Direct electron pain production via virtual photons by moving charged particles is a unique electro-magnetic process having a substantial dependence on energy. Most electro-magnetic processes, including transition radiation, cease to be sensitive to the incident energy above 10 TeV/AMU. Thus, it is expected, that upon establishment of cross section and detection efficiency of this process, it may provide a new energy measuring technique above 10 TeV/AMU. Three accelerator exposures of emulsion chambers designed for measurements of direct electron-pains were performed. The objectives of the investigation were to provide the fundamental cross-section data in emulsion stacks to find the best-fit theoretical model, and to provide a calibration of measurements of direct electron-pairs in emulsion chamber configurations. This paper reports the design of the emulsion chambers, accelerator experiments, microscope measurements, and related considerations for future improvements of the measurements, and for possible applications to high energy cosmic ray experiments. Also discussed are the results from scanning 56m of emulsion tracks at 1200x magnification so that scanning efficiency is optimized. Measurements of the delta-ray range spectrum were also performed for much shorter track lengths, but with sufficiently large statistics in the number of measured delta-rays.

  8. Preparative and mechanistic studies toward the rational development of catalytic, enantioselective selenoetherification reactions.

    Science.gov (United States)

    Denmark, Scott E; Kalyani, Dipannita; Collins, William R

    2010-11-10

    A systematic investigation into the Lewis base catalyzed, asymmetric, intramolecular selenoetherification of olefins is described. A critical challenge for the development of this process was the identification and suppression of racemization pathways available to arylseleniranium ion intermediates. This report details a thorough study of the influences of the steric and electronic modulation of the arylselenenyl group on the configurational stability of enantioenriched seleniranium ions. These studies show that the 2-nitrophenyl group attached to the selenium atom significantly attenuates the racemization of seleniranium ions. A variety of achiral Lewis bases catalyze the intramolecular selenoetherification of alkenes using N-(2-nitrophenylselenenyl)succinimide as the electrophile along with a Brønsted acid. Preliminary mechanistic studies suggest the intermediacy of ionic Lewis base-selenium(II) adducts. Most importantly, a broad survey of chiral Lewis bases revealed that 1,1'-binaphthalene-2,2'-diamine (BINAM)-derived thiophosphoramides catalyze the cyclization of unsaturated alcohols in the presence of N-(2-nitrophenylselenenyl)succinimide and methanesulfonic acid. A variety of cyclic seleno ethers were produced in good chemical yields and in moderate to good enantioselectivities, which constitutes the first catalytic, enantioselective selenofunctionalization of unactivated olefins.

  9. Characterization of an enantioselective odorant receptor in the yellow fever mosquito Aedes aegypti.

    Directory of Open Access Journals (Sweden)

    Jonathan D Bohbot

    2009-09-01

    Full Text Available Enantiomers differ only in the left or right handedness (chirality of their orientations and exhibit identical chemical and physical properties. In chemical communication systems, enantiomers can be differentially active at the physiological and behavioral levels. Only recently were enantioselective odorant receptors demonstrated in mammals while their existence in insects has remained hypothetical. Using the two-microelectrode voltage clamp of Xenopus oocytes, we show that the yellow fever mosquito, Aedes aegypti, odorant receptor 8 (AaOR8 acts as a chiral selective receptor for the (R-(--enantiomer of 1-octen-3-ol, which in the presence of other kairomones is an attractant used by blood-sucking insects to locate their hosts. In addition to steric constraints, chain length and degree of unsaturation play important roles in this recognition process. This is the first characterization of an enantioselective odorant receptor in insects and the results demonstrate that an OR alone, without helper proteins, can account for chiral specificity exhibited by olfactory sensory neurons (OSNs.

  10. Influence of gasoline inhalation on the enantioselective pharmacokinetics of fluoxetine in rats.

    Science.gov (United States)

    Cardoso, Juciane Lauren Cavalcanti; Lanchote, Vera Lucia; Pereira, Maria Paula Marques; Capela, Jorge Manuel Vieira; Lepera, José Salvador

    2013-03-01

    Fluoxetine is used clinically as a racemic mixture of (+)-(S) and (-)-(R) enantiomers for the treatment of depression. CYP2D6 catalyzes the metabolism of both fluoxetine enantiomers. We aimed to evaluate whether exposure to gasoline results in CYP2D inhibition. Male Wistar rats exposed to filtered air (n = 36; control group) or to 600 ppm of gasoline (n = 36) in a nose-only inhalation exposure chamber for 6 weeks (6 h/day, 5 days/week) received a single oral 10-mg/kg dose of racemic fluoxetine. Fluoxetine enantiomers in plasma samples were analyzed by a validated analytical method using LC-MS/MS. The separation of fluoxetine enantiomers was performed in a Chirobiotic V column using as the mobile phase a mixture of ethanol:ammonium acetate 15 mM. Higher plasma concentrations of the (+)-(S)-fluoxetine enantiomer were found in the control group (enantiomeric ratio AUC((+)-(S)/(-)-(R)) = 1.68). In animals exposed to gasoline, we observed an increase in AUC(0-∞) for both enantiomers, with a sharper increase seen for the (-)-(R)-fluoxetine enantiomer (enantiomeric ratio AUC((+)-(S)/(-)-(R)) = 1.07), resulting in a loss of enantioselectivity. Exposure to gasoline was found to result in the loss of enantioselectivity of fluoxetine, with the predominant reduction occurring in the clearance of the (-)-(R)-fluoxetine enantiomer (55% vs. 30%). Copyright © 2013 Wiley Periodicals, Inc.

  11. Hydrothermal synthesis, crystal structures, and enantioselective adsorption property of bis(L-histidinato)nickel(II) monohydrate

    Science.gov (United States)

    Ramos, Christian Paul L.; Conato, Marlon T.

    2018-05-01

    Despite the numerous researches in metal-organic frameworks (MOFs), there are only few reports on biologically important amino acids, histidine in particular, on its use as bridging ligand in the construction of open-framework architectures. In this work, hydrothermal synthesis was used to prepare a compound based on Ni2+ and histidine. The coordination assembly of imidazole side chain of histidine with divalent nickel ions in aqueous condition yielded purple prismatic solids. Single crystal X-ray diffraction (XRD) analysis of the product revealed structure for Ni(C6H8N3O2)2 • H2O that has a monoclinic (C2) structure with lattice parameters, a = 29.41, b = 8.27, c = 6.31 Å, β = 90.01 ˚. Circular dichroism - optical rotatory dispersion (CD-ORD), Powder X-ray diffraction (PXRD) and Fourier transform - infrared spectroscopy (FT-IR) analyses are conducted to further characterize the crystals. Enantioselective adsorption analysis using racemic mixture of 2-butanol confirmed bis(L-histidinato)nickel(II) monohydrate MOF crystal's enantioselective property preferentially favoring the adsorption of (S)-2-butanol isomer.

  12. Enantioselective Analytical- and Preparative-Scale Separation of Hexabromocyclododecane Stereoisomers Using Packed Column Supercritical Fluid Chromatography

    Directory of Open Access Journals (Sweden)

    Nicole Riddell

    2016-11-01

    Full Text Available Hexabromocyclododecane (HBCDD is an additive brominated flame retardant which has been listed in Annex A of the Stockholm Convention for elimination of production and use. It has been reported to persist in the environment and has the potential for enantiomer-specific degradation, accumulation, or both, making enantioselective analyses increasingly important. The six main stereoisomers of technical HBCDD (i.e., the (+ and (− enantiomers of α-, β-, and γ-HBCDD were separated and isolated for the first time using enantioselective packed column supercritical fluid chromatography (pSFC separation methods on a preparative scale. Characterization was completed using published chiral liquid chromatography (LC methods and elution profiles, as well as X-ray crystallography, and the isolated fractions were definitively identified. Additionally, the resolution of the enantiomers, along with two minor components of the technical product (δ- and ε-HBCDD, was investigated on an analytical scale using both LC and pSFC separation techniques, and changes in elution order were highlighted. Baseline separation of all HBCDD enantiomers was achieved by pSFC on an analytical scale using a cellulose-based column. The described method emphasizes the potential associated with pSFC as a green method of isolating and analyzing environmental contaminants of concern.

  13. Enantioselective Analytical- and Preparative-Scale Separation of Hexabromocyclododecane Stereoisomers Using Packed Column Supercritical Fluid Chromatography.

    Science.gov (United States)

    Riddell, Nicole; Mullin, Lauren Gayle; van Bavel, Bert; Ericson Jogsten, Ingrid; McAlees, Alan; Brazeau, Allison; Synnott, Scott; Lough, Alan; McCrindle, Robert; Chittim, Brock

    2016-11-10

    Hexabromocyclododecane (HBCDD) is an additive brominated flame retardant which has been listed in Annex A of the Stockholm Convention for elimination of production and use. It has been reported to persist in the environment and has the potential for enantiomer-specific degradation, accumulation, or both, making enantioselective analyses increasingly important. The six main stereoisomers of technical HBCDD (i.e., the (+) and (-) enantiomers of α-, β-, and γ-HBCDD) were separated and isolated for the first time using enantioselective packed column supercritical fluid chromatography (pSFC) separation methods on a preparative scale. Characterization was completed using published chiral liquid chromatography (LC) methods and elution profiles, as well as X-ray crystallography, and the isolated fractions were definitively identified. Additionally, the resolution of the enantiomers, along with two minor components of the technical product (δ- and ε-HBCDD), was investigated on an analytical scale using both LC and pSFC separation techniques, and changes in elution order were highlighted. Baseline separation of all HBCDD enantiomers was achieved by pSFC on an analytical scale using a cellulose-based column. The described method emphasizes the potential associated with pSFC as a green method of isolating and analyzing environmental contaminants of concern.

  14. A selective electrocatalyst-based direct methanol fuel cell operated at high concentrations of methanol.

    Science.gov (United States)

    Feng, Yan; Liu, Hui; Yang, Jun

    2017-06-01

    Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag 2 S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm -2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol.

  15. A selective electrocatalyst–based direct methanol fuel cell operated at high concentrations of methanol

    Science.gov (United States)

    Feng, Yan; Liu, Hui; Yang, Jun

    2017-01-01

    Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag2S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm−2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol. PMID:28695199

  16. High magnetic field science and its application in the United States current status and future directions

    CERN Document Server

    National Research Council of the National Academies

    2013-01-01

    The Committee to Assess the Current Status and Future Direction of High Magnetic Field Science in the United States was convened by the National Research Council in response to a request by the National Science Foundation. This report answers three questions: (1) What is the current state of high-field magnet science, engineering, and technology in the United States, and are there any conspicuous needs to be addressed? (2) What are the current science drivers and which scientific opportunities and challenges can be anticipated over the next ten years? (3) What are the principal existing and planned high magnetic field facilities outside of the United States, what roles have U.S. high field magnet development efforts played in developing those facilities, and what potentials exist for further international collaboration in this area? A magnetic field is produced by an electrical current in a metal coil. This current exerts an expansive force on the coil, and a magnetic field is "high" if it challenges the str...

  17. Dual Cage High Power Induction Motor with Direct Start-up. Design and FEM Analysis

    Directory of Open Access Journals (Sweden)

    LIVADARU, L.

    2013-05-01

    Full Text Available This paper presents an investigation on the design of high-power induction motor with special constraints. Direct online start-up and pull-up torque of rather high value represent two of the imposed requirements. Three different structures are analyzed, which involve deep bars, magnetic wedges and double cage respectively. The proposed solution advances a new rotor structure with two different rotor cages. The first cage acts mainly during start-up and is made of iron with both electric and magnetic properties. The second one is made of copper and represents the main rotor winding. It has a particular cross-section of the bars in order to carry into effect the required constraints both during start-up and steady-state. The proposed models are finally evaluated by means of finite element method analysis.

  18. Optical intensity modulation direct detection versus heterodyne detection: A high-SNR capacity comparison

    KAUST Repository

    Chaaban, Anas

    2016-09-15

    An optical wireless communications system which employs either intensity-modulation and direct-detection (IM-DD) or heterodyne detection (HD) is considered. IM-DD has lower complexity and cost than HD, but on the other hand, has lower capacity. It is therefore interesting to investigate the capacity gap between the two systems. The main focus of this paper is to investigate this gap at high SNR. Bounds on this gap are established for two cases: between IM-DD and HD, and between IM-DD and an HD-PAM which is an HD system employing pulse-amplitude modulation (PAM). While the gap between IM-DD and HD increases as the signal-to-noise ratio (SNR) increases, the gap between IM-DD and an HD-PAM is upper bounded by a constant at high SNR. © 2015 IEEE.

  19. Multiple direct exchange in a Yang-Mills theory at high energy

    International Nuclear Information System (INIS)

    McCoy, B.M.; Wu, T.T.

    1976-01-01

    For eighth and higher orders, we obtain the leading high-energy behavior of the sum of all one-layer Feynman diagrams in Yang-Mills theory. These are the contributions from Feynman diagrams where the two incident fast particles exchange directly Yang-Mills bosons that are much less energetic. The incident particles may be either bosons or fermions of arbitrary isospin, and the result is also generalized to include the case of the Higgs scalar. The scattering amplitudes in all these cases are closely related, and all behave as s ln/sub n/ -1 s in the 2n + 2 order. Furthermore, in this leading order for n > or = 2, the exchanged isospins are always 0 and 2, no matter how high the isospins of the incident particles are

  20. Combined local current distribution measurements and high resolution neutron radiography of operating direct methanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, Alexander; Wippermann, Klaus [Forschungszentrum Juelich GmbH (Germany). Inst. of Energy Research, IEF-3: Fuel Cells; Sanders, Tilman [RWTH Aachen (DE). Inst. for Power Electronics and Electrical Drives (ISEA); Arlt, Tobias [Helmholtz Centre Berlin (Germany). Inst. for Applied Materials

    2010-07-01

    Neutron radiography allows the investigation of the local fluid distribution in direct methanol fuel cells (DMFCs) under operating conditions. Spatial resolutions in the order of some tens of micrometers at the full test cell area are achieved. This offers the possibility to study practice-oriented, large stack cells with an active area of several hundred cm{sup 2} as well as specially designed, small test cells with an area of some cm{sup 2}. Combined studies of high resolution neutron radiography and segmented cell measurements are especially valuable, because they enable a correlation of local fluid distribution and local performance [1, 2]. The knowledge of this interdependency is essential to optimise the water management and performance respecting a homogeneous fluid, current and temperature distribution and to achieve high performance and durability of DMFCs. (orig.)

  1. Optical intensity modulation direct detection versus heterodyne detection: A high-SNR capacity comparison

    KAUST Repository

    Chaaban, Anas; Alouini, Mohamed-Slim

    2016-01-01

    An optical wireless communications system which employs either intensity-modulation and direct-detection (IM-DD) or heterodyne detection (HD) is considered. IM-DD has lower complexity and cost than HD, but on the other hand, has lower capacity. It is therefore interesting to investigate the capacity gap between the two systems. The main focus of this paper is to investigate this gap at high SNR. Bounds on this gap are established for two cases: between IM-DD and HD, and between IM-DD and an HD-PAM which is an HD system employing pulse-amplitude modulation (PAM). While the gap between IM-DD and HD increases as the signal-to-noise ratio (SNR) increases, the gap between IM-DD and an HD-PAM is upper bounded by a constant at high SNR. © 2015 IEEE.

  2. Catalytic silica particles via template-directed molecular imprinting

    Energy Technology Data Exchange (ETDEWEB)

    Markowitz, M.A.; Kust, P.R.; Deng, G.; Schoen, P.E.; Dordick, J.S.; Clark, D.S.; Gaber, B.P.

    2000-02-22

    The surfaces of silica particle were molecularly imprinted with an {alpha}-chymotrypsin transition-state analogue (TSA) by utilizing the technique of template-directed synthesis of mineralized materials. The resulting catalytic particles hydrolyzed amides in an enantioselective manner. A mixture of a nonionic surfactant and the acylated chymotrysin TSA, with the TSA acting as the headgroup at the surfactant-water interface, was used to form a microemulsion for silica particle formation. Incorporation of amine-, dihydroimidazole-, and carboxylate-terminated trialkoxysilanes into the particles during imprinting resulted in enhancement of the rates of amide hydrolysis. Acylated imprint molecules formed more effective imprints in the presence of the functionalized silanes than nonacylated imprint molecules. Particles surface-imprinted with the chymotrypsin TSA were selective for the trypsin substrate, and particles surface-imprinted with the L-isomer of the enzyme TSA were enantioselective for the D-isomer of the substrate.

  3. Surface preparation for high purity alumina ceramics enabling direct brazing in hydrogen atmospheres

    Science.gov (United States)

    Cadden, Charles H.; Yang, Nancy Yuan Chi; Hosking, Floyd M.

    2001-01-01

    The present invention relates to a method for preparing the surface of a high purity alumina ceramic or sapphire specimen that enables direct brazing in a hydrogen atmosphere using an active braze alloy. The present invention also relates to a method for directly brazing a high purity alumina ceramic or sapphire specimen to a ceramic or metal member using this method of surface preparation, and to articles produced by this brazing method. The presence of silicon, in the form of a SiO.sub.2 -containing surface layer, can more than double the tensile bond strength in alumina ceramic joints brazed in a hydrogen atmosphere using an active Au-16Ni-0.75 Mo-1.75V filler metal. A thin silicon coating applied by PVD processing can, after air firing, produce a semi-continuous coverage of the alumina surface with a SiO.sub.2 film. Room temperature tensile strength was found to be proportional to the fraction of air fired surface covered by silicon-containing films. Similarly, the ratio of substrate fracture versus interface separation was also related to the amount of surface silicon present prior to brazing. This process can replace the need to perform a "moly-manganese" metallization step.

  4. Highly tilted liquid crystalline materials possessing a direct phase transition from antiferroelectric to isotropic phase

    Energy Technology Data Exchange (ETDEWEB)

    Milewska, K.; Drzewiński, W. [Institute of Chemistry, Military University of Technology, 00-908 Warsaw (Poland); Czerwiński, M., E-mail: mczerwinski@wat.edu.pl [Institute of Chemistry, Military University of Technology, 00-908 Warsaw (Poland); Dąbrowski, R. [Institute of Chemistry, Military University of Technology, 00-908 Warsaw (Poland); Piecek, W. [Institute of Applied Physics, Military University of Technology, 00-908 Warsaw (Poland)

    2016-03-01

    Pure compounds and multicomponent mixtures with a broad temperature range of high tilted liquid crystalline antiferroelectric phase and a direct phase transition from antiferroelectric to isotropic phase, were obtained. X-ray diffraction analysis confirms these kinds of materials form a high tilted anticlinic phase, with a fixed layer spacing and very weak dependency upon temperature, after the transition from the isotropic phase. Due to this, not only pure orthoconic antiferroelectric liquid crystals but also those with a moderate tilt should generate a good dark state. Furthermore, due to the increased potential for forming anticlinic forces, such materials could minimize a commonly observed asymmetry of a rise and fall switching times at a surface stabilized geometry. - Highlights: • The new class of liquid crystalline materials with the direct SmC{sub A}*. • Iso phase transition were obtained. • Materials possess the layer spacing fixed and very weak dependent upon temperature. • Smectic layers without shrinkage are observed. • A good dark state can be generate in SSAFLC.

  5. Control performances of a piezoactuator direct drive valve system at high temperatures with thermal insulation

    Science.gov (United States)

    Han, Yung-Min; Han, Chulhee; Kim, Wan Ho; Seong, Ho Yong; Choi, Seung-Bok

    2016-09-01

    This technical note presents control performances of a piezoactuator direct drive valve (PDDV) operated at high temperature environment. After briefly discussing operating principle and mechanical dimensions of the proposed PDDV, an appropriate size of the PDDV is manufactured. As a first step, the temperature effect on the valve performance is experimentally investigated by measuring the spool displacement at various temperatures. Subsequently, the PDDV is thermally insulated using aerogel and installed in a large-size heat chamber in which the pneumatic-hydraulic cylinders and sensors are equipped. A proportional-integral-derivative feedback controller is then designed and implemented to control the spool displacement of the valve system. In this work, the spool displacement is chosen as a control variable since it is directly related to the flow rate of the valve system. Three different sinusoidal displacements with different frequencies of 1, 10 and 50 Hz are used as reference spool displacement and tracking controls are undertaken up to 150 °C. It is shown that the proposed PDDV with the thermal insulation can provide favorable control responses without significant tracking errors at high temperatures.

  6. Ultrafast and directional diffusion of lithium in phosphorene for high-performance lithium-ion battery.

    Science.gov (United States)

    Li, Weifeng; Yang, Yanmei; Zhang, Gang; Zhang, Yong-Wei

    2015-03-11

    Density functional theory calculations have been performed to investigate the binding and diffusion behavior of Li in phosphorene. Our studies reveal the following findings: (1) Li atom forms strong binding with phosphorus atoms and exists in the cationic state; (2) the shallow energy barrier (0.08 eV) of Li diffusion on monolayer phosphorene along zigzag direction leads to an ultrahigh diffusivity, which is estimated to be 10(2) (10(4)) times faster than that on MoS2 (graphene) at room temperature; (3) the large energy barrier (0.68 eV) along armchair direction results in a nearly forbidden diffusion, and such strong diffusion anisotropy is absent in graphene and MoS2; (4) a remarkably large average voltage of 2.9 V is predicted in the phosphorene-based Li-ion battery; and (5) a semiconducting to metallic transition induced by Li intercalation of phosphorene gives rise to a good electrical conductivity, ideal for use as an electrode. Given these advantages, it is expected that phosphorene will present abundant opportunities for applications in novel electronic device and lithium-ion battery with a high rate capability and high charging voltage.

  7. Directed evolution strategies for enantiocomplementary haloalkane dehalogenases: from chemical waste to enantiopure building blocks.

    Science.gov (United States)

    van Leeuwen, Jan G E; Wijma, Hein J; Floor, Robert J; van der Laan, Jan-Metske; Janssen, Dick B

    2012-01-02

    We used directed evolution to obtain enantiocomplementary haloalkane dehalogenase variants that convert the toxic waste compound 1,2,3-trichloropropane (TCP) into highly enantioenriched (R)- or (S)-2,3-dichloropropan-1-ol, which can easily be converted into optically active epichlorohydrins-attractive intermediates for the synthesis of enantiopure fine chemicals. A dehalogenase with improved catalytic activity but very low enantioselectivity was used as the starting point. A strategy that made optimal use of the limited capacity of the screening assay, which was based on chiral gas chromatography, was developed. We used pair-wise site-saturation mutagenesis (SSM) of all 16 noncatalytic active-site residues during the initial two rounds of evolution. The resulting best R- and S-enantioselective variants were further improved in two rounds of site-restricted mutagenesis (SRM), with incorporation of carefully selected sets of amino acids at a larger number of positions, including sites that are more distant from the active site. Finally, the most promising mutations and positions were promoted to a combinatorial library by using a multi-site mutagenesis protocol with restricted codon sets. To guide the design of partly undefined (ambiguous) codon sets for these restricted libraries we employed structural information, the results of multiple sequence alignments, and knowledge from earlier rounds. After five rounds of evolution with screening of only 5500 clones, we obtained two strongly diverged haloalkane dehalogenase variants that give access to (R)-epichlorohydrin with 90 % ee and to (S)-epichlorohydrin with 97 % ee, containing 13 and 17 mutations, respectively, around their active sites. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst

    Science.gov (United States)

    Gao, Peng; Li, Shenggang; Bu, Xianni; Dang, Shanshan; Liu, Ziyu; Wang, Hui; Zhong, Liangshu; Qiu, Minghuang; Yang, Chengguang; Cai, Jun; Wei, Wei; Sun, Yuhan

    2017-10-01

    Although considerable progress has been made in carbon dioxide (CO2) hydrogenation to various C1 chemicals, it is still a great challenge to synthesize value-added products with two or more carbons, such as gasoline, directly from CO2 because of the extreme inertness of CO2 and a high C-C coupling barrier. Here we present a bifunctional catalyst composed of reducible indium oxides (In2O3) and zeolites that yields a high selectivity to gasoline-range hydrocarbons (78.6%) with a very low methane selectivity (1%). The oxygen vacancies on the In2O3 surfaces activate CO2 and hydrogen to form methanol, and C-C coupling subsequently occurs inside zeolite pores to produce gasoline-range hydrocarbons with a high octane number. The proximity of these two components plays a crucial role in suppressing the undesired reverse water gas shift reaction and giving a high selectivity for gasoline-range hydrocarbons. Moreover, the pellet catalyst exhibits a much better performance during an industry-relevant test, which suggests promising prospects for industrial applications.

  9. A new processing scheme for ultra-high resolution direct infusion mass spectrometry data

    Science.gov (United States)

    Zielinski, Arthur T.; Kourtchev, Ivan; Bortolini, Claudio; Fuller, Stephen J.; Giorio, Chiara; Popoola, Olalekan A. M.; Bogialli, Sara; Tapparo, Andrea; Jones, Roderic L.; Kalberer, Markus

    2018-04-01

    High resolution, high accuracy mass spectrometry is widely used to characterise environmental or biological samples with highly complex composition enabling the identification of chemical composition of often unknown compounds. Despite instrumental advancements, the accurate molecular assignment of compounds acquired in high resolution mass spectra remains time consuming and requires automated algorithms, especially for samples covering a wide mass range and large numbers of compounds. A new processing scheme is introduced implementing filtering methods based on element assignment, instrumental error, and blank subtraction. Optional post-processing incorporates common ion selection across replicate measurements and shoulder ion removal. The scheme allows both positive and negative direct infusion electrospray ionisation (ESI) and atmospheric pressure photoionisation (APPI) acquisition with the same programs. An example application to atmospheric organic aerosol samples using an Orbitrap mass spectrometer is reported for both ionisation techniques resulting in final spectra with 0.8% and 8.4% of the peaks retained from the raw spectra for APPI positive and ESI negative acquisition, respectively.

  10. Developing A Directional High-Dose Rate (d-HDR) Brachytherapy Source

    Science.gov (United States)

    Heredia, Athena Yvonne

    Conventional sources used in brachytherapy provide nearly isotropic or radially symmetric dose distributions. Optimizations of dose distributions have been limited to varied dwell times at specified locations within a given treatment volume, or manipulations in source position for seed implantation techniques. In years past, intensity modulated brachytherapy (IMBT) has been used to reduce the amount of radiation to surrounding sensitive structures in select intracavitary cases by adding space or partial shields. Previous work done by Lin et al., at the University of Wisconsin-Madison, has shown potential improvements in conformality for brachytherapy treatments using a directionally shielded low dose rate (LDR) source for treatments in breast and prostate. Directional brachytherapy sources irradiate approximately half of the radial angles around the source, and adequately shield a quarter of the radial angles on the opposite side, with sharp gradient zones between the treated half and shielded quarter. With internally shielded sources, the radiation can be preferentially emitted in such a way as to reduce toxicities in surrounding critical organs. The objective of this work is to present findings obtained in the development of a new directional high dose rate (d-HDR) source. To this goal, 103Pd (Z = 46) is reintroduced as a potential radionuclide for use in HDR brachytherapy. 103Pd has a low average photon energy (21 keV) and relatively short half -life (17 days), which is why it has historically been used in low dose rate applications and implantation techniques. Pd-103 has a carrier-free specific activity of 75000 Ci/g. Using cyclotron produced 103Pd, near carrier-free specific activities can be achieved, providing suitability for high dose rate applications. The evolution of the d-HDR source using Monte Carlo simulations is presented, along with dosimetric parameters used to fully characterize the source. In addition, a discussion on how to obtain elemental

  11. Enantioselective total synthesis of (+)-brefeldin A and 7-epi-brefeldin A.

    Science.gov (United States)

    Wu, Yikang; Shen, Xin; Yang, Yong-Qing; Hu, Qi; Huang, Jia-Hui

    2004-05-28

    A convergent enantioselective route to brefeldin A (BFA) and 7-epi-BFA was developed. The key C-4/C-5 chiral centers were established by using chiral auxiliary induced intermolecular asymmetric aldolization in the presence of TiCl(4) and TMEDA. The results with the thiazolidinethione/TiCl(4) mediated intermolecular asymmetric aldolization added some new information about the scope and limitations to the existing knowledge of that type of reactions (which so far was essentially limited to the reactions with N-propionyl thiazolidinethiones). During the course a method for protecting the liable aldol hydroxyl groups by using inexpensive TBSCl in DMF with 2,6-lutidine as the base was developed to replace the otherwise unavoidable TBSOTf procedure. Due to the excessive steric hindrance, removal of the auxiliary was much more difficult than most literature cases. Cleavage of the oxazolidinone by reduction was almost impossible. The thiazolidinethione auxiliary was relatively easier to remove. However, several reactions reported for facile removal of thiazolidinethione auxiliaries in the literature still failed. Reductive removal of the thiazolidinethione auxiliary was most effectively realized with LiBH(4) in diethyl ether in the presence of 1 equiv of MeOH (a modification of a literature procedure for removal of oxazolidinone auxiliaries in less hindered substrates). Apart from the auxiliary removal, oxidation of the alcohol into aldehyde and the deprotection of the dithiolane protecting group were also rather difficult in the present context. A range of methods were screened before final solutions were found. The five-membered ring was constructed by employing an intramolecular Mukaiyama reaction after many attempts with the intramolecular aldolization under a variety of conditions failed. The rate of elimination of the alkoxyl to form the alpha,beta-double bond of the key intermediate cyclopentenone 49 with DBU was highly solvent dependent (very sluggish in CH(2)Cl(2

  12. Interspecies differences in the enantioselectivity of epoxide hydrolases in Cryptococcus laurentii (Kufferath) C.E. Skinner and Cryptococcus podzolicus (Bab'jeva & Reshetova) Golubev

    CSIR Research Space (South Africa)

    Botes, AL

    2005-01-01

    Full Text Available Isolates representing Cryptococcus laurentii and Cryptococcus podzolicus, originating from soil of a heath land indigenous to South Africa, were screened for the presence of enantioselective epoxide hydrolases for 2, 2-disubstituted epoxides...

  13. Recyclable enantioselective catalysts based on copper(II) complexes of 2-(pyridine-2-yl)imidazolidine-4-thione: their application in asymmetric Henry reactions

    Czech Academy of Sciences Publication Activity Database

    Nováková, G.; Drabina, P.; Frumarová, Božena; Sedlák, M.

    2016-01-01

    Roč. 358, č. 15 (2016), s. 2541-2552 ISSN 1615-4150 Institutional support: RVO:61389013 Keywords : asymmetric catalysis * enantioselectivity * heterogeneous catalysis Subject RIV: CC - Organic Chemistry Impact factor: 5.646, year: 2016

  14. High-Brightness Blue Light-Emitting Diodes Enabled by a Directly Grown Graphene Buffer Layer.

    Science.gov (United States)

    Chen, Zhaolong; Zhang, Xiang; Dou, Zhipeng; Wei, Tongbo; Liu, Zhiqiang; Qi, Yue; Ci, Haina; Wang, Yunyu; Li, Yang; Chang, Hongliang; Yan, Jianchang; Yang, Shenyuan; Zhang, Yanfeng; Wang, Junxi; Gao, Peng; Li, Jinmin; Liu, Zhongfan

    2018-06-08

    Single-crystalline GaN-based light-emitting diodes (LEDs) with high efficiency and long lifetime are the most promising solid-state lighting source compared with conventional incandescent and fluorescent lamps. However, the lattice and thermal mismatch between GaN and sapphire substrate always induces high stress and high density of dislocations and thus degrades the performance of LEDs. Here, the growth of high-quality GaN with low stress and a low density of dislocations on graphene (Gr) buffered sapphire substrate is reported for high-brightness blue LEDs. Gr films are directly grown on sapphire substrate to avoid the tedious transfer process and GaN is grown by metal-organic chemical vapor deposition (MOCVD). The introduced Gr buffer layer greatly releases biaxial stress and reduces the density of dislocations in GaN film and In x Ga 1- x N/GaN multiple quantum well structures. The as-fabricated LED devices therefore deliver much higher light output power compared to that on a bare sapphire substrate, which even outperforms the mature process derived counterpart. The GaN growth on Gr buffered sapphire only requires one-step growth, which largely shortens the MOCVD growth time. This facile strategy may pave a new way for applications of Gr films and bring several disruptive technologies for epitaxial growth of GaN film and its applications in high-brightness LEDs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Direct-to-consumer television advertising exposure, diagnosis with high cholesterol, and statin use.

    Science.gov (United States)

    Niederdeppe, Jeff; Byrne, Sahara; Avery, Rosemary J; Cantor, Jonathan

    2013-07-01

    While statin drugs are recommended for secondary prevention of coronary heart disease (CHD), there is no medical consensus on whether or not a statin should be added to lifestyle change efforts for primary prevention of CHD. Previous research suggests that exposure to direct-to-consumer advertising (DTCA) increases drug demand among those at comparatively low risk. Research has yet to examine whether individual-level DTCA exposure may influence statin use among men and women at high, moderate, or low risk for future cardiac events. To determine the relationship between estimated exposure to DTCA for statin drugs and two clinical variables: diagnosis with high cholesterol and statin use. We used logistic regression to analyze repeated cross-sectional surveys of the United States population, merged with data on the frequency of DTCA appearances on national, cable, and local television, between 2001 and 2007. American adults (n=106,685) aged 18 and older. Levels of exposure to statin DTCA, based on ad appearances and TV viewing patterns; self-reports of whether or not a respondent has been diagnosed with high cholesterol, and whether or not a respondent took a statin in the past year. Adjusting for potential confounders, we estimate that exposure to statin ads increased the odds of being diagnosed with high cholesterol by 16 to 20 %, and increased statin use by 16 to 22 %, among both men and women (p<0.05). These associations were driven almost exclusively by men and women at low risk for future cardiac events. There was also evidence of a negative association between DTCA exposure and statin use among high-risk women (p<0.05) CONCLUSIONS: This study provides new evidence that DTCA may promote over-diagnosis of high cholesterol and over-treatment for populations where risks of statin use may outweigh potential benefits.

  16. Metal-Free Catalytic Enantioselective C–B Bond Formation: (Pinacolato)boron Conjugate Additions to α,β-Unsaturated Ketones, Esters, Weinreb Amides and Aldehydes Promoted by Chiral N-Heterocyclic Carbenes

    Science.gov (United States)

    Wu, Hao; Radomkit, Suttipol; O’Brien, Jeannette M.; Hoveyda, Amir H.

    2012-01-01

    The first broadly applicable metal-free enantioselective method for boron conjugate addition (BCA) to α,β-unsaturated carbonyls is presented. The C–B bond forming reactions are promoted in the presence of 2.5–7.5 mol % of a readily accessible C1-symmetric chiral imidazolinium salt, which is converted, in situ, to the catalytically active diastereo- and enantiomerically pure N-heterocyclic carbene (NHC) by the common organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu). In addition to the commercially available bis(pinacolato)diboron [B2(pin)2], and in contrast to reactions with the less sterically demanding achiral NHCs, the presence of MeOH is required for high efficiency. Acyclic and cyclic α,β-unsaturated ketones, as well as acyclic esters, Weinreb amides and aldehydes can serve as suitable substrates; the desired β-boryl carbonyls are isolated in up to 94% yield and >98:2 enantiomer ratio (er). Transformations are often carried out at ambient temperature. In certain cases, such as when the relatively less reactive unsaturated amides are used, elevated temperatures are required (50–66 °C); nonetheless, reactions remain highly enantioselective. The utility of the NHC-catalyzed method is demonstrated through comparison with the alternative Cu-catalyzed protocols; in cases involving a polyfunctional substrate, unique profiles in chemoselectivity are exhibited by the metal-free approach (e.g., conjugate addition vs reaction with an alkyne, allene or aldehyde). PMID:22559866

  17. Wireless Capacitive Pressure Sensor With Directional RF Chip Antenna for High Temperature Environments

    Science.gov (United States)

    Scardelletti, M. C.; Jordan, J. L.; Ponchak, G. E.; Zorman, C. A.

    2015-01-01

    This paper presents the design, fabrication and characterization of a wireless capacitive pressure sensor with directional RF chip antenna that is envisioned for the health monitoring of aircraft engines operating in harsh environments. The sensing system is characterized from room temperature (25 C) to 300 C for a pressure range from 0 to 100 psi. The wireless pressure system consists of a Clapp-type oscillator design with a capacitive MEMS pressure sensor located in the LC-tank circuit of the oscillator. Therefore, as the pressure of the aircraft engine changes, so does the output resonant frequency of the sensing system. A chip antenna is integrated to transmit the system output to a receive antenna 10 m away.The design frequency of the wireless pressure sensor is 127 MHz and a 2 increase in resonant frequency over the temperature range of 25 to 300 C from 0 to 100 psi is observed. The phase noise is less than minus 30 dBcHz at the 1 kHz offset and decreases to less than minus 80 dBcHz at 10 kHz over the entire temperature range. The RF radiation patterns for two cuts of the wireless system have been measured and show that the system is highly directional and the MEMS pressure sensor is extremely linear from 0 to 100 psi.

  18. Direct Photolithography on Molecular Crystals for High Performance Organic Optoelectronic Devices.

    Science.gov (United States)

    Yao, Yifan; Zhang, Lei; Leydecker, Tim; Samorì, Paolo

    2018-05-23

    Organic crystals are generated via the bottom-up self-assembly of molecular building blocks which are held together through weak noncovalent interactions. Although they revealed extraordinary charge transport characteristics, their labile nature represents a major drawback toward their integration in optoelectronic devices when the use of sophisticated patterning techniques is required. Here we have devised a radically new method to enable the use of photolithography directly on molecular crystals, with a spatial resolution below 300 nm, thereby allowing the precise wiring up of multiple crystals on demand. Two archetypal organic crystals, i.e., p-type 2,7-diphenyl[1]benzothieno[3,2- b][1]benzothiophene (Dph-BTBT) nanoflakes and n-type N, N'-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) nanowires, have been exploited as active materials to realize high-performance top-contact organic field-effect transistors (OFETs), inverter and p-n heterojunction photovoltaic devices supported on plastic substrate. The compatibility of our direct photolithography technique with organic molecular crystals is key for exploiting the full potential of organic electronics for sophisticated large-area devices and logic circuitries, thus paving the way toward novel applications in plastic (opto)electronics.

  19. High Performance Computation of a Jet in Crossflow by Lattice Boltzmann Based Parallel Direct Numerical Simulation

    Directory of Open Access Journals (Sweden)

    Jiang Lei

    2015-01-01

    Full Text Available Direct numerical simulation (DNS of a round jet in crossflow based on lattice Boltzmann method (LBM is carried out on multi-GPU cluster. Data parallel SIMT (single instruction multiple thread characteristic of GPU matches the parallelism of LBM well, which leads to the high efficiency of GPU on the LBM solver. With present GPU settings (6 Nvidia Tesla K20M, the present DNS simulation can be completed in several hours. A grid system of 1.5 × 108 is adopted and largest jet Reynolds number reaches 3000. The jet-to-free-stream velocity ratio is set as 3.3. The jet is orthogonal to the mainstream flow direction. The validated code shows good agreement with experiments. Vortical structures of CRVP, shear-layer vortices and horseshoe vortices, are presented and analyzed based on velocity fields and vorticity distributions. Turbulent statistical quantities of Reynolds stress are also displayed. Coherent structures are revealed in a very fine resolution based on the second invariant of the velocity gradients.

  20. Adaptive Modulation for DFIG and STATCOM With High-Voltage Direct Current Transmission.

    Science.gov (United States)

    Tang, Yufei; He, Haibo; Ni, Zhen; Wen, Jinyu; Huang, Tingwen

    2016-08-01

    This paper develops an adaptive modulation approach for power system control based on the approximate/adaptive dynamic programming method, namely, the goal representation heuristic dynamic programming (GrHDP). In particular, we focus on the fault recovery problem of a doubly fed induction generator (DFIG)-based wind farm and a static synchronous compensator (STATCOM) with high-voltage direct current (HVDC) transmission. In this design, the online GrHDP-based controller provides three adaptive supplementary control signals to the DFIG controller, STATCOM controller, and HVDC rectifier controller, respectively. The mechanism is to observe the system states and their derivatives and then provides supplementary control to the plant according to the utility function. With the GrHDP design, the controller can adaptively develop an internal goal representation signal according to the observed power system states, therefore, to achieve more effective learning and modulating. Our control approach is validated on a wind power integrated benchmark system with two areas connected by HVDC transmission lines. Compared with the classical direct HDP and proportional integral control, our GrHDP approach demonstrates the improved transient stability under system faults. Moreover, experiments under different system operating conditions with signal transmission delays are also carried out to further verify the effectiveness and robustness of the proposed approach.

  1. Enantioselective organocatalyzed Oxa-Michael-Aldol cascade reactions: Construction of chiral 4H-chromenes with a trifluoromethylated tetrasubstituted carbon stereocenter

    KAUST Repository

    Zhang, Jing

    2015-03-13

    The first organocatalytic asymmetric synthesis of 4H-chromenes bearing a trifluoromethylated tetrasubstituted carbon center is presented. Chiral secondary amines promote the oxa-Michael-aldol cascade reaction between alkynals and 2-trifluoroacetylphenols via iminium-allenamine activation to produce pharmaceutically important heterocycles with excellent enantioselectivities. The proposed reaction can be scaled-up easily with maintenance of the excellent enantioselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Stereoselective reactions. XXXII. Enantioselective deprotonation of 4-tert-butylcyclohexanone by fluorine-containing chiral lithium amides derived from 1-phenylethylamine and 1-(1-naphthyl)ethylamine.

    Science.gov (United States)

    Aoki, K; Koga, K

    2000-04-01

    Enantioselective deprotonation of 4-tert-butylcyclohexanone was examined using 1-phenylethylamine- and 1-(1-naphthyl)ethylamine-derived chiral lithium amides having an alkyl or a fluoroalkyl substituent at the amide nitrogen. The lithium amides having a 2,2,2-trifluoroethyl group on the amide nitrogen are easily accessible in both enantiomeric forms, and were found to induce good enantioselectivity in the present reaction.

  3. Voltage Balancing Method on Expert System for 51-Level MMC in High Voltage Direct Current Transmission

    Directory of Open Access Journals (Sweden)

    Yong Chen

    2016-01-01

    Full Text Available The Modular Multilevel Converters (MMC have been a spotlight for the high voltage and high power transmission systems. In the VSC-HVDC (High Voltage Direct Current based on Voltage Source Converter transmission system, the energy of DC link is stored in the distributed capacitors, and the difference of capacitors in parameters and charge rates causes capacitor voltage balance which affects the safety and stability of HVDC system. A method of MMC based on the expert system for reducing the frequency of the submodules (SMs of the IGBT switching frequency is proposed. Firstly, MMC with 51 levels for HVDC is designed. Secondly, the nearest level control (NLC for 51-level MMC is introduced. Thirdly, a modified capacitor voltage balancing method based on expert system for MMC-based HVDC transmission system is proposed. Finally, a simulation platform for 51-level Modular Multilevel Converter is constructed by using MATLAB/SIMULINK. The results indicate that the strategy proposed reduces the switching frequency on the premise of keeping submodule voltage basically identical, which greatly reduces the power losses for MMC-HVDC system.

  4. High-Definition transcranial direct current stimulation in early onset epileptic encephalopathy: a case study.

    Science.gov (United States)

    Meiron, Oded; Gale, Rena; Namestnic, Julia; Bennet-Back, Odeya; David, Jonathan; Gebodh, Nigel; Adair, Devin; Esmaeilpour, Zeinab; Bikson, Marom

    2018-01-01

    Early onset epileptic encephalopathy is characterized by high daily seizure-frequency, multifocal epileptic discharges, severe psychomotor retardation, and death at infancy. Currently, there are no effective treatments to alleviate seizure frequency and high-voltage epileptic discharges in these catastrophic epilepsy cases. The current study examined the safety and feasibility of High-Definition transcranial direct current stimulation (HD-tDCS) in reducing epileptiform activity in a 30-month-old child suffering from early onset epileptic encephalopathy. HD-tDCS was administered over 10 intervention days spanning two weeks including pre- and post-intervention video-EEG monitoring. There were no serious adverse events or side effects related to the HD-tDCS intervention. Frequency of clinical seizures was not significantly reduced. However, interictal sharp wave amplitudes were significantly lower during the post-intervention period versus baseline. Vital signs and blood biochemistry remained stable throughout the entire study. These exploratory findings support the safety and feasibility of 4 × 1 HD-tDCS in early onset epileptic encephalopathy and provide the first evidence of HD-tDCS effects on paroxysmal EEG features in electroclinical cases under the age of 36 months. Extending HD-tDCS treatment may enhance electrographic findings and clinical effects.

  5. High rate deposition of thin film cadmium sulphide by pulsed direct current magnetron sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Lisco, F., E-mail: F.Lisco@lboro.ac.uk [Centre for Renewable Energy Systems Technology (CREST), School of Electronic, Electrical and Systems Engineering, Loughborough University, Leicestershire LE11 3TU (United Kingdom); Kaminski, P.M.; Abbas, A.; Bowers, J.W.; Claudio, G. [Centre for Renewable Energy Systems Technology (CREST), School of Electronic, Electrical and Systems Engineering, Loughborough University, Leicestershire LE11 3TU (United Kingdom); Losurdo, M. [Institute of Inorganic Methodologies and of Plasmas, IMIP-CNR, via Orabona 4, 70126 Bari (Italy); Walls, J.M. [Centre for Renewable Energy Systems Technology (CREST), School of Electronic, Electrical and Systems Engineering, Loughborough University, Leicestershire LE11 3TU (United Kingdom)

    2015-01-01

    Cadmium Sulphide (CdS) is an important n-type semiconductor widely used as a window layer in thin film photovoltaics Copper Indium Selenide, Copper Indium Gallium (di)Selenide, Copper Zinc Tin Sulphide and Cadmium Telluride (CdTe). Cadmium Sulphide has been deposited using a number of techniques but these techniques can be slow (chemical bath deposition and Radio Frequency sputtering) or the uniformity and the control of thickness can be relatively difficult (close space sublimation). In this paper we report on the development of a process using pulsed Direct Current magnetron sputtering which allows nanometre control of thin film thickness using time only. The CdS thin films deposited in this process are highly uniform and smooth. They exhibit the preferred hexagonal structure at room temperature deposition and they have excellent optical properties. Importantly, the process is highly stable despite the use of a semi-insulating magnetron target. Moreover, the process is very fast. The deposition rate using 1.5 kW of power to a 6-inch circular magnetron was measured to be greater than 8 nm/s. This makes the process suitable for industrial deployment. - Highlights: • Pulsed DC magnetron sputtering of CdS • High deposition rate deposition • Uniform, pinhole free films.

  6. High-Performance Direct Methanol Fuel Cells with Precious-Metal-Free Cathode.

    Science.gov (United States)

    Li, Qing; Wang, Tanyuan; Havas, Dana; Zhang, Hanguang; Xu, Ping; Han, Jiantao; Cho, Jaephil; Wu, Gang

    2016-11-01

    Direct methanol fuel cells (DMFCs) hold great promise for applications ranging from portable power for electronics to transportation. However, apart from the high costs, current Pt-based cathodes in DMFCs suffer significantly from performance loss due to severe methanol crossover from anode to cathode. The migrated methanol in cathodes tends to contaminate Pt active sites through yielding a mixed potential region resulting from oxygen reduction reaction and methanol oxidation reaction. Therefore, highly methanol-tolerant cathodes must be developed before DMFC technologies become viable. The newly developed reduced graphene oxide (rGO)-based Fe-N-C cathode exhibits high methanol tolerance and exceeds the performance of current Pt cathodes, as evidenced by both rotating disk electrode and DMFC tests. While the morphology of 2D rGO is largely preserved, the resulting Fe-N-rGO catalyst provides a more unique porous structure. DMFC tests with various methanol concentrations are systematically studied using the best performing Fe-N-rGO catalyst. At feed concentrations greater than 2.0 m, the obtained DMFC performance from the Fe-N-rGO cathode is found to start exceeding that of a Pt/C cathode. This work will open a new avenue to use nonprecious metal cathode for advanced DMFC technologies with increased performance and at significantly reduced cost.

  7. Printing of highly conductive solution by alternating current electrohydrodynamic direct-write

    Science.gov (United States)

    Jiang, Jiaxin; Zheng, Gaofeng; Wang, Xiang; Zheng, Jianyi; Liu, Juan; Liu, Yifang; Li, Wenwang; Guo, Shumin

    2018-03-01

    Electrohydrodynamic Direct-Write (EDW) is a novel technology for the printing of micro/nano structures. In this paper, Alternating Current (AC) electrical field was introduced to improve the ejection stability of jet with highly conductive solution. By alternating the electrical field, the polarity of free charges on the surface of jet was changed and the average density of charge, as well as the repulsive force, was reduced to stabilize the jet. When the frequency of AC electrical field increased, the EDW process became more stable and the shape of deposited droplets became more regular. The diameter of printed droplets decreased and the deposition frequency increased with the increase of voltage frequency. The phenomenon of corona discharge was overcome effectively as well. To further evaluate the performance of AC EDW for highly conductive solution, more NaCl was added to the solution and the conductivity was increased to 2810μs/cm. With such high conductivity, the problem of serious corona discharge could still be prevented by AC EDW, and the diameter of printed droplets decreased significantly. This work provides an effective way to accelerate industrial applications of EDW.

  8. High rate deposition of thin film cadmium sulphide by pulsed direct current magnetron sputtering

    International Nuclear Information System (INIS)

    Lisco, F.; Kaminski, P.M.; Abbas, A.; Bowers, J.W.; Claudio, G.; Losurdo, M.; Walls, J.M.

    2015-01-01

    Cadmium Sulphide (CdS) is an important n-type semiconductor widely used as a window layer in thin film photovoltaics Copper Indium Selenide, Copper Indium Gallium (di)Selenide, Copper Zinc Tin Sulphide and Cadmium Telluride (CdTe). Cadmium Sulphide has been deposited using a number of techniques but these techniques can be slow (chemical bath deposition and Radio Frequency sputtering) or the uniformity and the control of thickness can be relatively difficult (close space sublimation). In this paper we report on the development of a process using pulsed Direct Current magnetron sputtering which allows nanometre control of thin film thickness using time only. The CdS thin films deposited in this process are highly uniform and smooth. They exhibit the preferred hexagonal structure at room temperature deposition and they have excellent optical properties. Importantly, the process is highly stable despite the use of a semi-insulating magnetron target. Moreover, the process is very fast. The deposition rate using 1.5 kW of power to a 6-inch circular magnetron was measured to be greater than 8 nm/s. This makes the process suitable for industrial deployment. - Highlights: • Pulsed DC magnetron sputtering of CdS • High deposition rate deposition • Uniform, pinhole free films

  9. Experiences of High School Students about the Predictors of Tobacco Use: a Directed Qualitative Content Analysis

    Directory of Open Access Journals (Sweden)

    Mahmoud Ghasemi

    2015-12-01

    Full Text Available Background and Objectives: Tobacco use is one of the most important risk factors that increases the burden of diseases worldwide. Based on the increasing speed of tobacco use, the aim of the present study was to explain the experiences of high school students about the determiners of use and non-use of tobacco (cigarettes and hookah based on the theory of protection motivation. Materials and Methods: The present study is a qualitative study based on content analysis that has been carried out for five months from 22, November of 2014 to 20, April of 2015 on male high schools in Noshahr. Data were collected in the form of semi-structured interviews from 21 male high school students of whom 7 smoked cigarettes, 7 used hookah and 7 of them did not use any type of tobacco. Data analysis was carried out through the use of directed qualitative content analysis. Results: Data analysis led to the extraction of 99 primary codes that were categorized into 9 predetermined levels of protection motivation theory including perceived sensitivity, perceived intensity, fear, perceived self-efficacy, response expense, efficiency of the perceived answer, external perceived reward, internal perceived reward, protection motivation. The findings of the study showed that the most important predictors for the use of tobacco were the structures of response expense and high perceived rewards and the most important predictors for non-use of tobacco were perceived sensitivity, perceived intensity and high self-efficacy of students. Conclusions: the findings of the present study showed that the pressure from peers, being present in a group using tobacco and the absence of alternative recreational activities are among the most important factors of using tobacco. So, it is suggested that planners of the health department take the comprehensive interventions to improve effective individual and environmental factors of using tobacco so that they could reduce smoking cigarettes

  10. Direct Observation of High-Temperature Superconductivity in One-Unit-Cell FeSe Films

    International Nuclear Information System (INIS)

    Zhang Wen-Hao; Zhang Jin-Song; Li Fang-Sen; Guo Ming-Hua; Ding Hao; Tang Chen-Jia; Wang Qing-Yan; He Ke; Ji Shuai-Hua; Chen Xi; Sun Yi; Zhao Yan-Fei; Xing Ying; Wang Hui-Chao; Zhang Hui-Min; Peng Jun-Ping; Li Zhi; Wang Meng; Fujita Takeshi; Hirata Akihiko

    2014-01-01

    We prepared one-unit-cell (1-UC) thick FeSe films on insulating SrTiO 3 substrates with non-superconducting FeTe protection layers by molecular beam epitaxy for ex situ studies. By direct transport and magnetic measurements, we provide definitive evidence for high temperature superconductivity in the 1-UC FeSe films with an onset T C above 40 K and an extremely large critical current density J C ∼1.7×10 6 A/cm 2 at 2 K, which are much higher than T C ∼8 K and J C ∼10 4 A/cm 2 for bulk FeSe, respectively. Our work may pave the way to enhancing and tailoring superconductivity by interface engineering. (express letter)

  11. Direct Printing of Stretchable Elastomers for Highly Sensitive Capillary Pressure Sensors.

    Science.gov (United States)

    Liu, Wenguang; Yan, Chaoyi

    2018-03-28

    We demonstrate the successful fabrication of highly sensitive capillary pressure sensors using an innovative 3D printing method. Unlike conventional capacitive pressure sensors where the capacitance changes were due to the pressure-induced interspace variations between the parallel plate electrodes, in our capillary sensors the capacitance was determined by the extrusion and extraction of liquid medium and consequent changes of dielectric constants. Significant pressure sensitivity advances up to 547.9 KPa -1 were achieved. Moreover, we suggest that our innovative capillary pressure sensors can adopt a wide range of liquid mediums, such as ethanol, deionized water, and their mixtures. The devices also showed stable performances upon repeated pressing cycles. The direct and versatile printing method combined with the significant performance advances are expected to find important applications in future stretchable and wearable electronics.

  12. Search for direct evidence for charm in hadronic interactions using a high-resolution bubble chamber

    CERN Multimedia

    2002-01-01

    A high-resolution rapid-cycling hydrogen bubble chamber will be used to search for direct evidence of charmed-particle production in $\\sim$350 GeV/c $\\pi^{-}$ interactions. The chamber is 20 cm in diameter and contains $\\sim$1l of liquid hydrogen. The bright field optical system is designed to achieve a resolution in space $\\simeq$ 20-30 $\\mu$m (optical depth of field 2-4 mm), which should allow the detection of charmed-particle decay vertices in complex events if $\\tau_{charm} \\geq 10^{-13}$ sec. An interaction trigger will be used to give an initial sensitivity $\\sim$5-10 events/$\\mu$b for a test run designed primarily to search for the signal and establish a cross-section and approximate lifetime for charm.

  13. High Transverse Momentum Direct Photon Production at Fermilab Fixed-Target Energies

    International Nuclear Information System (INIS)

    Apanasevich, Leonard

    2005-01-01

    This thesis describes a study of the production of high transverse momentum direct photons and π 0 mesons by proton beams at 530 and 800 GeV/c and π - beams at 515 GeV/c incident on beryllium, copper, and liquid hydrogen targets. The data were collected by Fermilab experiment E706 during the 1990 and 1991-92 fixed target runs. The apparatus included a large, finely segmented lead and liquid argon electromagnetic calorimeter and a charged particle spectrometer featuring silicon strip detectors in the target region and proportional wire chambers and drift tubes downstream of a large aperture analysis magnet. The inclusive cross sections are presented as functions of transverse momentum and rapidity. The measurements are compared with next-to-leading order perturbative QCD calculations and to results from previous experiments

  14. An ultra-high-speed direct digital frequency synthesizer implemented in GaAs HBT technology

    International Nuclear Information System (INIS)

    Chen Gaopeng; Wu Danyu; Jin Zhi; Liu Xinyu

    2010-01-01

    This paper presents a 10-GHz 8-bit direct digital synthesizer (DDS) microwave monolithic integrated circuit implemented in 1 μm GaAs HBT technology. The DDS takes a double-edge-trigger (DET) 8-stage pipeline accumulator with sine-weighted DAC-based ROM-less architecture, which can maximize the utilization ratio of the GaAs HBT's high-speed potential. With an output frequency up to 5 GHz, the DDS gives an average spurious free dynamic range of 23.24 dBc through the first Nyquist band, and consumes 2.4 W of DC power from a single -4.6 V DC supply. Using 1651 GaAs HBT transistors, the total area of the DDS chip is 2.4 x 2.0 mm 2 . (semiconductor integrated circuits)

  15. FARADAY CUP AWARD: High Sensitivity Tune Measurement using Direct Diode Detection

    CERN Document Server

    Gasior, M

    2012-01-01

    Direct Diode Detection (3D) is a technique developed at CERN initially for the LHC tune measurement system, to reach a sensitivity allowing observation of beam betatron oscillations with amplitudes below a micrometre. In this technique simple peak diode detectors are used to convert short beam pulses from a beam position pick-up into slowly varying signals. Their DC components, constituting a large background related to beam offsets, are suppressed by series capacitors, while the small signals related to beam oscillations are passed to the subsequent stages for amplification and filtering. As the demodulated beam oscillation signals are already in the kHz range, their processing is simple and they can be digitised with high resolution audio ADCs. This paper presents the history as well as the adventures of the 3D development and prototyping, along with some technical details. It documents a very efficient collaboration between CERN and Brookhaven National Laboratory (BNL), with contributions from other labora...

  16. Rationale for continuing R&D in direct coal conversion to produce high quality transportation fuels

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, R.D.; McIlvried, H.G. [Burns and Roe Services Corp., Pittsburgh, PA (United States); Gray, D. [Mitre Corp, McLean, VA (United States)] [and others

    1995-12-31

    For the foreseeable future, liquid hydrocarbon fuels will play a significant role in the transportation sector of both the United States and the world. Factors favoring these fuels include convenience, high energy density, and the vast existing infrastructure for their production and use. At present the U.S. consumes about 26% of the world supply of petroleum, but this situation is expected to change because of declining domestic production and increasing competition for imports from countries with developing economies. A scenario and time frame are developed in which declining world resources will generate a shortfall in petroleum supply that can be allieviated in part by utilizing the abundant domestic coal resource base. One option is direct coal conversion to liquid transportation fuels. Continued R&D in coal conversion technology will results in improved technical readiness that can significantly reduce costs so that synfuels can compete economically in a time frame to address the shortfall.

  17. Expansion of the high-voltage direct current transmission systems; Netzausbau mit Hochspannungs-Gleichstrom-Uebertragung

    Energy Technology Data Exchange (ETDEWEB)

    Spahic, Ervin; Benz, Thomas; Goerner, Raphael; Sass, Florian [ABB AG, Mannheim (Germany)

    2012-12-15

    In September 2010 the German federal government announced its energy concept for an environmentally friendly, reliable and affordable energy supply. This concept describes a ''path into the era of renewable energy'' up to the year 2050, with electricity production from photovoltaics and wind power taking centre stage. Since the expansion of renewable energy production is mainly taking place in the North (wind power) and the South (PV), this poses a great challenge to the electricity networks. It necessitates the expansion of power transmission systems, notably for transporting electricity generated by wind power in the North to the consumer centres in Western and Southern Germany. However, progress to this end has been very slow. For this reason a technical question now presents itself, namely whether high-voltage direct current technology could possibly offer a solution to the electricity transport problems associated with the energy turnaround.

  18. Immobilized Burkholderia cepacia Lipase on pH-Responsive Pullulan Derivatives with Improved Enantioselectivity in Chiral Resolution

    Directory of Open Access Journals (Sweden)

    Li Xu

    2018-01-01

    Full Text Available A kind of pH-responsive particle was synthesized using modified pullulan polysaccharide. The synthesized particle possessed a series of merits, such as good dispersity, chemical stability and variability of particle size, making it a suitable carrier for enzyme immobilization. Then, Burkholderia cepacia lipase (BCL, a promising biocatalyst in transesterification reaction, was immobilized on the synthesized particle. The highest catalytic activity and immobilization efficiency were achieved at pH 6.5 because the particle size was obviously enlarged and correspondingly the adsorption surface for BCL was significantly increased. The immobilization enzyme loading was further optimized, and the derivative lipase was applied in chiral resolution. Under the optimal reaction conditions, the immobilized BCL showed a very good performance and significantly shortened the reaction equilibrium time from 30 h of the free lipase to 2 h with a conversion rate of 50.0% and ees at 99.2%. The immobilized lipase also exhibited good operational stability; after being used for 10 cycles, it still retained over 80% of its original activity. Moreover, it could keep more than 80% activity after storage for 20 days at room temperature in a dry environment. In addition, to learn the potential mechanism, the morphology of the particles and the immobilized lipase were both characterized with a scanning electron microscope and confocal laser scanning microscopy. It was found that the enlarged spherical surface of the particle in low pH values probably led to high immobilized efficiency, resulting in the improvement of enantioselectivity activity in chiral resolution.

  19. Highly directional transurethral ultrasound applicators with rotational control for MRI-guided prostatic thermal therapy

    Energy Technology Data Exchange (ETDEWEB)

    Ross, Anthony B [Thermal Therapy Research Group, UCSF Radiation Oncology, San Francisco, CA (United States); Diederich, Chris J [Thermal Therapy Research Group, UCSF Radiation Oncology, San Francisco, CA (United States); Nau, William H [Thermal Therapy Research Group, UCSF Radiation Oncology, San Francisco, CA (United States); Gill, Harcharan [Department of Urology, Stanford University, Stanford, CA (United States); Bouley, Donna M [Department of Comparative Medicine, Stanford University, Stanford, CA (United States); Daniel, Bruce [Department of Radiology, Stanford University, Stanford, CA (United States); Rieke, Viola [Department of Radiology, Stanford University, Stanford, CA (United States); Butts, R Kim [Department of Radiology, Stanford University, Stanford, CA (United States); Sommer, Graham [Department of Radiology, Stanford University, Stanford, CA (United States)

    2004-01-21

    Transurethral ultrasound applicators with highly directional energy deposition and rotational control were investigated for precise treatment of benign prostatic hyperplasia (BPH) and adenocarcinoma of the prostate (CaP). Two types of catheter-based applicators were fabricated, using either sectored tubular (3.5 mm OD x 10 mm) or planar transducers (3.5 mm x 10 mm). They were constructed to be MRI compatible, minimally invasive and allow for manual rotation of the transducer array within a 10 mm cooling balloon. In vivo evaluations of the applicators were performed in canine prostates (n 3) using MRI guidance (0.5 T interventional magnet). MR temperature imaging (MRTI) utilizing the proton resonance frequency shift method was used to acquire multiple-slice temperature overlays in real time for monitoring and guiding the thermal treatments. Post-treatment T1-weighted contrast-enhanced imaging and triphenyl tetrazolium chloride stained tissue sections were used to define regions of tissue coagulation. Single sonications with the tubular applicator ) produced coagulated zones covering a wedge of the prostate extending from 1-2 mm outside the urethra to the outer boundary of the gland (16 mm radial coagulation). Single sonications with the planar applicator (15-20 W, 10 min, {approx}8 MHz) generated thermal lesions of {approx}30 extending to the prostate boundary. Multiple sequential sonications (sweeping) of a planar applicator (12 W with eight rotations of 30 each) demonstrated controllable coagulation of a 270 contiguous section of the prostate extending to the capsule boundary. The feasibility of using highly directional transurethral ultrasound applicators with rotational capabilities to selectively coagulate regions of the prostate while monitoring and controlling the treatments with MRTI was demonstrated in this study.

  20. High Voltage Solar Array Arc Testing for a Direct Drive Hall Effect Thruster System

    Science.gov (United States)

    Schneider, Todd; Carruth, M. R., Jr.; Vaughn, J. A.; Jongeward, G. A.; Mikellides, I. G.; Ferguson, D.; Kerslake, T. W.; Peterson, T.; Snyder, D.; Hoskins, A.

    2004-01-01

    The deleterious effects of spacecraft charging are well known, particularly when the charging leads to arc events. The damage that results from arcing can severely reduce system lifetime and even cause critical system failures. On a primary spacecraft system such as a solar array, there is very little tolerance for arcing. Motivated by these concerns, an experimental investigation was undertaken to determine arc thresholds for a high voltage (200-500 V) solar array in a plasma environment. The investigation was in support of a NASA program to develop a Direct Drive Hall-Effect Thruster (D2HET) system. By directly coupling the solar array to a Hall-effect thruster, the D2HET program seeks to reduce mass, cost and complexity commonly associated with the power processing in conventional power systems. In the investigation, multiple solar array technologies and configurations were tested. The cell samples were biased to a negative voltage, with an applied potential difference between them, to imitate possible scenarios in solar array strings that could lead to damaging arcs. The samples were tested in an environment that emulated a low-energy, HET-induced plasma. Short duration trigger arcs as well as long duration sustained arcs were generated. Typical current and voltage waveforms associated with the arc events are presented. Arc thresholds are also defined in terms of voltage, current and power. The data will be used to propose a new, high-voltage (greater than 300 V) solar array design for which the likelihood of damage from arcing is minimal.

  1. Integrating high dimensional bi-directional parsing models for gene mention tagging.

    Science.gov (United States)

    Hsu, Chun-Nan; Chang, Yu-Ming; Kuo, Cheng-Ju; Lin, Yu-Shi; Huang, Han-Shen; Chung, I-Fang

    2008-07-01

    Tagging gene and gene product mentions in scientific text is an important initial step of literature mining. In this article, we describe in detail our gene mention tagger participated in BioCreative 2 challenge and analyze what contributes to its good performance. Our tagger is based on the conditional random fields model (CRF), the most prevailing method for the gene mention tagging task in BioCreative 2. Our tagger is interesting because it accomplished the highest F-scores among CRF-based methods and second over all. Moreover, we obtained our results by mostly applying open source packages, making it easy to duplicate our results. We first describe in detail how we developed our CRF-based tagger. We designed a very high dimensional feature set that includes most of information that may be relevant. We trained bi-directional CRF models with the same set of features, one applies forward parsing and the other backward, and integrated two models based on the output scores and dictionary filtering. One of the most prominent factors that contributes to the good performance of our tagger is the integration of an additional backward parsing model. However, from the definition of CRF, it appears that a CRF model is symmetric and bi-directional parsing models will produce the same results. We show that due to different feature settings, a CRF model can be asymmetric and the feature setting for our tagger in BioCreative 2 not only produces different results but also gives backward parsing models slight but constant advantage over forward parsing model. To fully explore the potential of integrating bi-directional parsing models, we applied different asymmetric feature settings to generate many bi-directional parsing models and integrate them based on the output scores. Experimental results show that this integrated model can achieve even higher F-score solely based on the training corpus for gene mention tagging. Data sets, programs and an on-line service of our gene

  2. Enantioselectivity of a recombinant epoxide hydrolase from Agrobacterium radiobacter

    NARCIS (Netherlands)

    Lutje Spelberg, Jeffrey H.; Rink, Rick; Kellogg, Richard M.; Janssen, Dick B.

    1998-01-01

    The recombinant epoxide hydrolase from Agrobacterium radiobacter AD1 was used to obtain enantiomerically pure epoxides by means of a kinetic resolution. Epoxides such as styrene oxide and various derivatives thereof and phenyl glycidyl ether were obtained in high enantiomeric excess and in

  3. Nano-laminate vs. direct deposition of high permittivity gadolinium scandate on silicon by high pressure sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Feijoo, P.C., E-mail: pedronska@fis.ucm.es [Dpto. Física Aplicada III (Electricidad y Electrónica), Universidad Complutense de Madrid, Fac. de CC. Físicas. Av/Complutense S/N, E-28040 Madrid (Spain); Pampillón, M.A.; San Andrés, E. [Dpto. Física Aplicada III (Electricidad y Electrónica), Universidad Complutense de Madrid, Fac. de CC. Físicas. Av/Complutense S/N, E-28040 Madrid (Spain); Fierro, J.L.G. [Instituto de Catálisis y Petroleoquímica, Consejo Superior de Investigaciones Científicas, C/Marie Curie 2, E-28049 Cantoblanco (Spain)

    2015-10-30

    In this work we use the high pressure sputtering technique to deposit the high permittivity dielectric gadolinium scandate on silicon substrates. This nonconventional deposition technique prevents substrate damage and allows for growth of ternary compounds with controlled composition. Two different approaches were assessed: the first one consists of depositing the material directly from a stoichiometric GdScO{sub 3} target; in the second one, we anneal a nano-laminate of < 0.5 nm thick Gd{sub 2}O{sub 3} and Sc{sub 2}O{sub 3} films in order to control the composition of the scandate. Metal–insulator–semiconductor capacitors were fabricated with platinum gates for electrical characterization. Accordingly, we grew a Gd-rich Gd{sub 2−x}Sc{sub x}O{sub 3} film that, in spite of higher leakage currents, presents a better effective relative permittivity of 21 and lower density of defects. - Highlights: • GdScO is deposited on Si as a high permittivity dielectric by two procedures. • Films sputtered from GdScO{sub 3} target are Sc-rich and present thick interface SiO{sub x}. • Gd-rich GdScO is obtained from a nano-laminate sputtered from Sc{sub 2}O{sub 3} and Gd{sub 2}O{sub 3}. • Gd{sub 1.8}Sc{sub 0.2}O{sub 3} shows good effective permittivity and electrical properties.

  4. Glucose Oxidase Directly Immobilized onto Highly Porous Gold Electrodes for Sensing and Fuel Cell applications

    International Nuclear Information System (INIS)

    Toit, Hendrik du; Di Lorenzo, Mirella

    2014-01-01

    Highlights: • Electrochemical adsorption of glucose oxidase (GOx) on highly porous gold (hPG); • Rapid one-step immobilisation protocol with no use of expensive and/or harsh reagents; • Linear response to glucose in the range 50 μM -10 mM; • Lower detection limit, stable over 5 days: 25 μM. • The use of the GOx-hPG in a fuel cell lead to the peak power density of 6 μW cm −2 . - Abstract: The successful implementation of redox-enzyme electrodes in biosensors and enzymatic biofuel cells has been the subject of extensive research. For high sensitivity and high energy-conversion efficiency, the effective electron transfer at the protein-electrode interface has a key role. This is difficult to achieve in the case of glucose oxidase, due to the fact that for this enzyme the redox centre is buried inside the structure, far from any feasible electrode binding sites. This study reports, a simple and rapid methodology for the direct immobilisation of glucose oxidase into highly porous gold electrodes. When the resulting electrode was tested as glucose sensor, a Michaelis-Menten kinetic trend was observed, with a detection limit of 25 μM. The bioelectrode sensitivity, calculated against the superficial surface area of the bioelectrode, was of 22.7 ± 0.1 μA mM −1 cm −2 . This glucose oxidase electrode was also tested as an anode in a glucose/O 2 enzymatic biofuel cell, leading to a peak power density of 6 μW cm −2 at a potential of 0.2 V

  5. Plant accident dynamics of high-temperature reactors with direct gas turbine cycle

    International Nuclear Information System (INIS)

    Waloch, M.L.

    1977-01-01

    In the paper submitted, a one-dimensional accident simulation model for high-temperature reactors with direct-cycle gas turbine (single-cycle facilities) is described. The paper assesses the sudden failure of a gas duct caused by the double-ended break of one out of several parallel pipes before and behind the reactor for a non-integrated plant, leading to major loads in the reactor region, as well as the complete loss of vanes of the compressor for an integrated plant. The results of the calculations show especially high loads for the break of a hot-gas pipe immediately behind the flow restrictors of the reactor outlet, because of prolonged effects of pressure gradients in the reactor region and the maximum core differential pressure. A plant accident dynamics calculation therefore allows to find a compromise between the requirements of stable compressor operation, on the one hand, and small loads in the reactor in the course of an accident, on the other, by establishing in a co-ordinated manner the narrowing ratio of the flow restrictors. (GL) [de

  6. Packaging of high-power bars for optical pumping and direct applications

    Science.gov (United States)

    Heinemann, Stefan; An, Haiyan; Barnowski, Tobias; Jiang, John; Negoita, Viorel; Roff, Robert; Vethake, Thilo; Boucke, Konstantin; Treusch, Georg

    2015-03-01

    Continuous cost reduction, improved reliability and modular platform guide the design of our next generation heatsink and packaging process. Power scaling from a single device effectively lowers the cost, while electrical insulation of the heatsink, low junction temperature and hard solder enable high reliability. We report on the latest results for scaling the output power of bars for optical pumping and materials processing. The epitaxial design and geometric structures are specific for the application, while packaging with minimum thermal impedance, low stress and low smile are generic features. The isolated heatsink shows a thermal impedance of 0.2 K/W and the maximum output power is limited by the requirement of a junction temperature of less than 68oC for high reliability. Low contact impedance are addressed for drive currents of 300 A. For pumping applications, bars with a fill factor of 60% are deployed emitting more than 300 W of output power with an efficiency of about 55% and 8 bars are arranged in a compact pump module emitting 2 kW of collimated power suitable for pumping disk lasers. For direct applications we target coupling kilowatts of output powers into fibers of 100 μm diameter with 0.1 NA based on dense wavelength multiplexing. Low fill factor bars with large optical waveguide and specialized coating also emit 300 W.

  7. Direct fabrication of high-resolution three-dimensional polymeric scaffolds using electrohydrodynamic hot jet plotting

    International Nuclear Information System (INIS)

    Wei, Chuang; Dong, Jingyan

    2013-01-01

    This paper presents the direct three-dimensional (3D) fabrication of polymer scaffolds with sub-10 µm structures using electrohydrodynamic jet (EHD-jet) plotting of melted thermoplastic polymers. Traditional extrusion-based fabrication approaches of 3D periodic porous structures are very limited in their resolution, due to the excessive pressure requirement for extruding highly viscous thermoplastic polymers. EHD-jet printing has become a high-resolution alternative to other forms of nozzle deposition-based fabrication approaches by generating micro-scale liquid droplets or a fine jet through the application of a large electrical voltage between the nozzle and the substrate. In this study, we successfully apply EHD-jet plotting technology with melted biodegradable polymer (polycaprolactone, or PCL) for the fabrication of 2D patterns and 3D periodic porous scaffold structures in potential tissue engineering applications. Process conditions (e.g. electrical voltage, pressure, plotting speed) have been thoroughly investigated to achieve reliable jet printing of fine filaments. We have demonstrated for the first time that the EHD-jet plotting process is capable of the fabrication of 3D periodic structures with sub-10 µm resolution, which has great potential in advanced biomedical applications, such as cell alignment and guidance. (paper)

  8. Controlling the stainless steel surface wettability by nanosecond direct laser texturing at high fluences

    Science.gov (United States)

    Gregorčič, P.; Šetina-Batič, B.; Hočevar, M.

    2017-12-01

    This work investigates the influence of the direct laser texturing at high fluences (DLT-HF) on surface morphology, chemistry, and wettability. We use a Nd:YAG laser ( λ = 1064 nm) with pulse duration of 95 ns to process stainless steel surface. The surface morphology and chemistry after the texturing is examined by using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and electron backscatter diffraction (EBSD), while the surface wettability is evaluated by measuring the static contact angle. Immediately after the texturing, the surface is superhydrophilic in a saturated Wenzel regime. However, this state is not stable and the superhydrophilic-to-superhydrophobic transition happens if the sample is kept in atmospheric air for 30 days. After this period, the laser-textured stainless steel surface expresses lotus-leaf-like behavior. By using a high-speed camera at 10,000 fps, we measured that the water droplet completely rebound from this superhydrophobic surface after the contact time of 12 ms.

  9. The Need for Direct High-Energy Cosmic-Ray Measurements

    Science.gov (United States)

    Jones, Frank C.; Streitmatter, Robert

    2004-01-01

    Measuring the chemical composition of the cosmic rays in the energy region of greater than or equal to 10(exp 12)eV would be highly useful in settling several nagging questions concerning the propagation of cosmic rays in the galaxy. In particular an accurate measurement of secondary to primary ratios such as Boron to Carbon would gibe clear evidence as to whether the propagation of cosmic rays is determined by a diffusion coefficient that varies with the particle's energy as E(sup 0.5) or E(sup 0.3). This would go a long ways in helping us to understand the anistropy (or lack thereof) of the highest energy cosmic rays and the power requirements for producing those particles at approximately equal to 10(exp 18) eV which are believed to be highest energy particles produced in the Galaxy. This would be only one of the benefits of a mission such as ACCESS to perform direct particle measurements on very high energy cosmic rays.

  10. Direct electron acceleration in plasma waveguides for compact high-repetition-rate x-ray sources

    International Nuclear Information System (INIS)

    Lin, M-W; Jovanovic, I

    2014-01-01

    Numerous applications in fundamental and applied research, security, and industry require robust, compact sources of x-rays, with a particular recent interest in monochromatic, spatially coherent, and ultrafast x-ray pulses in well-collimated beams. Such x-ray sources usually require production of high-quality electron beams from compact accelerators. Guiding a radially polarized laser pulse in a plasma waveguide has been proposed for realizing direct laser acceleration (DLA), where the electrons are accelerated by the axial electric field of a co-propagating laser pulse (Serafim et al 2000 IEEE Trans. Plasma Sci. 28 1190). A moderate laser peak power is required for DLA when compared to laser wakefield acceleration, thus offering the prospect for high repetition rate operation. By using a density-modulated plasma waveguide for DLA, the acceleration distance can be extended with pulse guiding, while the density-modulation with proper axial structure can realize the quasi-phase matching between the laser pulses and electrons for a net gain accumulation (York et al 2008 Phys. Rev. Lett. 100 195001; York et al 2008 J. Opt. Soc. Am. B 25 B137; Palastro et al 2008 Phys. Rev. E 77 036405). We describe the development and application of a test particle model and particle-in-cell model for DLA. Experimental setups designed for fabrication of optically tailored plasma waveguides via the ignitor-heater scheme, and for generation and characterization of radially polarized short pulses used to drive DLA, are presented. (paper)

  11. High temperature thermal conductivity measurements of UO2 by Direct Electrical Heating. Final report

    International Nuclear Information System (INIS)

    Bassett, B.

    1980-10-01

    High temperature properties of reactor type UO 2 pellets were measured using a Direct Electrical Heating (DEH) Facility. Modifications to the experimental apparatus have been made so that successful and reproducible DEH runs may be carried out while protecting the pellets from oxidation at high temperature. X-ray diffraction measurements on the UO 2 pellets have been made before and after runs to assure that sample oxidation has not occurred. A computer code has been developed that will model the experiment using equations that describe physical properties of the material. This code allows these equations to be checked by comparing the model results to collected data. The thermal conductivity equation for UO 2 proposed by Weilbacher has been used for this analysis. By adjusting the empirical parameters in Weilbacher's equation, experimental data can be matched by the code. From the several runs analyzed, the resulting thermal conductivity equation is lambda = 1/4.79 + 0.0247T/ + 1.06 x 10 -3 exp[-1.62/kT/] - 4410. exp[-3.71/kT/] where lambda is in w/cm K, k is the Boltzman constant, and T is the temperature in Kelvin

  12. Thermochemistry of some binary lead and transition metal compounds by high temperature direct synthesis calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Meschel, S.V., E-mail: meschel@jfi.uchicago.edu [Illinois Institute of Technology,Thermal Processing Technology Center, 10 W. 32nd Street, Chicago, Illinois 60615 (United States); Gordon Center for Integrated Science, 929 E. 57th Street, Chicago, Illinois 60637 (United States); Nash, P. [Illinois Institute of Technology,Thermal Processing Technology Center, 10 W. 32nd Street, Chicago, Illinois 60615 (United States); Chen, X.Q.; Wei, P. [Materials processing Modeling Division, Shenyang National Laboratory for Materials Science, Institute of Metals Research, 72 Wenhua Road, Shenyang City (China)

    2015-06-05

    Highlights: • Studied binary lead-transition metal alloys by high temperature calorimetry. • Determined the enthalpies of formation of 8 alloys. • Compared the measurements with predictions by the model of Miedema and by the ab initio method. - Abstract: The standard enthalpies of formation of some binary lead and transition metal compounds have been measured by high temperature direct synthesis calorimetry. The reported results are: Pb{sub 3}Sc{sub 5}(−61.3 ± 2.9); PbTi{sub 4}(−16.6 ± 2.4); Pb{sub 3}Y{sub 5}(−64.8 ± 3.6); Pb{sub 3}Zr{sub 5}(−50.6 ± 3.1); PbNb{sub 3}(−10.4 ± 3.4); PbRh(−16.5 ± 3.3); PbPd{sub 3}(−29.6 ± 3.1); PbPt(−34.7 ± 3.3) kJ/mole of atoms. We will compare our results with previously published measurements. We will also compare the experimental measurements with enthalpies of formation of transition metal compounds with elements in the same vertical column in the periodic table. We will compare our measurements with predicted values on the basis of the semi empirical model of Miedema and coworkers and with ab initio values when available.

  13. MOTHER MK II: An advanced direct cycle high temperature gas reactor

    International Nuclear Information System (INIS)

    Hart, R.S.; Kendall, J.M.; Marsden, B.J.

    2003-01-01

    The MOTHER (MOdular Thermal HElium Reactor) power plant concepts employ high temperature gas reactors utilizing TRISO fuel, graphite moderator, and helium coolant, in combination with a direct Brayton cycle for electricity generation. The helium coolant from the reactor vessel passes through a Power Conversion Unit (PCU), which includes a turbine-generator, recuperator, precooler, intercooler and turbine-compressors, before being returned to the reactor vessel. The PCU substitutes for the reactor coolant system pumps and steam generators and most of the Balance Of Plant (BOP), including the steam turbines and condensers, employed by conventional nuclear power plants utilizing water cooled reactors. This provides a compact, efficient, and relatively simple plant configuration. The MOTHER MK I conceptual design, completed in the 1987 - 1989 time frame, was developed to economically meet the energy demands for extracting and processing heavy oil from the tar sands of western Canada. However, considerable effort was made to maximize the market potential beyond this application. Consistent with the remote and very high labour rate environment in the tar sands region, simplification of maintenance procedures and facilitation of 'change-out' in lieu of in situ repair was a design focus. MOTHER MK I had a thermal output of 288 MW and produced 120 MW electrical when operated in the electricity only production mode. An annular Prismatic reactor core was utilized, largely to minimize day-to-day operations activities. Key features of the power conversion system included two Power Conversion Units (144 MW th each), the horizontal orientation of all rotating machinery and major heat exchangers axes, high speed rotating machinery (17,030 rpm for the turbine-compressors and 10,200 rpm for the power turbine-generator), gas (helium) bearings for all rotating machinery, and solid state frequency conversion from 170 cps (at full power) to the grid frequency. Recognizing that the on

  14. Pushing the speed limit in enantioselective supercritical fluid chromatography.

    Science.gov (United States)

    Regalado, Erik L; Welch, Christopher J

    2015-08-01

    Chromatographic enantioseparations on the order of a few seconds can be achieved by supercritical fluid chromatography using short columns packed with chiral stationary phases. The evolution of 'world record' speeds for the chromatographic separation of enantiomers has steadily dropped from an industry standard of 20-40 min just two decades ago, to a current ability to perform many enantioseparations in well under a minute. Improvements in instrument and column technologies enabled this revolution, but the ability to predict optimal separation time from an initial method development screening assay using the t(min cc) predictor greatly simplifies the development and optimization of high-speed chiral chromatographic separations. In this study, we illustrate how the use of this simple tool in combination with the workhorse technique of supercritical fluid chromatography on customized short chiral columns (1-2 cm length) allows us to achieve ultrafast enantioseparations of pharmaceutically relevant compounds on the 5-20 s scale, bringing the technique of high-throughput enantiopurity analysis out of the specialist realm and into the laboratories of most researchers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Direct observation of organic layer growth by dynamic spectro-microscopy using high-brilliance synchrotron

    International Nuclear Information System (INIS)

    Umbach, E.

    2004-01-01

    It was always the dream of scientists to watch microscopic objects directly on an atomic scale, to follow their dynamical behaviour, and to know everything about them, i.e. to get as much spectroscopic information as possible. While instruments have become available which may fulfill two of these wishes simultaneously, it is much more difficult to get all three at once. The development of so called spectro-microscopes which operate at 3rd generation synchrotron sources nourishes the hope that this dream will become true in the near future. The talk intends to show how much can be learned about organic thin films and interfaces if high-brilliance synchrotron radiation is combined with new instruments, for instance a high energy resolution beamline and a high-spatial resolution spectro-microscope. While the former is standard technology of today, the latter is a new development, combining brilliant undulator radiation of variable polarization with a specially developed, energy-filtered low energy electron microscope. First, it will be shown that many new details about the electronic structure of organic materials and their interaction with one another or with an interface can be obtained using high-resolution photoemission and x-ray absorption. For instance, from a careful analysis of the fine structure of photoemission spectra one can derive details about the interface bonding, about the interaction between molecules, and about the dynamic response of the molecular system upon creation of a core hole. Or, from a careful analysis of the fine structure of high resolution x-ray absorption spectra one gets insight into the intermolecular interaction, the coupling between electronic and vibronic excitations, and even about the shapes of potential curves. Second, the dynamic growth of highly-ordered organic thin films will be followed as a function of molecule and preparation conditions. The formation of islands, the inner structure of organic crystallites, diffusion

  16. Directional preference and functional outcomes among subjects classified at high psychosocial risk using STarT.

    Science.gov (United States)

    Werneke, Mark W; Edmond, Susan; Young, Michelle; Grigsby, David; McClenahan, Brian; McGill, Troy

    2018-03-14

    Physiotherapy has an important role in managing patients with non-specific low back pain who experience elevated psychosocial distress or risk for chronic disability. In terms of evidence-based physiotherapy practice, cognitive-behavioural approaches for patients at high psychosocial risk are the recommended management to improve patient treatment outcomes. Evidence also suggests that directional preference (DP) is an important treatment effect modifier for prescribing specific exercises for patients to improve outcomes. Little is known about the influence of treatment techniques based on DP on outcomes for patients classified as high psychosocial risk using the Subgroups for Targeted Treatment (STarT) Back Screening Tool. This study aimed to examine the association between functional status (FS) at rehabilitation discharge for patients experiencing low back pain classified at high STarT psychosocial risk and whose symptoms showed a DP versus No-DP. High STarT risk patients (n = 138) completed intake surveys, that is, the lumbar FS of Focus On Therapeutic Outcomes, Inc., and STarT, and were evaluated for DP by physiotherapists credentialed in McKenzie methods. The FS measure of Focus On Therapeutic Outcomes, Inc., was repeated at discharge. DP and No-DP prevalence rates were calculated. Associations between first-visit DP and No-DP and change in FS were assessed using univariate and multivariate regression models controlling for 11 risk-adjusted variables. One hundred nine patients classified as high STarT risk had complete intake and discharge FS and DP data. Prevalence rate for DP was 65.1%. A significant and clinically important difference (7.98 FS points; p = .03) in change in function at discharge between DP and No-DP was observed after controlling for all confounding variables in the final model. Findings suggest that interventions matched to DP are effective for managing high psychological risk patients and may provide physiotherapists with an

  17. High-resolution melt PCR analysis for genotyping of Ureaplasma parvum isolates directly from clinical samples.

    Science.gov (United States)

    Payne, Matthew S; Tabone, Tania; Kemp, Matthew W; Keelan, Jeffrey A; Spiller, O Brad; Newnham, John P

    2014-02-01

    Ureaplasma sp. infection in neonates and adults underlies a variety of disease pathologies. Of the two human Ureaplasma spp., Ureaplasma parvum is clinically the most common. We have developed a high-resolution melt (HRM) PCR assay for the differentiation of the four serovars of U. parvum in a single step. Currently U. parvum strains are separated into four serovars by sequencing the promoter and coding region of the multiple-banded antigen (MBA) gene. We designed primers to conserved sequences within this region for PCR amplification and HRM analysis to generate reproducible and distinct melt profiles that distinguish clonal representatives of serovars 1, 3, 6, and 14. Furthermore, our HRM PCR assay could classify DNA extracted from 74 known (MBA-sequenced) test strains with 100% accuracy. Importantly, HRM PCR was also able to identify U. parvum serovars directly from 16 clinical swabs. HRM PCR performed with DNA consisting of mixtures of combined known serovars yielded profiles that were easily distinguished from those for single-serovar controls. These profiles mirrored clinical samples that contained mixed serovars. Unfortunately, melt curve analysis software is not yet robust enough to identify the composition of mixed serovar samples, only that more than one serovar is present. HRM PCR provides a single-step, rapid, cost-effective means to differentiate the four serovars of U. parvum that did not amplify any of the known 10 serovars of Ureaplasma urealyticum tested in parallel. Choice of reaction reagents was found to be crucial to allow sufficient sensitivity to differentiate U. parvum serovars directly from clinical swabs rather than requiring cell enrichment using microbial culture techniques.

  18. Low-Mode Conformational Search Method with Semiempirical Quantum Mechanical Calculations: Application to Enantioselective Organocatalysis.

    Science.gov (United States)

    Kamachi, Takashi; Yoshizawa, Kazunari

    2016-02-22

    A conformational search program for finding low-energy conformations of large noncovalent complexes has been developed. A quantitatively reliable semiempirical quantum mechanical PM6-DH+ method, which is able to accurately describe noncovalent interactions at a low computational cost, was employed in contrast to conventional conformational search programs in which molecular mechanical methods are usually adopted. Our approach is based on the low-mode method whereby an initial structure is perturbed along one of its low-mode eigenvectors to generate new conformations. This method was applied to determine the most stable conformation of transition state for enantioselective alkylation by the Maruoka and cinchona alkaloid catalysts and Hantzsch ester hydrogenation of imines by chiral phosphoric acid. Besides successfully reproducing the previously reported most stable DFT conformations, the conformational search with the semiempirical quantum mechanical calculations newly discovered a more stable conformation at a low computational cost.

  19. 3,3'-Diaryl-BINOL phosphoric acids as enantioselective extractants of benzylic primary amines.

    Science.gov (United States)

    Verkuijl, Bastiaan J V; de Vries, Johannes G; Feringa, Ben L

    2011-01-01

    We report that 3,3'-diaryl-BINOL phosphoric acids are effective enantioselective extractants in chiral separation methods based on reactive liquid-liquid extraction. These new extractants are capable of separating racemic benzylic primary amine substrates. The effect of the nature of the substituents at the 3,3'-positions of the host were examined as well as the structure of the substrate, together with important parameters such as the organic solvent, the pH of the aqueous phase, and the host stoichiometry. Titration of the substrate with the host was monitored by FTIR, NMR, UV-Vis, and CD spectroscopy, which provided insight into the structure of the host-guest complex involved in extraction. Copyright © 2010 Wiley-Liss, Inc.

  20. Enantioselective disposition of omeprazole, pantoprazole, and lansoprazole in a same Brazilian subjects group.

    Science.gov (United States)

    Cassiano, Neila M; Oliveira, Regina V; Bernasconi, Gilberto C R; Cass, Quezia B

    2012-04-01

    This work reports the result of the enantioselective disposition of pantoprazole, omeprazole, and lansoprazole in a same group of Brazilian health subjects. Ten nongenotyped healthy subjects were used for this study. Each subject received a single oral dose of 80 mg of pantoprazole, 40 mg of omeprazole, and 30 mg of lansoprazole, and the plasma concentrations of the enantiomers were measured for 8 h postdose. For pantoprazole and omeprazole, among the 10 volunteers investigated, only one volunteer (Subject # 4) presented higher plasma concentrations of the (+)-enantiomer than those of (-)-enantiomer. Nevertheless, the area under the concentration-time curve of the (+)-lansoprazole was higher than those the (-)-lansoprazole for all subjects. The comparison of proton pump inhibitors' enantiomers disposition from a single group volunteer demonstrated that pantoprazole and omeprazole can be used to differentiate extensive from poor CYP2C19 metabolizer while lansoprazole cannot do it. Copyright © 2011 Wiley Periodicals, Inc.

  1. Calix[4]arene-Based Enantioselective Fluorescent Sensors for the Recognition of N-Acetyl-aspartate

    Institute of Scientific and Technical Information of China (English)

    QING Guang-Yan; CHEN Zhi-Hong; WANG Feng; YANG Xi; MENG Ling-Zhi; HE Yong-Bing

    2008-01-01

    Two-armed chiral anion receptors (1 and 2), calix[4]arenes bearing dansyl fluorophore and (1R,2R)- or(1S,2S)-1,2-diphenylethylenediamine binding sites, were prepared and examined for their chiral amino acid anion binding abilities by the fluorescence spectra in dimethylsulfoxide (DMSO). The results of non-linear curve fitting indicate that 1 or 2 forms a 1 : 1 stoichiometry complex with N-acetyl-L-or D-aspartate by multiple hydrogen bonding interactions, exhibiting good enantioselective fluorescent recognition for the enantiomers of N-acetyl-as-partate, [receptor 1: Kass(D)/Kass(L)=6.74; receptor 2: Kass(L)/Kass(D)=6.48]. The clear fluorescent response difference indicates that receptors 1 and 2 could be used as a fluorescent chemosensor for N-Acetyl-aspartate.

  2. Enantioanalysis of S-deprenyl using enantioselective, potentiometric membrane electrodes based on C60 derivatives

    International Nuclear Information System (INIS)

    Stefan-van Staden, Raluca-Ioana

    2010-01-01

    Enantioselective, potentiometric membrane electrodes based on (1,2-methanofullerene C 60 )-61-carboxylic acid, diethyl (1,2-methanofullerene C 60 )-61-61-dicarboxylate and tert-butyl (1,2-methanofullerene C 60 )-61-carboxylic acid were proposed for the enantioanalysis of S-deprenyl in pharmaceutical compounds. Molecular modeling calculations were performed to prove the reliability of the proposed electrodes. The different characteristics involved in this analysis were explained, namely (i) the stability of each molecule using total energy, hardness and dipole moment, and (ii) the explanation of the mechanism of interaction using intermolecular forces (moderate hydrogen bond interactions), atomic charges and electrostatic potential. Electronic structures as well as molecular interaction have been investigated using Hartree-Fock theory, 3-21G(*) basis set. Stability and feasibility of all the generated structures were supported by their respective energy minima and fundamental frequencies.

  3. Enantioselective analysis of ibuprofen and its biotransformation products in water/sediment systems,

    DEFF Research Database (Denmark)

    Sundström, Maria; Escola, Monica; Radke, Michael

    2015-01-01

    of the sediments in the aquatic systems has neither been taken in account previously. In this study, four water-sediment systems were chosen according to anthropogenic exposure and sediment conditions. A low anthropogenic impact lake (Largen), a river receiving wastewater (Fyrisån) and two sediments (anoxic......As ibuprofen degrades enantioselectively in activated sludge, the same process is assumed to occur in surface lake-water and in river-water based biofilms. Yet, the effects of the wastewater inflow, containing non-racemic ibuprofen, into natural systems have never been studied. The role......-7 days in Tvären and B1 respectively. Largen sediments, not impacted by wastewater, degraded ibuprofen faster than Fyrisån sediments did. Yet, these two sediments sediments showed no significant difference with respect to the degradation rates of the ibuprofen enantiomers. A connection between wastewater...

  4. Desalination and reuse of high-salinity shale gas produced water: drivers, technologies, and future directions.

    Science.gov (United States)

    Shaffer, Devin L; Arias Chavez, Laura H; Ben-Sasson, Moshe; Romero-Vargas Castrillón, Santiago; Yip, Ngai Yin; Elimelech, Menachem

    2013-09-03

    In the rapidly developing shale gas industry, managing produced water is a major challenge for maintaining the profitability of shale gas extraction while protecting public health and the environment. We review the current state of practice for produced water management across the United States and discuss the interrelated regulatory, infrastructure, and economic drivers for produced water reuse. Within this framework, we examine the Marcellus shale play, a region in the eastern United States where produced water is currently reused without desalination. In the Marcellus region, and in other shale plays worldwide with similar constraints, contraction of current reuse opportunities within the shale gas industry and growing restrictions on produced water disposal will provide strong incentives for produced water desalination for reuse outside the industry. The most challenging scenarios for the selection of desalination for reuse over other management strategies will be those involving high-salinity produced water, which must be desalinated with thermal separation processes. We explore desalination technologies for treatment of high-salinity shale gas produced water, and we critically review mechanical vapor compression (MVC), membrane distillation (MD), and forward osmosis (FO) as the technologies best suited for desalination of high-salinity produced water for reuse outside the shale gas industry. The advantages and challenges of applying MVC, MD, and FO technologies to produced water desalination are discussed, and directions for future research and development are identified. We find that desalination for reuse of produced water is technically feasible and can be economically relevant. However, because produced water management is primarily an economic decision, expanding desalination for reuse is dependent on process and material improvements to reduce capital and operating costs.

  5. Enantioselective inhibition of carprofen towards UDP-glucuronosyltransferase (UGT) 2B7.

    Science.gov (United States)

    Fang, Zhong-Ze; Wang, Haina; Cao, Yun-Feng; Sun, Dong-Xue; Wang, Li-Xuan; Hong, Mo; Huang, Ting; Chen, Jian-Xing; Zeng, Jia

    2015-03-01

    UDP-glucuronosyltransferases (UGTs)-catalyzed glucuronidation conjugation reaction plays an important role in the elimination of many important clinical drugs and endogenous substances. The present study aims to investigate the enantioselective inhibition of carprofen towards UGT isoforms. In vitro a recombinant UGT isoforms-catalyzed 4-methylumbelliferone (4-MU) glucuronidation incubation mixture was used to screen the inhibition potential of (R)-carprofen and (S)-carprofen towards multiple UGT isoforms. The results showed that (S)-carprofen exhibited stronger inhibition potential than (R)-carprofen towards UGT2B7. However, no significant difference was observed for the inhibition of (R)-carprofen and (S)-carprofen towards other UGT isoforms. Furthermore, the inhibition kinetic behavior was compared for the inhibition of (S)-carprofen and (R)-carprofen towards UGT2B7. A Lineweaver-Burk plot showed that both (S)-carprofen and (R)-carprofen exhibited competitive inhibition towards UGT2B7-catalyzed 4-MU glucuronidation. The inhibition kinetic parameter (Ki ) was calculated to be 7.0 μM and 31.1 μM for (S)-carprofen and (R)-carprofen, respectively. Based on the standard for drug-drug interaction, the threshold for (S)-carprofen and (R)-carprofen to induce a drug-drug interaction is 0.7 μM and 3.1 μM, respectively. In conclusion, enantioselective inhibition of carprofen towards UDP-glucuronosyltransferase (UGT) 2B7 was demonstrated in the present study. Using the in vitro inhibition kinetic parameter, the concentration threshold of (S)-carprofen and (R)-carprofen to possibly induce the drug-drug interaction was obtained. Therefore, clinical monitoring of the plasma concentration of (S)-carprofen is more important than (R)-carprofen to avoid a possible drug-drug interaction between carprofen and the drugs mainly undergoing UGT2B7-catalyzed metabolism. © 2014 Wiley Periodicals, Inc.

  6. Future space-based direct imaging platforms: high fidelity simulations and instrument testbed development

    Science.gov (United States)

    Hicks, Brian A.; Eberhardt, Andrew; SAINT, VNC, LUVOIR

    2017-06-01

    The direct detection and characterization of habitable zone (HZ) Earth-like exoplanets is predicated on light gathering power of a large telescope operating with tens of millicarcsecond angular resolution, and at contrast scales on the order of 0.1 ppb. Accessing a statistically significant sample of planets to search for habitable worlds will likely build on the knowledge and insfrastructure gained through JWST, later advancing to assembly in space or formation flying approaches that may eventually be used to achieve even greater photometric sensitivity or resolution. in order to address contrast, a means of starlight suppression is needed that contends with complex aperture diffraction. The Visible Nulling Coronagraph (VNC) is one such approach that destructively interferes starlight to enable detection and characterization of extrasolar objects.The VNC is being incorporated into an end-to-end telescope-coronagraph system demonstrator called the Segmented Aperture Interferometric Nulling Testbed (SAINT). Development of the VNC has a rich legacy, and successfully demonstrating its capability with SAINT will mark milestones towards meeting the high-contrast direct imaging needs of future large space telescopes. SAINT merges the VNC with an actively-controlled segmented aperture telescope via a fine pointing system and aims to demonstrate 1e-8 contrast nulling of a segmented aperture at an inner working angle of four diffraction radii over a 20 nm visible bandpass. The system comprises four detectors for wavefront sensing, one of which is the high-contrast focal plane. The detectors provide feedback to control the segmented telescope primary mirror, a fast steering mirror, a segmented deformable mirror, and a delay stage. All of these components must work in concert with passive optical elements that are designed, fabricated, and aligned pairwise to achieve the requisite wavefront symmetry needed to push the state of the art in broadband destructive interferometric

  7. Direct interferometric measurement of the atomic dipole phase in high-order harmonic generation

    International Nuclear Information System (INIS)

    Chiara Corsi; Angela Pirri; Emiliano Sali

    2006-01-01

    Complete test of publication follows. For low gas densities and negligible ionization, the so-called atomic dipole phase, connected with the electronic dynamics involved in the generation process, is the main source of phase modulation and incoherence of high-order harmonics. To accurately determine these laser-intensity-induced phase shifts is therefore of great importance, both for the possible spectroscopic applications of harmonics and for the controlled generation of attosecond pulses. In a semiclassical description, only two electronic trajectories contribute to generate plateau harmonics during each pump optical half-cycle. Electrons appearing in the continuum by tunnel ionization may follow two different quantum paths, namely a long (l) and a short (s) trajectory before recombination. According to the SFA approximation, the harmonic of q th order acquires a phase proportional to the electronic classical action, and simply given by: ψ 0 j (r,t) -α q j I(r,t) with j = l, s where α q j are non-linear phase coefficients, roughly proportional to the time that the originating electron spends in the continuum before recombination. The space and time variation of the laser intensity (I(r,t), causes just a little phase modulation for the s-trajectory harmonic component, while the l-trajectory component becomes strongly chirped and spatially defocused; this gives rise to two spatially-separated regions having different temporal coherence. Here we report the first direct measurement of such atomic dipole phase in the process of high-order harmonic generation. Differently from previous measurements based in the most natural way, i.e., by interferometry. Two phase-locked pump pulses generate two phase-locked harmonic pulses in two nearby positions in a gas jet; one of them is used as a fixed phase reference while the generating intensity of the other is varied. The shift of the XUV interference fringes observed in the far field then gives a direct estimate of the

  8. 3-Isoxazolidinone: A New Achiral Template for Enantioselective Transformations

    International Nuclear Information System (INIS)

    Sibi, Mukund P.; Gustafson, Brandon; Coulomb, Julien

    2010-01-01

    Cycloadditions with the α-methylacrylate 3 were investigated next in an effort to evaluate if rotamer control installed in the template plays a role in the efficiency of the reaction (eqn 2). These results are shown in Table 2. Cycloaddition using magnesium triflimide/9 gave the cycloadduct as a nearly 1:1 mixture in low yield with no selectivity (entry 1). Zinc triflimide as a Lewis acid was also ineffective (entry 2). Iron triflimide/9 gave the endo/exo adducts in high yield and modest selectivity (entry 3). Reaction with copper triflate/9 was less effective and gave the adducts in modest selectivity (entry 4). Interestingly, the products were enantiomeric to that obtained with iron and zinc Lewis acids. Cooling the reaction temperature to 0 or .20 .deg. C led to substantial improvement in selectivity (entries 5 and 6). However, the chemical yields were very low. Doubling the catalyst loading to 30 mol % led to improvement in chemical yield but the selectivities remained the same

  9. 3-Isoxazolidinone: A New Achiral Template for Enantioselective Transformations

    Energy Technology Data Exchange (ETDEWEB)

    Sibi, Mukund P.; Gustafson, Brandon; Coulomb, Julien [North Dakota State Univ., Fargo (United States)

    2010-03-15

    Cycloadditions with the α-methylacrylate 3 were investigated next in an effort to evaluate if rotamer control installed in the template plays a role in the efficiency of the reaction (eqn 2). These results are shown in Table 2. Cycloaddition using magnesium triflimide/9 gave the cycloadduct as a nearly 1:1 mixture in low yield with no selectivity (entry 1). Zinc triflimide as a Lewis acid was also ineffective (entry 2). Iron triflimide/9 gave the endo/exo adducts in high yield and modest selectivity (entry 3). Reaction with copper triflate/9 was less effective and gave the adducts in modest selectivity (entry 4). Interestingly, the products were enantiomeric to that obtained with iron and zinc Lewis acids. Cooling the reaction temperature to 0 or .20 .deg. C led to substantial improvement in selectivity (entries 5 and 6). However, the chemical yields were very low. Doubling the catalyst loading to 30 mol % led to improvement in chemical yield but the selectivities remained the same.

  10. Biocatalytic site- and enantioselective oxidative dearomatization of phenols

    Science.gov (United States)

    Baker Dockrey, Summer A.; Lukowski, April L.; Becker, Marc R.; Narayan, Alison R. H.

    2018-02-01

    The biocatalytic transformations used by chemists are often restricted to simple functional-group interconversions. In contrast, nature has developed complexity-generating biocatalytic reactions within natural product pathways. These sophisticated catalysts are rarely employed by chemists, because the substrate scope, selectivity and robustness of these catalysts are unknown. Our strategy to bridge the gap between the biosynthesis and synthetic chemistry communities leverages the diversity of catalysts available within natural product pathways. Here we show that, starting from a suite of biosynthetic enzymes, catalysts with complementary substrate scope as well as selectivity can be identified. This strategy has been applied to the oxidative dearomatization of phenols, a chemical transformation that rapidly builds molecular complexity from simple starting materials and cannot be accomplished with high selectivity using existing catalytic methods. Using enzymes from biosynthetic pathways, we have successfully developed a method to produce ortho-quinol products with controlled site- and stereoselectivity. Furthermore, we have capitalized on the scalability and robustness of this method in gram-scale reactions as well as multi-enzyme and chemoenzymatic cascades.

  11. Enantioselective metabolism of hydroxychloroquine employing rats and mice hepatic microsomes

    Directory of Open Access Journals (Sweden)

    Carmem Dickow Cardoso

    2009-12-01

    Full Text Available Hydroxychloroquine (HCQ is an important chiral drug used, mainly, in the treatment of rheumatoid arthritis, systemic lupus erythematosus and malaria, and whose pharmacokinetic and pharmacodynamic properties look to be stereoselective. Respecting the pharmacokinetic properties, some previous studies indicate that the stereoselectivity could express itself in the processes of metabolism, distribution and excretion and that the stereoselective metabolism looks to be a function of the studied species. So, the in vitro metabolism of HCQ was investigated using hepatic microsomes of rats and mice. The microsomal fraction of livers of Wistar rats and Balb-C mice was separated by ultracentrifugation and 500 μL were incubated for 180 minutes with 10 μL of racemic HCQ 1000 μg mL-1. Two stereospecific analytical methods, high performance liquid chromatography (HPLC and capillary electrophoresis (CE, were used to separate and quantify the formed metabolites. It was verified that the main formed metabolite is the (--(R-desethyl hydroxychloroquine for both animal species.A hidroxicloroquina (HCQ é um importante fármaco quiral usado, principalmente, no tratamento de artrite reumatóide, lupus eritematoso sistêmico e malária e cujas propriedades farmacocinéticas e farmacodinâmicas parecem ser estereosseletivas. Em relação às propriedades farmacocinéticas, alguns estudos prévios indicam que a estereosseletividade pode se expressar nos processos de metabolismo, distribuição e excreção e que o metabolismo estereosseletivo parece ser função da espécie estudada. Sendo assim, o metabolismo in vitro da HCQ foi investigado usando microssomas de fígado de ratos e de camundongos. A fração microssômica de fígados de ratos Wistar e de camundongos Balb-C foi isolada por ultracentrifugação e 500 μL foram incubados por 180 minutos com 10 μL de HCQ racêmica 1000 μg mL-1. Dois métodos analíticos estereoespecíficos, por cromatografia líquida de

  12. A direct evidence for high carbon dioxide and radon-222 discharge in Central Nepal

    International Nuclear Information System (INIS)

    Perrier, F.; Byrdina, S.; Richon, P.; Bollinger, L.; Bureau, S.; Richon, P.; France-Lanord, Ch.; Rajaure, S.; Koirala, Bharat Prasad; Shrestha, Prithvi Lal; Gautam, Umesh Prasad; Tiwari, Dilli Ram; Sapkota, Soma Nath; Revil, A.; Revil, A.; Contraires, S.

    2009-01-01

    Gas discharges have been identified at the Syabru-Bensi hot springs, located at the front of the High Himalaya in Central Nepal, in the Main Central Thrust zone. The hot spring waters are characterized by a temperature reaching 61 C, high salinity, high alkalinity and δ 13 C varying from +0. 7 parts per thousand to +4. 8 parts per thousand. The gas is mainly dry carbon dioxide, with a δ 13 C of -0. 8 parts per thousand. The diffuse carbon dioxide flux, mapped by the accumulation chamber method, reached a value of 19000 g m -2 day -1 , which is comparable with values measured on active volcanoes. Similar values have been observed over a two-year time interval and the integral around the main gas discharge amounts to 0. 25 ± 0. 07 mol s -1 , or 350 ± 100 ton a -1 . The mean radon-222 concentration in spring water did not exceed 2. 5 Bq L -1 , exponentially decreasing with water temperature. In contrast, in gas bubbles collected in the water or in the dry gas discharges, the radon concentration varied from 16 000 to 41000 Bq m -3 . In the soil, radon concentration varied from 25000 to more than 50000 Bq m -3 . Radon flux, measured at more than fifty points, reached extreme values, larger than 2 Bq m -2 s -1 , correlated to the larger values of the carbon dioxide flux. Our direct observation confirms previous studies which indicated large degassing in the Himalaya. The proposed understanding is that carbon dioxide is released at mid-crustal depth by metamorphic reactions within the Indian basement, transported along pre-existing faults by meteoric hot water circulation, and degassed before reaching surface. This work, first, confirms that further studies should be undertaken to better constrain the carbon budget of the Himalaya, and, more generally, the contribution of mountain building to the global carbon balance. Furthermore, the evidenced gas discharges provide a unique natural laboratory for methodological studies, and appear particularly important to study as

  13. Outcomes of implementation of enhanced goal directed therapy in high-risk patients undergoing abdominal surgery

    Directory of Open Access Journals (Sweden)

    Lakshmi Kumar

    2015-01-01

    Full Text Available Background and Aims: Advanced monitoring targeting haemodynamic and oxygenation variables can improve outcomes of surgery in high-risk patients. We aimed to assess the impact of goal directed therapy (GDT targeting cardiac index (CI and oxygen extraction ratio (O 2 ER on outcomes of high-risk patients undergoing abdominal surgery. Methods: In a prospective randomised trial, forty patients (American Society of Anaesthesiologists II and III undergoing major abdominal surgeries were randomised into two groups. In-Group A mean arterial pressure ≥ 65 mmHg, central venous pressure ≥ 8-10 mmHg, urine output ≥ 0.5 mL/kg/h and central venous oxygen saturation ≥ 70% were targeted intra-operatively and 12 h postoperatively. In-Group-B (enhanced GDT, in addition to the monitoring in-Group-A, CI ≥ 2.5 L/min/m 2 and O 2 ER ≤ 27% were targeted. The end-points were lactate levels and base deficit during and after surgery. The secondary end points were length of Intensive Care Unit (ICU and hospital stay and postoperative complications. Wilcoxon Mann Whitney and Chi-square tests were used for statistical assessment. Results: Lactate levels postoperatively at 4 and 8 h were lower in-Group-B (P < 0.05. The mean base deficit at 3, 4, 5 and 6 h intra-operatively and postoperatively after 4, 8 and 12 h were lower in-Group-B (P < 0.05. There were no significant differences in ICU stay (2.10 ± 1.52 vs. 2.90 ± 2.51 days or hospital stay (10.85 + 4.39 vs. 13.35 + 6.77 days between Group A and B. Conclusions: Implementation of enhanced GDT targeting CI and OER was associated with improved tissue oxygenation.

  14. Directly patching high-level exchange-correlation potential based on fully determined optimized effective potentials

    Science.gov (United States)

    Huang, Chen; Chi, Yu-Chieh

    2017-12-01

    The key element in Kohn-Sham (KS) density functional theory is the exchange-correlation (XC) potential. We recently proposed the exchange-correlation potential patching (XCPP) method with the aim of directly constructing high-level XC potential in a large system by patching the locally computed, high-level XC potentials throughout the system. In this work, we investigate the patching of the exact exchange (EXX) and the random phase approximation (RPA) correlation potentials. A major challenge of XCPP is that a cluster's XC potential, obtained by solving the optimized effective potential equation, is only determined up to an unknown constant. Without fully determining the clusters' XC potentials, the patched system's XC potential is "uneven" in the real space and may cause non-physical results. Here, we developed a simple method to determine this unknown constant. The performance of XCPP-RPA is investigated on three one-dimensional systems: H20, H10Li8, and the stretching of the H19-H bond. We investigated two definitions of EXX: (i) the definition based on the adiabatic connection and fluctuation dissipation theorem (ACFDT) and (ii) the Hartree-Fock (HF) definition. With ACFDT-type EXX, effective error cancellations were observed between the patched EXX and the patched RPA correlation potentials. Such error cancellations were absent for the HF-type EXX, which was attributed to the fact that for systems with fractional occupation numbers, the integral of the HF-type EXX hole is not -1. The KS spectra and band gaps from XCPP agree reasonably well with the benchmarks as we make the clusters large.

  15. Direct numerical simulation of reactor two-phase flows enabled by high-performance computing

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Jun; Cambareri, Joseph J.; Brown, Cameron S.; Feng, Jinyong; Gouws, Andre; Li, Mengnan; Bolotnov, Igor A.

    2018-04-01

    Nuclear reactor two-phase flows remain a great engineering challenge, where the high-resolution two-phase flow database which can inform practical model development is still sparse due to the extreme reactor operation conditions and measurement difficulties. Owing to the rapid growth of computing power, the direct numerical simulation (DNS) is enjoying a renewed interest in investigating the related flow problems. A combination between DNS and an interface tracking method can provide a unique opportunity to study two-phase flows based on first principles calculations. More importantly, state-of-the-art high-performance computing (HPC) facilities are helping unlock this great potential. This paper reviews the recent research progress of two-phase flow DNS related to reactor applications. The progress in large-scale bubbly flow DNS has been focused not only on the sheer size of those simulations in terms of resolved Reynolds number, but also on the associated advanced modeling and analysis techniques. Specifically, the current areas of active research include modeling of sub-cooled boiling, bubble coalescence, as well as the advanced post-processing toolkit for bubbly flow simulations in reactor geometries. A novel bubble tracking method has been developed to track the evolution of bubbles in two-phase bubbly flow. Also, spectral analysis of DNS database in different geometries has been performed to investigate the modulation of the energy spectrum slope due to bubble-induced turbulence. In addition, the single-and two-phase analysis results are presented for turbulent flows within the pressurized water reactor (PWR) core geometries. The related simulations are possible to carry out only with the world leading HPC platforms. These simulations are allowing more complex turbulence model development and validation for use in 3D multiphase computational fluid dynamics (M-CFD) codes.

  16. Current guidelines for high-density lipoprotein cholesterol in therapy and future directions

    Directory of Open Access Journals (Sweden)

    Subedi BH

    2014-04-01

    Full Text Available Bishnu H Subedi,1,2 Parag H Joshi,1 Steven R Jones,1 Seth S Martin,1 Michael J Blaha,1 Erin D Michos1 1Johns Hopkins Ciccarone Center for the Prevention of Heart Disease, 2Greater Baltimore Medical Center, Baltimore, MD, USA Abstract: Many studies have suggested that a significant risk factor for atherosclerotic cardiovascular disease (ASCVD is low high-density lipoprotein cholesterol (HDL-C. Therefore, increasing HDL-C with therapeutic agents has been considered an attractive strategy. In the prestatin era, fibrates and niacin monotherapy, which cause modest increases in HDL-C, reduced ASCVD events. Since their introduction, statins have become the cornerstone of lipoprotein therapy, the benefits of which are primarily attributed to decrease in low-density lipoprotein cholesterol. Findings from several randomized trials involving niacin or cholesteryl ester transfer protein inhibitors have challenged the concept that a quantitative elevation of plasma HDL-C will uniformly translate into ASCVD benefits. Consequently, the HDL, or more correctly, HDL-C hypothesis has become more controversial. There are no clear guidelines thus far for targeting HDL-C or HDL due to lack of solid outcomes data for HDL specific therapies. HDL-C levels are only one marker of HDL out of its several structural or functional properties. Novel approaches are ongoing in developing and assessing agents that closely mimic the structure of natural HDL or replicate its various functions, for example, reverse cholesterol transport, vasodilation, anti-inflammation, or inhibition of platelet aggregation. Potential new approaches like HDL infusions, delipidated HDL, liver X receptor agonists, Apo A-I upregulators, Apo A mimetics, and gene therapy are in early phase trials. This review will outline current therapies and describe future directions for HDL therapeutics. Keywords: high-density lipoprotein, lipids, cholesterol, atherosclerosis, cardiovascular disease, therapy

  17. Radiolytic preparation of thin Au film directly on resin substrate using high-energy electron beam

    Energy Technology Data Exchange (ETDEWEB)

    Ohkubo, Yuji, E-mail: okubo@upst.eng.osaka-u.ac.jp [Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan); Seino, Satoshi; Nakagawa, Takashi; Kugai, Junichiro [Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan); Ueno, Koji [Japan Electron Beam Irradiation Service Ltd., 5-3 Ozushima, Izumiohtsu, Osaka 595-0074 (Japan); Yamamoto, Takao A. [Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan)

    2016-04-01

    A novel method for preparing thin Au films directly on resin substrates using an electron beam was developed. The thin Au films were prepared on a resin substrate by the reduction of Au ions in an aqueous solution via irradiation with a high-energy electron beam (4.8 MeV). This reduction method required 7 s of the irradiation time of the electron beam. Furthermore, no reductant or catalyst was needed. As the concentration of Au ions in the precursor solution was increased, the amount of Au deposited on the resin substrate increased, too, and the structure of the prepared Au film changed. As a result, the film color changed as well. Cross-sectional scanning electron microscope images of the thus-prepared Au film indicated that the Au films were consisted of two layers: a particle layer and a bottom bulk layer. There was strong adhesion between the Au films and the underlying resin substrates. This was confirmed by the tape-peeling test and through ultrasonic cleaning. After both processes, Au remained on the resin substrates, while most of the particle-like moieties were removed. This indicated that the thin Au films prepared via irradiation with a high-energy electron beam adhered strongly to the resin substrates. - Highlights: • A thin gold (Au) film was formed by EBIRM for the first time. • The irradiation time of the electron beam was less than 10 s. • Thin Au films were obtained without reductant or catalyst. • Au films were consisted of two layers: a particle layer and a bottom bulk layer. • There was strong adhesion between the bottom bulk layer and the underlying resin substrates.

  18. High-capacity quantum secure direct communication with two-photon six-qubit hyperentangled states

    Science.gov (United States)

    Wu, FangZhou; Yang, GuoJian; Wang, HaiBo; Xiong, Jun; Alzahrani, Faris; Hobiny, Aatef; Deng, FuGuo

    2017-12-01

    This study proposes the first high-capacity quantum secure direct communication (QSDC) with two-photon six-qubit hyper-entangled Bell states in two longitudinal momentum and polarization degrees of freedom (DOFs) of photon pairs, which can be generated using two 0.5 mm-thick type-I β barium borate crystal slabs aligned one behind the other and an eight-hole screen. The secret message can be independently encoded on the photon pairs with 64 unitary operations in all three DOFs. This protocol has a higher capacity than previous QSDC protocols because each photon pair can carry 6 bits of information, not just 2 or 4 bits. Our QSDC protocol decreases the influence of decoherence from environment noise by exploiting the decoy photons to check the security of the transmission of the first photon sequence. Compared with two-way QSDC protocols, our QSDC protocol is immune to an attack by an eavesdropper using Trojan horse attack strategies because it is a one-way quantum communication. The QSDC protocol has good applications in the future quantum communication because of all these features.

  19. Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

    Science.gov (United States)

    Mikolajczuk-Zychora, A.; Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B.; Mazurkiewicz-Pawlicka, M.; Stobinski, L.; Ciecierska, E.; Zimoch, A.; Opałło, M.

    2016-12-01

    One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

  20. Direct Creation of Highly Conductive Laser-Induced Graphene Nanocomposites from Polymer Blends.

    Science.gov (United States)

    Yazdi, Alireza Zehtab; Navas, Ivonne Otero; Abouelmagd, Ahmed; Sundararaj, Uttandaraman

    2017-09-01

    The current state-of-the-art mixing strategies of nanoparticles with insulating polymeric components have only partially utilized the unique electrical conductivity of graphene in nanocomposite systems. Herein, this paper reports a nonmixing method of direct creation of polymer/graphene nanocomposites from polymer blends via laser irradiation. Polycarbonate-laser-induced graphene (PC-LIG) nanocomposite is produced from a PC/polyetherimide (PC/PEI) blend after exposure to commercially available laser scribing with a power of ≈6 W and a speed of ≈2 cm s -1 . Extremely high electrical conductivities are obtained for the PC-LIG nanocomposites, ranging from 26 to 400 S m -1 , depending on the vol% of the starting PEI phase in the blend. To the authors' knowledge, these conductivity values are at least one order of magnitude higher than the values that are previously reported for conductive polymer/graphene nanocomposites prepared via mixing strategies. The comprehensive microscopy and spectroscopy characterizations reveal a complete graphitization of the PEI phase with columnar microstructure embedded in the PC phase. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.