WorldWideScience

Sample records for enantioselective protonation reaction

  1. 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

  2. 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.

  3. 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.

  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. 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.

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

    KAUST Repository

    Lee, Richmond

    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.

  7. 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.

  8. 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.

  9. Chiral Pyridinium Phosphoramide as a Dual Brønsted Acid Catalyst for Enantioselective Diels-Alder Reaction.

    Science.gov (United States)

    Nishikawa, Yasuhiro; Nakano, Saki; Tahira, Yuu; Terazawa, Kanako; Yamazaki, Ken; Kitamura, Chitoshi; Hara, Osamu

    2016-05-06

    Chiral pyridinium phosphoramide 1·HX was designed to be a new class of chiral Brønsted acid catalyst in which both the pyridinium proton and the adjacent imide-like proton activated by the electron-withdrawing pyridinium moiety could work cooperatively as strong dual proton donors. The potential of 1·HX was shown in the enantioselective Diels-Alder reactions of 1-amino dienes with various dienophiles including N-unsubstituted maleimide, which has yet to be successfully used in an asymmetric Diels-Alder reaction.

  10. Enantioselective solvent-free Robinson annulation reactions

    Indian Academy of Sciences (India)

    Unknown

    solvents to effect an asymmetric synthesis is an important step forward towards ... In continuation of our preliminary communication 2, we wish to ..... formation of chiral enamine 74 from the reaction of S-proline with pro-R carbonyl group.

  11. 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

  12. 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.

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. 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

  2. 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).

  3. 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.

  4. 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.

  5. Enantioselective Collision-Activated Dissociation of Gas-Phase Tryptophan Induced by Chiral Recognition of Protonated l-Alanine Peptides

    Science.gov (United States)

    Fujihara, Akimasa; Matsuyama, Hiroki; Tajiri, Michiko; Wada, Yoshinao; Hayakawa, Shigeo

    2017-06-01

    Enantioselective dissociation in the gas phase is important for enantiomeric enrichment and chiral transmission processes in molecular clouds regarding the origin of homochirality in biomolecules. Enantioselective collision-activated dissociation (CAD) of tryptophan (Trp) and the chiral recognition ability of l-alanine peptides ( l-Ala n ; n = 2-4) were examined using a linear ion trap mass spectrometer. CAD spectra of gas-phase heterochiral H+( d-Trp)( l-Ala n ) and homochiral H+( l-Trp)( l-Ala n ) noncovalent complexes were obtained as a function of the peptide size n. The H2O-elimination product was observed in CAD spectra of both heterochiral and homochiral complexes for n = 2 and 4, and in homochiral H+( l-Trp)( l-Ala3), indicating that the proton is attached to the l-alanine peptide, and H2O loss occurs from H+( l-Ala n ) in the noncovalent complexes. H2O loss did not occur in heterochiral H+( d-Trp)( l-Ala3), where NH3 loss and (H2O + CO) loss were the primary dissociation pathways. In heterochiral H+( d-Trp)( l-Ala3), the protonation site is the amino group of d-Trp, and NH3 loss and (H2O + CO) loss occur from H+( d-Trp). l-Ala peptides recognize d-Trp through protonation of the amino group for peptide size n = 3. NH3 loss and (H2O + CO) loss from H+( d-Trp) proceeds via enantioselective CAD in gas-phase heterochiral H+( d-Trp)( l-Ala3) at room temperature, whereas l-Trp dissociation was not observed in homochiral H+( l-Trp)( l-Ala3). These results suggest that enantioselective dissociation induced by chiral recognition of l-Ala peptides through protonation could play an important role in enantiomeric enrichment and chiral transmission processes of amino acids.

  6. 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.

  7. Review of inelastic proton-proton reactions

    CERN Document Server

    Morrison, Douglas Robert Ogston

    1973-01-01

    The most important new results on inelastic proton-proton scattering obtained with the new machines, I.S.R. and N.A.L., are: (1) The inelastic cross-section increases monotonically with energy from threshold to 1500 GeV/c. Above 6 GeV/c the energy variation has a s /sup +0.04/ behaviour. (2) Scaling is observed at I.S.R. energies in pion production. Confirmation is obtained of the hypothesis of limiting fragmentation. (3) The results are in general, consistent with the two-component model-one class of events being produced by diffraction dissociation and the other by a short-range-order process (e.g. the multiperipheral model). (4) There are indications that the protons have a granular structure; this from observation of secondaries of large transverse momenta. (33 refs).

  8. 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

  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. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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...

  15. Proton conduction based on intracrystalline chemical reaction

    International Nuclear Information System (INIS)

    Schuck, G.; Lechner, R.E.; Langer, K.

    2002-01-01

    Proton conductivity in M 3 H(SeO 4 ) 2 crystals (M=K, Rb, Cs) is shown to be due to a dynamic disorder in the form of an intracrystalline chemical equilibrium reaction: alternation between the association of the monomers [HSeO 4 ] 1- and [SeO 4 ] 2- resulting in the dimer [H(SeO 4 ) 2 ] 3- (H-bond formation) and the dissociation of the latter into the two monomers (H-bond breaking). By a combination of quasielastic neutron scattering and FTIR spectroscopy, reaction rates were obtained, as well as rates of proton exchange between selenate ions, leading to diffusion. The results demonstrate that this reaction plays a central role in the mechanism of proton transport in these solid-state protonic conductors. (orig.)

  16. 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.

  17. 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.

  18. Proton-transfer reactions in ionized gases

    International Nuclear Information System (INIS)

    Stiller, W.; Schmidt, R.; Schuster, R.

    1985-01-01

    Ion-molecule reactions play an important role in various radiolytic processes, e.g. gas-pulse radiolysis, environmental research. For a discussion of mechanisms rate coefficients have to be assessed. Here gas-phase rate coefficients of ion-(polar) molecule reactions are calculated using the ideas of interaction potentials, reactive cross-sections and distribution functions of the translational energies of both the reactants (ions I, molecules M). The starting point of our approach, directed especially to gas-phase proton-transfer reactions, is the idea that the rate coefficient k can be calculated as an ion-molecule capture-rate coefficient multiplied by a 'steric factor' representing the probability for proton transfer. Mutual capture of the reaction partners within a possible reaction zone is caused by the physical interaction between an ion and a polar molecule. A model is discussed. Results are presented. (author)

  19. 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.

  20. 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.

  1. Bimolecular reactions of carbenes: Proton transfer mechanism

    Science.gov (United States)

    Abu-Saleh, Abd Al-Aziz A.; Almatarneh, Mansour H.; Poirier, Raymond A.

    2018-04-01

    Here we report the bimolecular reaction of trifluoromethylhydroxycarbene conformers and the water-mediated mechanism of the 1,2-proton shift for the unimolecular trans-conformer by using quantum chemical calculations. The CCSD(T)/cc-pVTZ//MP2/cc-pVDZ potential-energy profile of the bimolecular reaction of cis- and trans-trifluoromethylhydroxycarbene, shows the lowest gas-phase barrier height of 13 kJ mol-1 compared to the recently reported value of 128 kJ mol-1 for the unimolecular reaction. We expect bimolecular reactions of carbene's stereoisomers will open a valuable field for new and useful synthetic strategies.

  2. Proton-proton reaction rates at extreme energies

    International Nuclear Information System (INIS)

    Nagano, Motohiko

    1993-01-01

    Results on proton-antiproton reaction rates (total cross-section) at collision energies of 1.8 TeV from experiments at Fermilab have suggested a lower rate of increase with energy compared to the extrapolation based on results previously obtained at CERN's proton-antiproton collider (CERN Courier, October 1991). Now an independent estimate of the values for the proton-proton total cross-section for collision energies from 5 to 30 TeV has been provided by the analysis of cosmic ray shower data collected over ten years at the Akeno Observatory operated by the Institute for Cosmic Ray Research of University of Tokyo. These results are based on the inelastic cross-section for collisions of cosmic ray protons with air nuclei at energies in the range10 16-18 eV. A new extensive air shower experiment was started at Akeno, 150 km west of Tokyo, in 1979 with a large array of detectors, both on the ground and under a 1-metre concrete absorber. This measured the total numbers of electrons and muons of energies above 1GeV for individual showers with much better accuracy than before. Data collection was almost continuous for ten years without any change in the triggering criteria for showers above10 16 eV. The mean free path for proton-air nuclei collisions has been determined from the zenith angle of the observed frequency of air showers which have the same effective path length for development in the atmosphere and the same primary energy

  3. η production in proton-nucleus reactions

    International Nuclear Information System (INIS)

    Cassing, W.; Batko, G.; Vetter, T.; Wolf, G.

    1991-01-01

    The production of η-mesons in proton-nucleus reactions is analysed with respect to primary nucleon-nucleon (NN→NN η ) and secondary pion-nucleon (πN→ηN) production processes on the basis of Hartree-Fock groundstate momentum distributions and free on-shell production processes. The folding model adopted compares well for meson production with more involved simulations based on VUU transport equations. Similar to K + production in proton-nucleus reactions the η-mesons are primarily produced by the πN→ηN channel. However, η-mesons are absorbed in nuclei via excitation of the N * (1535) resonance which leads to strong distortions of the primordial spectra. On the other hand, the experimental mass dependence of the differential cross sections might yield information about the in-medium properties of this resonance. (orig.)

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Kinetic enantioselectivity of a protonated bis(diamido)-bridged basket resorcin[4]arene towards alanine peptides.

    Science.gov (United States)

    Fraschetti, C; Montagna, M; Crestoni, M E; Calcaterra, A; Aiello, F; Santi, L; Filippi, A

    2017-02-01

    Efficient enantiodiscrimination of some alanine-containing di- and tri-peptides by using chiral protonated bis(diamido)-bridged basket resorcin[4]arenes depends on several factors, including the basicity of the amino acid residues at the C- and N-termini of the peptide.

  10. Proton capture reactions and nuclear structure

    International Nuclear Information System (INIS)

    Kikstra, S.W.

    1989-01-01

    Experimental studies are described of the structure of 40 Ca and 42 Sc with measurements at proton-capture of (p, gamma) reactions. Where possible, an attempt has been made to interpret the results of the measurements in termsof existing models. The 40 Ca and 42 Sc nuclides were excited by bombarding 39 K and 41 Ca targets, respectively with low energy protons (E p = 0.3-3.0 MeV), that were produced by the Utrecht 3MV van de Graaff accelerator. From the measured energy and intensity of the gamma-rays created in the subsequent decay of the cuclei, information was obtained on the existence and properties of their excited states. In addition properties of two T = 3/2 levels at high excitation energy of the 9 Be nucleus were investigated. These levels were excited by the resonant absorption of gamma-rays from the 11 B(p, gamma) 12 C reaction. The results of the measurements are interpreted by a comparison to the analoque β-decay of 9 Li and to shell model calculations. The total decay energy of the superallowed O + → O + transition between the ground states of 42 Sc and 42 Ca was determined by measurements in Utrecht of the proton separation energy S p of 42 Sc and in Oak Ridge of S n of 42 Sc and 42 Ca. The results were used for verification of the conserved vector current hypothesis, which implies that the ft values of all superallowed O + → O + β-decays are the same. An attempt was made to describe properties of odd-parity states of A = 37-41 nuclei with a variant of the Warburton, Becker, Millener and Brown (WBMB) interaction.Finally a new method for the assignment of nuclear spins by a simple statistical analysis of spectroscopic information is proposed. (author). 169 refs.; 22 figs.; 24 schemes; 29 tabs

  11. Enantioselective Synthesis of α-Mercapto-β-amino Esters via Rh(II)/Chiral Phosphoric Acid-Cocatalyzed Three-Component Reaction of Diazo Compounds, Thiols, and Imines.

    Science.gov (United States)

    Xiao, Guolan; Ma, Chaoqun; Xing, Dong; Hu, Wenhao

    2016-12-02

    An enantioselective method for the synthesis of α-mercapto-β-amino esters has been developed via a rhodium(II)/chiral phosphoric acid-cocatalyzed three-component reaction of diazo compounds, thiols, and imines. This transformation is proposed to proceed through enantioselective trapping of the sulfonium ylide intermediate generated in situ from the diazo compound and thiol by the phosphoric acid-activated imine. With this method, a series of α-mercapto-β-amino esters were obtained in good yields with moderate to good stereoselectivities.

  12. Protonation Reaction of Benzonitrile Radical Anion and Absorption of Product

    DEFF Research Database (Denmark)

    Holcman, Jerzy; Sehested, Knud

    1975-01-01

    The rate constant for the protonation of benzonitrile radical anions formed in pulse radiolysis of aqueous benzonitrile solutions is (3.5 ± 0.5)× 1010 dm3 mol–1 s–1. A new 270 nm absorption band is attributed to the protonated benzonitrile anion. The pK of the protonation reaction is determined t...

  13. 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.

  14. Enantioselective copper catalysed intramolecular C-H insertion reactions of α-diazo-β-keto sulfones, α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones; the influence of the carbene substituent.

    Science.gov (United States)

    Shiely, Amy E; Slattery, Catherine N; Ford, Alan; Eccles, Kevin S; Lawrence, Simon E; Maguire, Anita R

    2017-03-22

    Enantioselectivities in C-H insertion reactions, employing the copper-bis(oxazoline)-NaBARF catalyst system, leading to cyclopentanones are highest with sulfonyl substituents on the carbene carbon, and furthermore, the impact is enhanced by increased steric demand on the sulfonyl substituent (up to 91%ee). Enantioselective intramolecular C-H insertion reactions of α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones are reported for the first time.

  15. 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.

  16. Higher-order human telomeric G-quadruplex DNA metalloenzymes enhance enantioselectivity in the Diels-Alder reaction.

    Science.gov (United States)

    Li, Yinghao; Jia, Guoqing; Wang, Changhao; Cheng, Mingpan; Li, Can

    2015-03-02

    Short human telomeric (HT) DNA sequences form single G-quadruplex (G4 ) units and exhibit structure-based stereocontrol for a series of reactions. However, for more biologically relevant higher-order HT G4 -DNAs (beyond a single G4 unit), the catalytic performances are unknown. Here, we found that higher-order HT G4 -DNA copper metalloenzymes (two or three G4 units) afford remarkably higher enantioselectivity (>90 % ee) and a five- to sixfold rate increase, compared to a single G4 unit, for the Diels-Alder reaction. Electron paramagnetic resonance (EPR) and enzymatic kinetic studies revealed that the distinct catalytic function between single and higher-order G4 -DNA copper metalloenzymes can be attributed to different Cu(II) coordination environments and substrate specificity. Our finding suggests that, like protein enzymes and ribozymes, higher-order structural organization is crucial for G4 -DNA-based catalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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...

  18. Parallel proton transfer pathways in aqueous acid-base reactions

    NARCIS (Netherlands)

    Cox, M.J.; Bakker, H.J.

    2008-01-01

    We study the mechanism of proton transfer (PT) between the photoacid 8-hydroxy-1,3, 6-pyrenetrisulfonic acid (HPTS) and the base chloroacetate in aqueous solution. We investigate both proton and deuteron transfer reactions in solutions with base concentrations ranging from 0.25M to 4M. Using

  19. 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.

  20. Comparison of dynamical aspects of nonadiabatic electron, proton, and proton-coupled electron transfer reactions

    International Nuclear Information System (INIS)

    Hatcher, Elizabeth; Soudackov, Alexander; Hammes-Schiffer, Sharon

    2005-01-01

    The dynamical aspects of a model proton-coupled electron transfer (PCET) reaction in solution are analyzed with molecular dynamics simulations. The rate for nonadiabatic PCET is expressed in terms of a time-dependent probability flux correlation function. The impact of the proton donor-acceptor and solvent dynamics on the probability flux is examined. The dynamical behavior of the probability flux correlation function is dominated by a solvent damping term that depends on the energy gap correlation function. The proton donor-acceptor motion does not impact the dynamical behavior of the probability flux correlation function but does influence the magnitude of the rate. The approximations previously invoked for the calculation of PCET rates are tested. The effects of solvent damping on the proton donor-acceptor vibrational motion are found to be negligible, and the short-time solvent approximation, in which only equilibrium fluctuations of the solvent are considered, is determined to be valid for these types of reactions. The analysis of PCET reactions is compared to previous analyses of single electron and proton transfer reactions. The dynamical behavior is qualitatively similar for all three types of reactions, but the time scale of the decay of the probability flux correlation function is significantly longer for single proton transfer than for PCET and single electron transfer due to a smaller solvent reorganization energy for proton transfer

  1. One-Pot Synthesis of Novel Chiral β-Amino Acid Derivatives by Enantioselective Mannich Reactions Catalyzed by Squaramide Cinchona Alkaloids

    Directory of Open Access Journals (Sweden)

    Kankan Zhang

    2013-05-01

    Full Text Available An efficient one-pot synthesis of novel β-amino acid derivatives containing a thiadiazole moiety was developed using a chiral squaramide cinchona alkaloid as organocatalyst. The reactions afforded chiral β-amino acid derivatives in moderate yields and with moderate to excellent enantioselectivities. The present study demonstrated for the first time the use of a Mannich reaction catalyzed by a chiral bifunctional organocatalyst for the one-pot synthesis of novel β-amino acid derivatives bearing a 1,3,4-thiadiazole moiety on nitrogen.

  2. Solid-phase extraction combined with dispersive liquid-liquid microextraction and chiral liquid chromatography-tandem mass spectrometry for the simultaneous enantioselective determination of representative proton-pump inhibitors in water samples.

    Science.gov (United States)

    Zhao, Pengfei; Deng, Miaoduo; Huang, Peiting; Yu, Jia; Guo, Xingjie; Zhao, Longshan

    2016-09-01

    This report describes, for the first time, the simultaneous enantioselective determination of proton-pump inhibitors (PPIs-omeprazole, lansoprazole, pantoprazole, and rabeprazole) in environmental water matrices based on solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME) and chiral liquid chromatography-tandem mass spectrometry. The optimized results of SPE-DLLME were obtained with PEP-2 column using methanol-acetonitrile (1/1, v/v) as elution solvent, dichloroethane, and acetonitrile as extractant and disperser solvent, respectively. The separation and determination were performed using reversed-phase chromatography on a cellulose chiral stationary phase, a Chiralpak IC (250 mm × 4.6 mm, 5 μm) column, under isocratic conditions at 0.6 mL min(-1) flow rate. The analytes were detected in multiple reaction monitoring (MRM) mode by triple quadrupole mass spectrometry. Isotopically labeled internal standards were used to compensate matrix interferences. The method provided enrichment factors of around 500. Under optimal conditions, the mean recoveries for all eight enantiomers from the water samples were 89.3-107.3 % with 0.9-10.3 % intra-day RSD and 2.3-8.1 % inter-day RSD at 20 and 100 ng L(-1) levels. Correlation coefficients (r (2)) ≥ 0.999 were achieved for all enantiomers within the range of 2-500 μg L(-1). The method detection and quantification limits were at very low levels, within the range of 0.67-2.29 ng L(-1) and 2.54-8.68 ng L(-1), respectively. This method was successfully applied to the determination of the concentrations and enantiomeric fractions of the targeted analytes in wastewater and river water, making it applicable to the assessment of the enantiomeric fate of PPIs in the environment. Graphical Abstract Simultaneous enantioselective determination of representative proton-pump inhibitors in water samples.

  3. Regioselectivity and Enantioselectivity in Nickel-Catalysed Reductive Coupling Reactions of Alkynes

    Science.gov (United States)

    Moslin, Ryan M.; Miller-Moslin, Karen; Jamison, Timothy F.

    2011-01-01

    Nickel-catalysed reductive coupling reactions of alkynes have emerged as powerful synthetic tools for the selective preparation of functionalized alkenes. One of the greatest challenges associated with these transformations is control of regioselectivity. Recent work from our laboratory has provided an improved understanding of several of the factors governing regioselectivity in these reactions, and related studies have revealed that the reaction mechanism can differ substantially depending on the ligand employed. A discussion of stereoselective transformations and novel applications of nickel catalysis in coupling reactions of alkynes is also included. PMID:17971951

  4. Nuclear reactions excited by recoil protons on a nuclear reactor

    International Nuclear Information System (INIS)

    Mukhammedov, S.; Khaydarov, A.; Barsukova, E.G.

    2006-01-01

    The nuclear reactions excited by recoil protons and of the detection possibility of the various chemical elements with the use of these secondary nucleus reactions were investigated. The recoil protons are produced on a nuclear reactor in the result of (n, p) inelastic and elastic scattering interaction of fast neutrons with nuclei of hydrogen. It is well known that the share of fast neutrons in energetic spectrum of reactor's neutrons in comparison with the share of thermal neutrons is small. . Consequently, the share of recoil protons produced in the result of fast neutron interaction with nuclei of light elements, capable to cause the nuclear reactions, is also small, des, due to Coulomb barrier of nuclei the recoil protons can cause the nuclear reactions only on nuclei of light and some middle elements. Our studies show that observable yields have radio nuclides excited in the result of nuclear reactions on Li, B, O, V and Cu. Our experimental results have demonstrated that the proton activation analysis based on the application of secondary nuclear reactions is useful technique to determine large contents of various light and medium chemical elements. Detection limits for studied chemical elements are estimated better than 10 ppm

  5. Single proton transfer reactions on odd-even nuclei

    International Nuclear Information System (INIS)

    Blasi, N.

    1984-01-01

    This thesis is devoted to the study of one proton transfer reactions, performed with the use of the magnetic spectrograph QMG/2 of the KVI, in two regions of the mass table. Stripping and pickup reactions on the odd-A target nuclei 193 Ir and 197 Au are described in the first part. The experimental spectroscopic factors obtained are used to test several collective models that are based on coupling between bosons (phonons) and fermions. In the second part, the proton stripping reactions on 113 In and 115 In are studied. Shell model calculations are performed and applied to the experimental results. (Auth.)

  6. Highly enantioselective access to cannabinoid-type tricyles by organocatalytic Diels–Alder reactions

    Directory of Open Access Journals (Sweden)

    Stefan Bräse

    2012-08-01

    Full Text Available After prosperous domino reactions towards benzopyrans, the products were used as the starting material in Lewis acid catalyzed and organocatalytic Diels–Alder reactions to build up a tricyclic system. Herein, an asymmetric induction up to 96% enantiomeric excess was obtained by the use of imidazolidinone catalysts. This approach can be utilized to construct the tricyclic system in numerous natural products, in particular the scaffold of tetrahydrocannabinol (THC being the most representative one. Compared with other published methods, condensation with a preexisting cyclohexane moiety in the precursor is needed to gain the heterogenic tricycle systems, whereas we present a novel strategy towards cannabinoid derivatives based on a flexible modular synthesis.

  7. 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.

  8. Acute skin reactions observed in fractionated proton irradiation

    International Nuclear Information System (INIS)

    Arimoto, Takuro; Maruhashi, Noboru; Takada, Yoshihisa; Hayakawa, Yoshinori; Inada, Tetsuo; Kitagawa, Toshio

    1989-01-01

    Between May 1985 and July 1987, 49 skin reactions of 43 patients treated by proton irradiation were observed at the Particle Radiation Medical Science Center (PARMS), the University of Tsukuba. Taking the peak skin score as an endpoint, the radiobiological effects [relative biological effectiveness (RBE) and time-dose relationship] of the proton beam in multi-fractionated treatments were estimated. Factors influencing the skin dose, such as the prescribed tumor dose, tumor site, and number of applied fields, were also analyzed. The following conclusions regarding acute skin reactions to the clinical use of proton irradiation were obtained: 1) the physical skin-sparing effect of proton irradiation in single-field irradiation, especially in superficial regions, is not large compared with that of high-energy photon irradiation; 2) multidirectional proton irradiation significantly reduced the skin dose and severity of acute reasons; 3) the radiobiological effects of the proton beam, RBE and the time factor, estimated in human skin in multi-fractional treatment were slightly smaller than those of X-rays, i.e., 0.92 and -0.25±0.09, respectively. (author)

  9. 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.

  10. 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.

  11. Dynamics of Anti-Proton -- Protons and Anti-Proton -- Nucleus Reactions

    CERN Document Server

    Galoyan, A; Uzhinsky, V

    2016-01-01

    A short review of simulation results of anti-proton-proton and anti-proton-nucleus interactions within the framework of Geant4 FTF (Fritiof) model is presented. The model uses the main assumptions of the Quark-Gluon-String Model or Dual Parton Model. The model assumes production and fragmentation of quark-anti-quark and diquark-anti-diquark strings in the mentioned interactions. Key ingredients of the model are cross sections of string creation processes and an usage of the LUND string fragmentation algorithm. They allow one to satisfactory describe a large set of experimental data, especially, a strange particle production, Lambda hyperons and K mesons.

  12. Proton transfers in the Strecker reaction revealed by DFT calculations

    Directory of Open Access Journals (Sweden)

    Shinichi Yamabe

    2014-08-01

    Full Text Available The Strecker reaction of acetaldehyde, NH3, and HCN to afford alanine was studied by DFT calculations for the first time, which involves two reaction stages. In the first reaction stage, the aminonitrile was formed. The rate-determining step is the deprotonation of the NH3+ group in MeCH(OH-NH3+ to form 1-aminoethanol, which occurs with an activation energy barrier (ΔE≠ of 9.6 kcal/mol. The stereochemistry (R or S of the aminonitrile product is determined at the NH3 addition step to the carbonyl carbon of the aldehyde. While the addition of CN− to the carbon atom of the protonated imine 7 appears to scramble the stereochemistry, the water cluster above the imine plane reinforces the CN− to attack the imine group below the plane. The enforcement hinders the scrambling. In the second stage, the aminonitrile transforms to alanine, where an amide Me-CH(NH2-C(=O-NH2 is the key intermediate. The rate-determining step is the hydrolysis of the cyano group of N(amino-protonated aminonitrile which occurs with an ΔE≠ value of 34.7 kcal/mol. In the Strecker reaction, the proton transfer along the hydrogen bonds plays a crucial role.

  13. Medium effects on spin observables of proton knockout reactions

    International Nuclear Information System (INIS)

    Krein, G.; Maris, T.A.J.; Rodrigues, B.B.; Veit, E.A.

    1994-07-01

    Medium modifications of the properties of bound nucleons and mesons are investigated by means of medium energy quasi free proton knockout reactions with polarized incident protons. The sensitivity of the spin observables of these reactions to modifications of the nucleon and meson properties is studied using the Bonn one-boson exchange model of the nucleon-nucleon interaction. A method proposed to extract the pp analysing power in medium from the (p, 2 p) asymmetries indicates a reduction of this quantity compared to its free space value. This reduction is linked to modifications of masses and coupling constants of the nucleons and mesons in the nucleus. The implications of these modifications for another spin observable to be measured in the future are discussed. (author). 39 refs, 9 figs

  14. Medium effects on spin observables of proton knockout reactions

    Energy Technology Data Exchange (ETDEWEB)

    Krein, G [Instituto de Fisica Teorica (IFT), Sao Paulo, SP (Brazil); Maris, T A.J.; Rodrigues, B B; Veit, E A [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Inst. de Fisica

    1994-07-01

    Medium modifications of the properties of bound nucleons and mesons are investigated by means of medium energy quasi free proton knockout reactions with polarized incident protons. The sensitivity of the spin observables of these reactions to modifications of the nucleon and meson properties is studied using the Bonn one-boson exchange model of the nucleon-nucleon interaction. A method proposed to extract the pp analysing power in medium from the (p, 2 p) asymmetries indicates a reduction of this quantity compared to its free space value. This reduction is linked to modifications of masses and coupling constants of the nucleons and mesons in the nucleus. The implications of these modifications for another spin observable to be measured in the future are discussed. (author). 39 refs, 9 figs.

  15. Two-proton correlation functions in nuclear reactions

    International Nuclear Information System (INIS)

    Verde, G.

    2001-01-01

    Full text: Proton-proton correlation functions can be used to study the space-time characteristics of nuclear reactions. For very short-lived sources, the maximum value of the correlation at 20 MeV/c, due to the attractive nature of the S-wave phase shift, provides a unique measure of the size of the emitting source. For long-lived sources, the height of this maximum depends, in addition, on the life time of the source. In this talk, we investigate the common reaction scenario involving both fast dynamical as well as slower emissions from evaporation and/or secondary decays of heavy fragments. We show that the maximum at 20 MeV/c depends both on the source dimension and on the fraction of coincident proton pairs produced in the early stage of the reaction, dominated by fast dynamical preequilibrium emission. The width of the peak at 20 MeV/c, on the other hand, is uniquely correlated to the size of the source. Hence, the size of the emitting source must be extracted from the width or, even better, from the entire shape of the correlation peak, and not from the height. By numerically inverting the measured correlation function, we show that existing data determine only the shape of the fast dynamical source and that its size changes little with proton momenta, contrary to previous analyses with Gaussian sources of zero-lifetime. We further show that the well documented dramatic decrease in the correlation maximum with decreasing total proton momentum reflects directly a corresponding decrease in the fraction of contributing proton pairs from preequilibrium emissions. This provides a powerful method to decompose the proton spectrum into a fraction that originates from fast dynamical emission and a complimentary fraction that originates from slower evaporative emission or secondary decays. We discuss also the comparison of such correlations to transport theories and the generalizations of these techniques to correlations between composite particles. Such studies can

  16. Production cross sections of proton-induced reactions on yttrium

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Sung-Chul; Song, Tae-Yung; Lee, Young-Ouk [Nuclear Data Center, Korea Atomic Energy Research Institute, Daejeon 34057 (Korea, Republic of); Kim, Guinyun, E-mail: gnkim@knu.ac.kr [Department of Physics, Kyungpook National University, Daegu 41566 (Korea, Republic of)

    2017-05-01

    The production cross sections of residual radionuclides such as {sup 86,88,89g}Zr, {sup 86g,87m,87g,88}Y, {sup 83g,85g}Sr, and {sup 83,84g}Rb in the {sup 89}Y(p,x) reaction were measured using a stacked-foil activation and offline γ-ray spectrometric technique with proton energies of 57 MeV and 69 MeV at the 100 MeV proton linac in the Korea Multi-purpose Accelerator Complex (KOMAC), Gyeongju, Korea. The induced activities of the activated samples were measured using a high purity germanium (HPGe) detector, and the proton flux was determined using the {sup nat}Cu(p,x){sup 62}Zn reaction. The measured data was compared with other experimental data and the data from the TENLD-2015 library based on the TALYS code. The present results are generally lower than those in literature, but are found to be in agreement with the shape of the excitation functions. The integral yields for the thick target using the measured cross sections are given.

  17. 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.

  18. Chiral relay: a novel strategy for the control and amplification of enantioselectivity in chiral Lewis acid promoted reactions.

    Science.gov (United States)

    Corminboeuf, Olivier; Quaranta, Laura; Renaud, Philippe; Liu, Mei; Jasperse, Craig P; Sibi, Mukund P

    2003-01-03

    Chiral Lewis acid catalysis has emerged as one of the premiere method to control stereochemistry. Much effort has gone into the design of superior ligands with increasing steric extension to shield distant reactive sites. We report here an alternative and complementary approach based on a "chiral relay". This strategy focuses on the improved design of achiral templates which may relay and amplify the stereochemistry from ligands. The essence of this strategy is that the chiral Lewis acid would effectively convert an achiral template into a chiral non-racemic template. This approach combines the advantages of enantioselective catalysis (substoichiometric amount of the chiral inducer) with the ones of chiral auxiliary control (efficient and predictable stereocontrol).

  19. 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.

  20. What's new in the proton transfer reaction from pyranine to water? A femtosecond study of the proton transfer dynamics

    International Nuclear Information System (INIS)

    Prayer, C.; Gustavsson, T.; Tran-Thi, T.-H.

    1996-01-01

    The proton transfer from excited pyranine to water is studied by the femtosecond fluorescence upconversion technique. It is shown for the first time that the proton transfer reaction in water proceeds by three successive steps: the solvent cage relaxation, the specific solute-solvent hydrogen-bond formation and finally the ion pair dissociation/diffusion

  1. Investigation of GeV proton-induced spallation reactions

    International Nuclear Information System (INIS)

    Hilscher, D.; Herbach, C.-M.; Jahnke, U.

    2003-01-01

    A reliable and precise modeling of GeV proton-induced spallation reactions is indispensable for the design of the spallation module and the target station of future accelerator driven hybrid reactors (ADS) or spallation neutron sources (ESS), in particular, to provide precise predictions for the neutron production, the radiation damage of materials (window), and the production of radioactivity ( 3 H, 7 Be etc.) in the target medium. Detailed experimental nuclear data are needed for sensitive validations and improvements of the models, whose predictive power is strongly dependent on the correct physical description of the three main stages of a spallation reaction: (i) the Intra-Nuclear-Cascade (INC) with the fast heating of the target nucleus, (ii) the de-excitation due to pre-equilibrium emission including the possibility of multi-fragmentation, and (iii) the statistical decay of thermally excited nuclei by evaporation of light particles and fission in the case of heavy nuclei. Key experimental data for this endeavour are absolute production cross sections and energy spectra for neutrons and light charged-particles (LCPs), emission of composite particles prior and post to the attainment of an equilibrated system, distribution of excitation energies deposited in the nuclei after the INC, and fission probabilities. The correlations of these quantities are particularly important to detect and identify possible deficiencies of the theoretical modeling of the various stages of a spallation reaction. Systematic measurements of such data are furthermore needed over large ranges of target nuclei and incident proton energies. Such data has been measured with the NESSI detector. An overview of new and previous results will be given. (authors)

  2. Membrane introduction proton-transfer-reaction mass spectrometry

    International Nuclear Information System (INIS)

    Alexander, M.; Boscaini, E.; Maerk, T.; Lindinger, W.

    2002-01-01

    Proton-transfer-reaction mass spectrometry (PTR-MS) is a rapidly expanding field with multiple applications in ion physics, atmospheric chemistry, food chemistry, volatile organic compounds monitoring and biology. Initial studies that combine PTR-MS and membrane introduction mass spectrometry (MIMS) were researched and outlined. First using PTR-MS, certain fundamental physical properties of a poly-dimethylsiloxane (PDMS) membrane including solubilities and diffusion coefficients were measured. Second, it was shown how the chemical selectivity of the (PDMS) can be used to extend the capabilities of the PTR-MS instrument by eliminating certain isobaric interferences and excluding water from volatile organic compounds (VOCs). Experiments with mixtures of several VOCs (toluene, benzene, acetone, propanal, methanol) are presented. (nevyjel)

  3. 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.

  4. Measurement of the polarization of cumulative protons in γA → pX reaction

    International Nuclear Information System (INIS)

    Avakyan, R.O.; Avakyan, E.O.; Avetisyan, A.Eh.

    1985-01-01

    The polarization of cumulative protons in γA → px reaction is measured in the range of proton energy (190+270) MeV for C, Cu, Sn, Pb nuclei. The measured polarization is practically independent of the energy of protons and the atomic number of nuclei

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. Measurement of proton capture reactions in the hot cycles: an evaluation of experimental methods

    Energy Technology Data Exchange (ETDEWEB)

    Leleux, P [Inst. de Physique Nucleaire, Univ. Catholique de Louvain, Louvain-la-Neuve (Belgium)

    1998-06-01

    In the hot cycles, most of the proton capture reactions involve radioactive nuclei in the entrance and exit channels. This paper evaluates the specific methods that were designed to measure such reactions. (orig.)

  10. Quantitative analysis of skin reaction by reflectance spectrophotometer. Acute reaction following proton therapy

    International Nuclear Information System (INIS)

    Kawashima, Mitsuhiko; Okumura, Toshiyuki; Tatsuzaki, Hideo; Tsuji, Hiroshi; Tsujii, Hirohiko.

    1994-01-01

    Acute reactions induced by proton irradiation were measured using a reflectance spectrophotometer, which is commonly used in the printing and textile industries. In this method, the skin color was expressed by three parameters, lightness (L * ), chroma (C * ) and hue (h). At first, in order to evaluate the accuracy of this spectrophotometer, the skin color of a normal volunteer was measured 100 times. The values of the three parameters for normal skin were as follows (mean values and standard deviation), L * : 68.64±0.29, C * : 19.08±0.13, h: 69.41±0.76. The standard deviations with regard to L * and h, were considered to be sufficiently small when compared with the changes of these parameters (prefix: Δ) in the irradiated sites (ΔL * * and h values significantly decreased with time, and the L * values were highly correlated with elapsed treatment days. The h values had a relatively low linear correlation compared with L * . The C * values had no trends as the treatment period was extended. Among these parameters, the L * values were the most valuable for assessment of proton-induced skin reactions, and it was suggested that the L * values measured with this spectrophotometer were a useful index for showing biological effects induced by proton irradiation. Further experiments are needed to apply this method to quantify the biological effects induced by other forms of ionizing radiation. (author)

  11. New Oxime Ligand with Potential for Proton-Coupled Electron-Transfer Reactions

    DEFF Research Database (Denmark)

    Deville, Claire; Sundberg, Jonas; McKenzie, Christine Joy

    Proton-coupled electron-transfer (PCET) is found in a range of oxidation-reduction reactions in biology.1 This mechanism is of interest for applications in energy conversion processes. The PCET reaction has been shown to be facilitated when the proton is transferred to an intramolecular basic sit...

  12. 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.

  13. Palladium-catalyzed cyclization reactions of 2-vinylthiiranes with heterocumulenes. Regioselective and enantioselective formation of thiazolidine, oxathiolane, and dithiolane derivatives.

    Science.gov (United States)

    Larksarp, C; Sellier, O; Alper, H

    2001-05-18

    The first palladium-catalyzed ring-expansion reaction of 2-vinylthiiranes with heterocumulenes to form sulfur-containing five-membered-ring heterocycles is described. This regioselective reaction requires 5 mol % of Pd(2)(dba)(3).CHCl(3) and 10 mol % of bidendate phosphine ligand (dppp, BINAP), at 50-80 degrees C, in THF. The reaction of 2-vinylthiiranes with carbodiimides, isocyanates, and ketenimines affords 1,3-thiazolidine derivatives, whereas the reaction with diphenylketene or isothiocyanates results in the formation of 1,3-oxathiolane or 1,3-dithiolane compounds in good to excellent isolated yields and in up to 78% ee.

  14. 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.

  15. Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium-Tyrosine Complex.

    Science.gov (United States)

    Lennox, J Christian; Dempsey, Jillian L

    2017-11-22

    A polypyridyl ruthenium complex with fluorinated bipyridine ligands and a covalently bound tyrosine moiety was synthesized, and its photo-induced proton-coupled electron transfer (PCET) reactivity in acetonitrile was investigated with transient absorption spectroscopy. Using flash-quench methodology with methyl viologen as an oxidative quencher, a Ru 3+ species is generated that is capable of initiating the intramolecular PCET oxidation of the tyrosine moiety. Using a series of substituted pyridine bases, the reaction kinetics were found to vary as a function of proton acceptor concentration and identity, with no significant H/D kinetic isotope effect. Through analysis of the kinetics traces and comparison to a control complex without the tyrosine moiety, PCET reactivity was found to proceed through an equilibrium electron transfer followed by proton transfer (ET-PT) pathway in which irreversible deprotonation of the tyrosine radical cation shifts the ET equilibrium, conferring a base dependence on the reaction. Comprehensive kinetics modeling allowed for deconvolution of complex kinetics and determination of rate constants for each elementary step. Across the five pyridine bases explored, spanning a range of 4.2 pK a units, a linear free-energy relationship was found for the proton transfer rate constant with a slope of 0.32. These findings highlight the influence that proton transfer driving force exerts on PCET reaction kinetics.

  16. Proton exchange in acid–base complexes induced by reaction coordinates with heavy atom motions

    International Nuclear Information System (INIS)

    Alavi, Saman; Taghikhani, Mahdi

    2012-01-01

    Highlights: ► Proton exchange in acid–base complexes is studied. ► The structures, binding energies, and normal mode vibrations are calculated. ► Transition state structures of proton exchange mechanism are determined. ► In the complexes studied, the reaction coordinate involves heavy atom rocking. ► The reaction coordinate is not simply localized in the proton movements. - Abstract: We extend previous work on nitric acid–ammonia and nitric acid–alkylamine complexes to illustrate that proton exchange reaction coordinates involve the rocking motion of the base moiety in many double hydrogen-bonded gas phase strong acid–strong base complexes. The complexes studied involve the biologically and atmospherically relevant glycine, formic, acetic, propionic, and sulfuric acids with ammonia/alkylamine bases. In these complexes, the magnitude of the imaginary frequencies associated with the proton exchange transition states are −1 . This contrasts with widely studied proton exchange reactions between symmetric carboxylic acid dimers or asymmetric DNA base pair and their analogs where the reaction coordinate is localized in proton motions and the magnitude of the imaginary frequencies for the transition states are >1100 cm −1 . Calculations on complexes of these acids with water are performed for comparison. Variations of normal vibration modes along the reaction coordinate in the complexes are described.

  17. 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.

  18. Hyperon production in photonuclear reactions on protons and deuterons : The Kappa(0)Sigma(+) channel

    NARCIS (Netherlands)

    Lohner, H; Bacelar, J; Castelijns, R; Messchendorp, J; Shende, S; Maeda, K; Tamura, H; Nakamura, SN; Hashimoto, O

    2004-01-01

    With the combined setup of the Crystal Barrel and TAPS photonspectrometers at ELSA in Bonn we have studied photonuclear reactions on protons and deuterons. From the series of experiments on single and multiple neutral meson emission we concentrate here on the hyperon production off protons and

  19. Polarization of cumulative protons in the reaction. gamma. A r arrow pX

    Energy Technology Data Exchange (ETDEWEB)

    Avakyan, R.O.; Avetisyan, A.E.; Arestakesyan, G.A.; Bartikyan, M.V.; Garibyan, Y.A.; Grigoryan, A.E.; Eganov, V.S.; Karapetyan, A.P.; Karapetyan, M.P.; Keropyan, I.A.; and others

    1989-02-01

    The polarization of cumulative protons has been measured in the reaction {gamma}{ital A}{r arrow}{ital pX} in the proton-energy region 170--270 MeV for C and Sn nuclei in bremsstrahlung beams produced by 4.5- and 1.5-GeV electrons. The measured polarization value is close to zero.

  20. Enantioselective syntheses of aeruginosin 298-A and its analogues using a catalytic asymmetric phase-transfer reaction and epoxidation.

    Science.gov (United States)

    Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Fukuta, Yuhei; Nemoto, Tetsuhiro; Shibasaki, Masakatsu

    2003-09-17

    We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogues, in which all stereocenters were controlled by a catalytic asymmetric phase-transfer reaction and epoxidation. Furthermore, drastic counteranion effects in phase-transfer catalysis were observed for the first time, making it possible to three-dimensionally fine-tune the catalyst (ketal part, aromatic part, and counteranion).

  1. Cross sections of nuclear reactions induced by protons, deuterons, and alpha particles. Pt.6. Phosphorus

    International Nuclear Information System (INIS)

    Tobailem, Jacques.

    1981-11-01

    Cross sections are reviewed for nuclear reactions induced by protons, deuterons, and alpha particles on phosphorus targets. When necessary, published experimental data are corrected, and, when possible, excitation functions are proposed [fr

  2. Fragment mass distribution of proton-induced spallation reaction with intermediate energy

    International Nuclear Information System (INIS)

    Fan Sheng; Ye Yanlin; Xu Chuncheng; Chen Tao; Sobolevsky, N.M.

    2000-01-01

    The test of part benchmark of SHIELD code is finished. The fragment cross section and mass distribution and excitation function of the residual nuclei from proton-induced spallation reaction on thin Pb target with intermediate energy have been calculated by SHIELD code. And the results are in good agreement with measured data. The fragment mass distribution of the residual nuclei from proton-induced spallation reaction on thick Pb target with incident energy 1.6 GeV have been simulated

  3. Enantioselective syntheses and biological studies of aeruginosin 298-A and its analogs: application of catalytic asymmetric phase-transfer reaction.

    Science.gov (United States)

    Fukuta, Yuhei; Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Nemoto, Tetsuhiro; Kisugi, Takaya; Okino, Tatsufumi; Shibasaki, Masakatsu

    2004-04-13

    Aeruginosin 298-A was isolated from the freshwater cyanobacterium Microcystis aeruginosa (NIES-298) and is an equipotent thrombin and trypsin inhibitor. A variety of analogs were synthesized to gain insight into the structure-activity relations. We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogs, in which all stereocenters were controlled by catalytic asymmetric phase-transfer reaction promoted by two-center asymmetric catalysts and catalytic asymmetric epoxidation promoted by a lanthanide-BINOL complex. Furthermore, serine protease inhibitory activities of aeruginosin 298-A and its analogs were examined.

  4. Investigating the nature of palladium chain-walking in the enantioselective redox-relay Heck reaction of alkenyl alcohols.

    Science.gov (United States)

    Hilton, Margaret J; Xu, Li-Ping; Norrby, Per-Ola; Wu, Yun-Dong; Wiest, Olaf; Sigman, Matthew S

    2014-12-19

    The mechanism of the redox-relay Heck reaction was investigated using deuterium-labeled substrates. Results support a pathway through a low energy palladium-alkyl intermediate that immediately precedes product formation, ruling out a tautomerization mechanism. DFT calculations of the relevant transition structures at the M06/LAN2DZ+f/6-31+G* level of theory show that the former pathway is favored by 5.8 kcal/mol. Palladium chain-walking toward the alcohol, following successive β-hydride eliminations and migratory insertions, is also supported in this study. The stereochemistry of deuterium labels is determined, lending support that the catalyst remains bound to the substrate during the relay process and that both cis- and trans-alkenes form from β-hydride elimination.

  5. Testing quantum chromodynamics in anti-proton reactions

    International Nuclear Information System (INIS)

    Brodsky, S.J.

    1987-10-01

    An experimental program with anti-protons at intermediate energy can serve as an important testing ground for QCD. Detailed predictions for exclusive cross sections at large momentum transfer based on perturbative QCD and the QCD sum rule form of the proton distribution amplitude are available for anti p p → γγ for both real and virtual photons. Meson-pair and lepton-pair final states also give sensitive tests of the theory. The production of charmed hadrons in exclusive anti p p channels may have a non-negligible cross section. Anti-proton interactions in a nucleus, particularly J/psi production, can play an important role in clarifying fundamental QCD issues, such as color transparency, critical length phenomena, and the validity of the reduced nuclear amplitude phenomenology

  6. Proton cycling, buffering, and reaction stoichiometry in natural waters

    NARCIS (Netherlands)

    Hofmann, A.F.; Middelburg, J.J.; Soetaert, K.; Wolf-Gladrow, D.A.; Meysman, F.J.R.

    2010-01-01

    Ongoing acidification of the global ocean necessitates a solid understanding of how biogeochemical processes are driving proton cycling and observed pH changes in natural waters. The standard way of calculating the pH evolution of an aquatic system is to specify first how biogeochemical processes

  7. 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.

  8. Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

    Science.gov (United States)

    Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; Roubelakis, Manolis M.; Maher, Andrew G.; Lee, Chang Hoon; Chambers, Matthew B.; Hammes-Schiffer, Sharon; Nocera, Daniel G.

    2014-01-01

    The hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring. PMID:25298534

  9. Probing the structure of unstable nuclei through the recoiled proton tagged knockout reaction

    International Nuclear Information System (INIS)

    Ye, Y.; Cao, Z.; Jiang, D.

    2010-01-01

    Recoiled proton tagged knockout reaction experiments were carried-out for 8 He at 82,5 MeV/u in RIKEN and for 6 He at 65 MeV/u in Lanzhou. The very preliminary results for the distinguish of the reaction mechanism are presented and compared to the kinematics calculation. (authors)

  10. Status of experimental data of proton-induced reactions for intermediate-energy nuclear data evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Yukinobu; Kawano, Toshihiko [Kyushu Univ., Fukuoka (Japan); Yamano, Naoki; Fukahori, Tokio

    1998-11-01

    The present status of experimental data of proton-induced reactions is reviewed, with particular attention to total reaction cross section, elastic and inelastic scattering cross section, double-differential particle production cross section, isotope production cross section, and activation cross section. (author)

  11. 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.

  12. Isotope effects for base-promoted, gas-phase proton transfer reactions

    International Nuclear Information System (INIS)

    Grabowski, J.J.; Cheng, Xueheng

    1991-01-01

    Proton transfer reactions are among the most basic, the most common and the most important of chemical transformations; despite their apparent simplicity, much is unknown about this most fundamental of all chemical processes. Active interest in understanding the underlying principles of organic proton transfer reactions continues because of efforts being made to develop the theory of elementary chemical processes, because of the resurgence of interest in mechanistic organic chemistry and because of the resurgence of interest in mechanistic organic chemistry processes, because of the resurgence of interest in mechanistic organic chemistry and because of the dynamic role played by proton transfers in biochemical transformations. As organic chemists, the authors have used the flowing afterglow technique to gain an appreciation of the fundamental issues involved in reaction mechanisms by examining such processes in a solvent-free environment under thermally-equilibrated (300 K) conditions. Recent characterization of the facile production of both acetate and the monoenolate anion from the interaction of hydroxide or fluoride with acetic acid reinforces the idea that much yet must be learned about proton transfers/proton abstractions in general. Earlier work by Riveros and co-workers on competitive H vs D abstraction from α-d 1 -toluenes and by Noest and Nibbering on competitive H vs D abstraction from α,α,α-d 3 -acetone, in combination with the acetic acid results, challenged the author's to assemble a comprehensive picture of the competitive nature of proton transfer reactions for anionic base-promoted processes

  13. Aprotic solvent systems provide mechanistic windows for biomolecular reactions: nucleic acid proton exchange

    International Nuclear Information System (INIS)

    McConnell, B.; Tan, A.

    1986-01-01

    Detection of general acid-base catalysis of proton transfer reactions in aqueous cytidine (or adenosine) is completely obscured by the highly reactive endocyclic protonated species of the nucleobase, whose amino proton lifetime is much shorter than that of the neutral form. In aqueous solution, protonation of the nucleobase always accompanies protonation of the buffer catalyzing exchange. However, in DMSO/water mixtures this is not the case; aqueous protonated acetate or chloroacetate can be added to cytidine in DMSO solutions without further dissociation of the buffer or significant protonation of cytidine N-3. Under these conditions general acid catalysis is observed, which involves an H-bonded complex between cytidine (N-3) and the buffer acid. Increased amino proton exchange in response to H-bond donation to C(N-3) is further suggested by increased 1 H NMR saturation-recovery rates with the formation of G-C base-pairs in DMSO and by the inverse dependence of amino proton exchange on nucleoside concentration

  14. Proton tungsten reactions at 400 GeV

    International Nuclear Information System (INIS)

    Cincheza, J.; Cohen, J.; Marin, A.

    1979-03-01

    We report from an experiment where 400 GeV protons interact with tungsten nuclei in thin wires laminated into nuclear emulsion. The mean multiplicities of black, grey and shower track producing particles are found to be 11.5+-0.4, 5.2+-0.2 and 20.0+-0.6 respectively. The correlations between different particle categories are studied and we find that the correlation between black and grey prongs is dependent on the target mass, while the correlation between the grey prongs and the shower particles are similar to the one found when lighter elements are used as targets. This provides evidence that the grey prong particles (recoiling protons) is a measure of the number of collisions inside the nucleus. (author)

  15. Sunflower oil ozonation. Following of the reaction by proton Nuclear Magnetic Resonance

    International Nuclear Information System (INIS)

    Diaz Gomez, Maritza F.

    2005-01-01

    Previous studies have demonstrated that the technique of Proton Nuclear Magnetic Resonance can be used for the pursuit of the reaction between the ozone and the unsaturated fatty acids. It's carried out the sunflower oil ozonization to different applied dose of ozone and the index of peroxides and the concentration of aldehydes are determined. The main reaction products were identified by Proton Nuclear Magnetic Resonance Spectroscopy (NMR 1 H). The intensities of the signs were used to follow the advance of the reaction between the ozone and the sunflower oil. It is was carried out until obtaining an index of peroxides of 1 202 mmol-equiv/kg. The intensities of the signs of the olefinic protons diminish with a gradual increment in the dose of applied ozone, but without ending up disappearing completely. The ozonides of Criegee obtained to applied dose of ozone of 107,1 mg/g were approximately bigger 7,4 times that those obtained at the beginning from the reaction to applied dose of ozone of 15,3 mg/g. The aldehydes protons were observed as a sign of weak intensity in all the spectra. The signs belonging to the olenifics protons of the hydroperoxides in d = 5,55 ppm increases with the increment of the applied dose of ozone. You concludes that to higher applied dose of ozone, haggler is the advance of the ozonization reaction, what belongs together with a bigger formation of oxygenated compounds

  16. Substitution and protonation reactions of nitrilotriaceta tochromium(lll) ions

    CSIR Research Space (South Africa)

    Visser, HG

    1994-04-01

    Full Text Available The reaction of NH4[Cr(NTA)(H2O)2] (NTA = nitrilotriacetic acid) with H+ has been studied at different temperatures and a rate constant of 1.27(3) x 10(-2) S-1 was obtained at 25.1-degrees-C. It is proposed that the reaction involves the formation...

  17. Effects of the anion salt nature on the rate constants of the aqueous proton exchange reactions.

    Science.gov (United States)

    Paredes, Jose M; Garzon, Andres; Crovetto, Luis; Orte, Angel; Lopez, Sergio G; Alvarez-Pez, Jose M

    2012-04-28

    The proton-transfer ground-state rate constants of the xanthenic dye 9-[1-(2-methyl-4-methoxyphenyl)]-6-hydroxy-3H-xanthen-3-one (TG-II), recovered by Fluorescence Lifetime Correlation Spectroscopy (FLCS), have proven to be useful to quantitatively reflect specific cation effects in aqueous solutions (J. M. Paredes, L. Crovetto, A. Orte, J. M. Alvarez-Pez and E. M. Talavera, Phys. Chem. Chem. Phys., 2011, 13, 1685-1694). Since these phenomena are more sensitive to anions than to cations, in this paper we have accounted for the influence of salts with the sodium cation in common, and the anion classified according to the empirical Hofmeister series, on the proton transfer rate constants of TG-II. We demonstrate that the presence of ions accelerates the rate of the ground-state proton-exchange reaction in the same order than ions that affect ion solvation in water. The combination of FLCS with a fluorophore undergoing proton transfer reactions in the ground state, along with the desirable feature of a pseudo-dark state when the dye is protonated, allows one unique direct determination of kinetic rate constants of the proton exchange chemical reaction. This journal is © the Owner Societies 2012

  18. 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.

  19. Free energy for protonation reaction in lithium-ion battery cathode materials

    International Nuclear Information System (INIS)

    Benedek, R.; Thackeray, M. M.; van de Walle, A.

    2008-01-01

    Calculations are performed of free energies for proton-for-lithium-ion exchange reactions in lithium-ion battery cathode materials. First-principles calculations are employed for the solid phases and tabulated ionization potential and hydration energy data for aqueous ions. Layered structures, spinel LiMn 2 O 4 , and olivine LiFePO 4 are considered. Protonation is most favorable energetically in layered systems, such as Li 2 MnO 3 and LiCoO 2 . Less favorable are ion-exchange in spinel LiMn 2 O 4 and LiV 3 O 8 . Unfavorable is the substitution of protons for Li in olivine LiFePO 4 , because of the large distortion of the Fe and P coordination polyhedra. The reaction free energy scales roughly linearly with the volume change in the reaction

  20. Two-proton transfer reactions on even Ni and Zn isotopes

    International Nuclear Information System (INIS)

    Boucenna, A.; Kraus, L.; Linck, I.; Tsan Ung Chan

    1988-01-01

    Two-proton transfer reactions induced by 112 MeV 12 C ions on even Ni and Zn isotopes are found to be less selective than the analogous two-neutron transfer reactions induced on the same targets in a similar incident energy range. The additional collective aspects observed in the proton transfer are examined in view of a semiphenomenological model of two quasi-particles coupled to a triaxial asymmetric rotor. Tentative spin and parity assignments emerge from this comparison, from crude shell model calculations and from systematic trends

  1. Analysis of trace gases at ppb levels by proton transfer reaction mass spectrometry (PTR-MS)

    International Nuclear Information System (INIS)

    Lindinger, W.; Hansel, A.

    1996-01-01

    A proton transfer reaction mass spectrometry (PTR-MS) system has been developed which allows for on-line measurements of trace gas components with concentrations as low as 1 ppb. The method is based on reactions of H 3 O + ions, which perform non-dissociative proton transfer to most of the common organic trace constituents but do not react with any of the components present in clean air. Examples of medical information obtained by means of breath analysis, of environmental trace analysis, and examples in the field of food chemistry demonstrate the wide applicability of the method. (Authors)

  2. Low-Energy Nuclear Reactions of Protons in Host Metals at Picometre Distance

    International Nuclear Information System (INIS)

    Heinrich Hora; George H. Miley; Jak C. Kelly

    2000-01-01

    A review is given for the explanation of the measurements of Miley (et al.) of a fully reproducible generation of nuclei of the whole periodic table by protons in host metals during a several-weeks reaction. Similar low-energy nuclear reactions (LENR) were observed by other groups. The fact that the heavy nuclides are not due to pollution can be seen from the fact that such very rare elements as thulium and terbium were detected by unique K-shell X-ray spectra. The nuclear reaction energy goes into the heavy nuclei as measured from much bigger traces in CR39 than from alphas. The fact that any reaction of the protons results in stable daughter nuclei is confirmed by the fact that the highest energy gain is resulting with stable reaction products. This has been explained in Ref. 2, and the energy gain for the heavy element generation by a compound reaction was discussed. The explanation is based on the model of the authors from 1989 to assume free motion of the protons contrary to localized crystalline states. A relation of the reaction time U on distance d of the reacting nuclei by a power law with an exponent 34.8 was derived. Based on few reproducible D-D reactions, a reaction time near the range of megaseconds and a reaction distance of nanometers was concluded. A splendid confirmation of the picometre-megasecond reactions was achieved by Li (et al.) from his direct quantum mechanical calculations of the hot fusion D-T reactions based on a one-step selective resonance tunneling model. Li (et al.) were able for the first time to derive the cross sections of the hot fusion. Li's application to picometre distance showed megasecond reaction times with no neutron or gamma emission. Because of the imaginary part in the Schroedinger potential, the problem of the level width is reduced by damping

  3. Facility for the measurement of proton polarization in nuclear reactions

    Energy Technology Data Exchange (ETDEWEB)

    Slobodrian, R J; Irshad, M; Labrie, R; Rioux, C; Roy, R; Pigeon, R [Laval Univ., Quebec City (Canada). Lab. de Physique Nucleaire

    1979-02-15

    A polarimetry facility based on high resolution and high efficiency silicon polarimeters with on-line particle identification is described. It has proven its capability to measure polarization in (/sup 3/He, p(pol)) reaction with cross section levels of 40 ..mu..b/sr.

  4. Proton transfer reaction time-of-flight mass spectrometry advancement in detection of hazardous substances

    International Nuclear Information System (INIS)

    Agarwal, B.

    2012-01-01

    Proton Transfer Reaction Mass Spectrometry (PTR-MS) is a mass spectrometric technique based on chemical ionization, which provides very rapid measurements (within seconds) of volatile organic compounds in air, usually without special sample preparation, and with a very low detection limit. The detection and study of product ion patterns of threat agents such as explosives and drugs and some major environmental pollutants (isocyanates and polychlorinated biphenyls (PCBs)) is explored in detail here using PTR-MS, specifically Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-TOF-MS). The proton transfer reaction (PTR) principle works on the detection of the compound in the vapor phase. For some compounds, which have extremely low vapor pressures, both sample and inlet line heating were needed. Generally, the protonated parent molecule (MH+) is found to be the dominant product ion, which therefore provides us with a higher level of confidence in the assignment of a trace compound. However, for several compounds, dissociative proton transfer can occur at various degrees resulting in other product ions. Analysis of other compounds, such as the presence of taggants and impurities were carried out, and in certain compounds unusual E/N anomalies were discovered (E/N is an instrumental set of parameters, where E is the electric field strength and N is the number density). Head space measurements above four different drinks (plain water, tea, red wine and white wine) spiked with four different 'date rape' drugs were also conducted. (author)

  5. SU-F-T-140: Assessment of the Proton Boron Fusion Reaction for Practical Radiation Therapy Applications Using MCNP6

    Energy Technology Data Exchange (ETDEWEB)

    Adam, D; Bednarz, B [University of Wisconsin, Madison, WI (United States)

    2016-06-15

    Purpose: The proton boron fusion reaction is a reaction that describes the creation of three alpha particles as the result of the interaction of a proton incident upon a 11B target. Theoretically, the proton boron fusion reaction is a desirable reaction for radiation therapy applications in that, with the appropriate boron delivery agent, it could potentially combine the localized dose delivery protons exhibit (Bragg peak) and the local deposition of high LET alpha particles in cancerous sites. Previous efforts have shown significant dose enhancement using the proton boron fusion reaction; the overarching purpose of this work is an attempt to validate previous Monte Carlo results of the proton boron fusion reaction. Methods: The proton boron fusion reaction, 11B(p, 3α), is investigated using MCNP6 to assess the viability for potential use in radiation therapy. Simple simulations of a proton pencil beam incident upon both a water phantom and a water phantom with an axial region containing 100ppm boron were modeled using MCNP6 in order to determine the extent of the impact boron had upon the calculated energy deposition. Results: The maximum dose increase calculated was 0.026% for the incident 250 MeV proton beam scenario. The MCNP simulations performed demonstrated that the proton boron fusion reaction rate at clinically relevant boron concentrations was too small in order to have any measurable impact on the absorbed dose. Conclusion: For all MCNP6 simulations conducted, the increase of absorbed dose of a simple water phantom due to the 11B(p, 3α) reaction was found to be inconsequential. In addition, it was determined that there are no good evaluations of the 11B(p, 3α) reaction for use in MCNPX/6 and further work should be conducted in cross section evaluations in order to definitively evaluate the feasibility of the proton boron fusion reaction for use in radiation therapy applications.

  6. Enantioselective Diels-Alder Reaction Using Chiral Mg Complexes Derived from Chiral 2-[2-[(Alkyl- or 2-[2-[(Arylsulfonyl)amino]phenyl]-4-phenyl-1,3-oxazoline.

    Science.gov (United States)

    Ichiyanagi, Tsuyoshi; Shimizu, Makoto; Fujisawa, Tamotsu

    1997-11-14

    Magnesium complexes derived from (R)-2-[2-[(alkyl- or (R)-2-[2-[(arylsulfonyl)amino]phenyl]-4-phenyl-1,3-oxazolines and methylmagnesium iodide were found to be efficient Lewis acid catalysts for the Diels-Alder reaction of 3-alkenoyl-1,3-oxazolidin-2-one with cyclopentadiene. Chiral ligands were easily prepared from readily available D-phenylglycinol in good yields. The reaction of 3-acryloyl-1,3-oxazolidin-2-one with cyclopentadiene catalyzed by a stoichiometric amount of the Lewis acid gave exclusively the endo-cycloaddition product in up to 92% ee. The sulfonamide group on the chiral ligand strongly influenced the enantiofacial selectivity: the use of a toluene-, benzene-, 1- or 2-naphthalene-, or methanesulfonamide group in the chiral ligand gave the endo-(2R)-cycloaddition product, while a trifluoromethanesulfonamide group predominantly gave its enantiomer, the endo-(2S)-cycloaddition product, in 65% ee. The scope and limitations of the catalytic effect of chiral Mg(II) complexes on the enantioselectivity of the Diels-Alder reaction were investigated. The reaction mechanism of the Mg(II)-catalyzed reaction is also discussed on the basis of the experimental results.

  7. Recent research on nuclear reaction using high-energy proton and neutron

    Energy Technology Data Exchange (ETDEWEB)

    Shibata, Tokushi [Tokyo Univ., Tanashi (Japan). Inst. for Nuclear Study

    1997-11-01

    The presently available high-energy neutron beam facilities are introduced. Then some interesting research on nuclear reaction using high-energy protons are reported such as the intermediate mass fragments emission and neutron spectrum measurements on various targets. As the important research using high-energy neutron, the (p,n) reactions on Mn, Fe, and Ni, the elastic scattering of neutrons, and the shielding experiments are discussed. (author)

  8. Test of supersymmetry in the 193Ir→194Pt proton stripping reactions

    International Nuclear Information System (INIS)

    Vergnes, M.; Rotbard, G.; Kalifa, J.; Berrier-Ronsin, G.; Vernotte, J.; Seltz, R.; Burke, D.G.

    1980-01-01

    A breakdown of the selection rules of the supersymmetry model is observed for the population of the 0 2 + and 2 2 + levels of 194 Pt in the 193 Ir → 194 Pt proton stripping reactions performed using the Orsay and Mc Master University tandem accelerators. The existence of other violations in the neighbouring nuclei leads to believe that we are seeing the limitations of the supersymmetry scheme itself, at least for particle transfer reactions

  9. Cross-sections of spallation residues produced in Proton –Induced reactions

    International Nuclear Information System (INIS)

    Al-Haydari, A.; Khan, A.A.; Abdul Ganai, A.; Hassan, G.S.

    2013-01-01

    The recent available GSI data for proton-induced spallation reactions by using inverse kinematics at different energies are analyzed for different reactions in terms of the percolation model together with the intranuclear cascade model (MCAS). The simulation results obtained for the cross sections of production of light ions and isotopes as a function of mass and charge number is calculated. Results of calculations are in good agreement with experiment

  10. A simple functional form for proton-208Pb total reaction cross sections

    International Nuclear Information System (INIS)

    Majumdar, S.; Deb, P.K.; Amos, K.

    2001-01-01

    A simple functional form has been found that gives a good representation of the total reaction cross sections for the scattering from 208 Pb of protons with energies in the range 30 to 300 MeV. The ratios of the total reaction cross sections calculated under this approximations compared well (to within a few percent) to those determined from the microscopic optical model potentials

  11. Capture reactions into borromean two-proton systems at rp-waiting points

    DEFF Research Database (Denmark)

    Hove, D.; Jensen, A. S.; Fynbo, H. O. U.

    2016-01-01

    of the radiative capture reactions can be determined. We present numerical results for $E1$ and $E2$ photon emission, and discuss occurrence preferences in general as well as relative sizes of these most likely processes. Finally, we present narrow estimated intervals for the proton capture rates relevant...

  12. Quasi-free knockout reactions with the proton-dripline nucleus {sup 17}Ne

    Energy Technology Data Exchange (ETDEWEB)

    Wamers, Felix; Aumann, Thomas [Institut fuer Kernphysik, TU, Darmstadt (Germany); Heil, Michael [Kernreaktionen und Nukleare Astrophysik, GSI, Darmstadt (Germany); Marganiec, Justyna [ExtreMe Matter Institute EMMI, GSI, Darmstadt (Germany); Plag, Ralf [Kernreaktionen und Nukleare Astrophysik, GSI, Darmstadt (Germany); Goethe Universitaet, Frankfurt a.M. (Germany); Collaboration: R3B-Collaboration

    2011-07-01

    {sup 17}Ne is a proton-dripline nucleus that has raised special interest in nuclear-structure physics in recent years. As a ({sup 15}O+2p) Borromean 3-body system, it is often considered to be a 2-proton-halo nucleus, yet lacking concluding experimental evidence about its structure. We have studied breakup reactions of 500 AMeV {sup 17}Ne secondary beams using the R{sup 3}B-LAND setup at GSI. One focus was on the quasi-free one-proton knockout in a proton-rich paraffin (CH{sub 2}) target in inverse kinematics, i.e., {sup 17}Ne(p,2p){sup 16}F{yields}{sup 15}O+p, in comparison to the one-proton knockout with a carbon target. Recoil protons have been detected with Si-Strip detectors and the surrounding 4{pi} NaI spectrometer ''Crystal Ball'', thus providing a clean signature for quasi-free knockout. First results on two-proton removal cross sections with CH{sub 2} and C targets will be presented, as well as transverse momentum distributions of the {sup 15}O core in {sup 17}Ne. Projectile-like forward protons after one-proton knockout from {sup 17}Ne have been measured in coincidence with the {sup 15}O residual core, leading to the relative-energy spectrum of the unbound {sup 16}F. Possible interpretations and implications regarding the structure of {sup 17}Ne are discussed.

  13. Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

    International Nuclear Information System (INIS)

    Janev, R.K.; Kato, T.; Wang, J.G.

    2001-05-01

    The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C x H y charge exchange reactions from thermal energies up to several hundreds keV for all C x H y molecules with x=1, 2, 3 and 1 ≤ y ≤ 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

  14. Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

    Energy Technology Data Exchange (ETDEWEB)

    Janev, R.K.; Kato, T. [National Inst. for Fusion Science, Toki, Gifu (Japan); Wang, J.G. [Department of Physics and Astronomy, University of Georgia, Athens (United States)

    2001-05-01

    The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C{sub x}H{sub y} charge exchange reactions from thermal energies up to several hundreds keV for all C{sub x}H{sub y} molecules with x=1, 2, 3 and 1 {<=} y {<=} 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

  15. 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.

  16. Experimental determination of proton induced reaction cross sections on {sup nat}Ni near threshold energy

    Energy Technology Data Exchange (ETDEWEB)

    Uddin, Md. Shuza [Atomic Energy Research Establishment, Dhaka (Bangladesh). Tandem Accelerator Facilities; Forschungszentrum Juelich GmbH (Germany). Inst. fuer Neurowissenschaften und Medizin, INM-5: Nuklearchemie; Chakraborty, Animesh Kumer [Atomic Energy Research Establishment, Dhaka (Bangladesh). Tandem Accelerator Facilities; Chittagong University of Engineering and Technology (Bangladesh). Dept. of Physics; Spellerberg, Stefan; Spahn, Ingo; Qaim, Syed M. [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Neurowissenschaften und Medizin, INM-5: Nuklearchemie; Shariff, Md. Asad; Das, Sopan [Atomic Energy Research Establishment, Dhaka (Bangladesh). Tandem Accelerator Facilities; Rashid, Md. Abdur [Chittagong University of Engineering and Technology (Bangladesh). Dept. of Physics

    2016-08-01

    A newly developed facility at the 3 MV Tandem Accelerator at Dhaka for measurement of proton induced reaction cross sections in the energy region below 5 MeV is outlined and tests for the beam characterization are described. The results were validated by comparison with the well-known excitation function of the {sup 64}Ni(p, n){sup 64}Cu reaction. Excitation functions of the reactions {sup nat}Ni(p, x){sup 60,61}Cu, {sup nat}Ni(p, x){sup 55,57,58m+g}Co and {sup nat}Ni(p, x){sup 57}Ni were also measured from threshold to 16 MeV using the stacked-foil technique, whereby irradiations were performed with 5 MeV protons available at the Tandem Accelerator and 16.7 MeV protons at the BC 1710 cyclotron at Juelich, Germany. The radioactivity was measured using HPGe γ-ray detectors. A few results are new, the others strengthen the database. In particular, the results of the reaction {sup nat}Ni(p, x){sup 61}Cu below 3 MeV could serve as beam monitor.

  17. Study of neutron-proton pairing in N=Z unstable nuclei through transfer reactions

    International Nuclear Information System (INIS)

    Le Crom, B.

    2016-01-01

    A nucleus is described as a set of independent neutrons and protons linked by a mean-field potential. However, in order to have a better description one needs to take into account some residual interactions such as pairing. Neutron-neutron and proton-proton pairings are well-studied but neutron-proton pairing is not well-known. np pairing can be isovector pairing such as nn and pp pairing or isoscalar which is yet unknown. Over-binding of N=Z nuclei could be a manifestation of np pairing. We have studied np pairing through transfer reactions. In this case, the cross-section of np pair transfer is expected to be enhanced in the presence of important np pairing. np pairing is expected to be important in N=Z nuclei with high J orbitals. Since the development of radioactive beam facilities, such beams are only available. The experiment was performed at GANIL with an efficient set-up so as to detect products from the (p, 3 He) transfer reaction. This reaction is affected by isovector and isoscalar np pairing. We used 56 Ni and 52 Fe beams so as to see the effect of the occupancy of 0f 7/2 shell on the np pairing. First, we analysed the data from the 56 Ni(p,d) 55 Ni reaction and we compared the results with the literature to validate analysis procedure. After analysing data from the 56 Ni(p, 3 He) 54 Co reaction and extracting the population of the various states of 54 Co, we obtained information about the relative intensity between isoscalar and isovector np pairing in 56 Ni showing the predominance of isovector np pairing in this nucleus. Moreover, in the framework of developing a new charged particle detector, research on the discrimination of light nuclei using pulse shape analysis was performed and is also presented. (author)

  18. The proton transfer reaction in malonaldehyde derivatives: Substituent effects and quasi-aromaticity of the proton bridge

    International Nuclear Information System (INIS)

    Palusiak, Marcin; Simon, Silvia; Sola, Miquel

    2007-01-01

    The proton transfer in malonaldehyde and in some of its derivatives have been considered in order to study the interrelation between the reaction barrier and the π-delocalization in the quasi-ring. A set of simple and mostly common substituents having different properties in resonance effect according to values of substituents constants were chosen in order to simulate the influence of substitution in position 2 or in position 1 (or 3) of malonaldehyde on the quasi-aromaticity and H-bonding. The following substituents have been taken into consideration: NO, NO 2 , CN, CHO, F, H, CH 3 , OCH 3 , OH, and NH 2 . Our results show that when the substituent is attached at position 2 of the quasi-ring, the resonance effect predominates over the field/inductive effect which leads to changes in H-bonding and quasi-aromaticity of the ring motif, while in the case of 1(3) substitution the field/inductive effect is significantly more effective influencing the HB strength, and thus, the proton transfer barrier. Somehow counterintuitively, for the 1(3) substituted systems, the most stable isomer is the one having the weakest HB and lower aromaticity. The reason for this surprising behaviour is discussed

  19. Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion.

    Science.gov (United States)

    Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2015-11-21

    Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton

  20. Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

    International Nuclear Information System (INIS)

    Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2015-01-01

    Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton

  1. Analysis for mass distribution of proton-induced reactions in intermediate energy range

    CERN Document Server

    Xiao Yu Heng

    2002-01-01

    The mass and charge distribution of residual products produced in the spallation reactions needs to be studied, because it can provide useful information for the disposal of nuclear waste and residual radioactivity generated by the spallation neutron target system. In present work, the Many State Dynamical Model (MSDM) is based on the Cascade-Exciton Model (CEM). The authors use it to investigate the mass distribution of Nb, Au and Pb proton-induced reactions in energy range from 100 MeV to 3 GeV. The agreement between the MSDM simulations and the measured data is good in this energy range, and deviations mainly show up in the mass range of 90 - 150 for the high energy proton incident upon Au and Pb

  2. CO2 as a C1-organic building block: Enantioselective electrocarboxylation of aromatic ketones with CO2catalyzed by cinchona alkaloids under mild conditions

    International Nuclear Information System (INIS)

    Chen, Bao-Li; Tu, Zhuo-Ying; Zhu, Hong-Wei; Sun, Wen-Wen; Wang, Huan; Lu, Jia-Xing

    2014-01-01

    Highlights: •Cinchona alkaloids catalysis achieve enantioselective electrocarboxylation of racemic aromatic ketones. •The applications of CO 2 enantioselective electrochemical fixation into optically active hydroxyl carboxylic acids have been expanded. •The applications of alkaloids have been expanded. •The applications of asymmetric synthesis by electrochemical methodology have been expanded. -- Abstract: The enantioselective electrocarboxylation of pro-chiral aromatic ketones (2-acetonaphthone, 1-(6-methoxy-2-naphthyl)ethanone, 1-(4-methoxy-1-naphthyl)ethanone) with atmospheric pressure of CO 2 catalyzed by cinchona alkaloids in the presence of phenol was investigated in an undivided cell for the first time to give optically active 2-hydroxy-2-arylpropionic acid. For the model compound 2-acetonaphthone, the influence of various reaction conditions, such as cathode material, current density, catalyst type, ratio of proton to catalyst and catalyst quantity, on the enantiomeric excesses (ee) and yield has been investigated. Under the optimized conditions of 2-acetonaphthone, all the aromatic ketones examined are converted into corresponding optically active 2-hydroxy-2-arylpropionic acids in moderate yield (32.2% - 41.3%) and ee (48.1% - 48.6%). In addition, the electrochemical behavior of 2-acetonaphthone has been studied by cyclic voltammetry (CV) in the absence and presence of CO 2 . Moreover, the probable reaction pathway was proposed accordingly

  3. Proton induced nuclear reactions on natural antimony up to 17 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Elbinawi, Alaa; Al-abyad, Mogahed; Hassan, Khaled F. [Atomic Energy Authority, Cairo (Egypt). Cyclotron Facility; Abd-Elmageed, Karima E. [Benha Univ. (Egypt). Dept. of Physics; Ditroi, Ferenc [Hungarian Academy of Sciences, Debrecen (Hungary). Inst. for Nuclear Research (ATOMKI)

    2016-08-01

    The activation cross sections of proton induced reactions on {sup nat}Sb target leading to the formation of the radioisotopes {sup 121m,g,123m}Te were measured. The experimental excitation functions were compared with the theoretical model calculations using the codes EMPIRE-3.1 and TALYS-1.4. The integral yields of the three radionuclides were calculated and the possibility of their production is discussed.

  4. Experimental cross-sections for proton-induced nuclear reactions on Mo-nat

    Czech Academy of Sciences Publication Activity Database

    Červenák, Jaroslav; Lebeda, Ondřej

    2016-01-01

    Roč. 380, AUG (2016), s. 32-49 ISSN 0168-583X R&D Projects: GA MŠk(CZ) LM2011019 Institutional support: RVO:61389005 Keywords : cross-sections * excitation functions * proton-induced nuclear reactions * natural molybdenum * Mo-99 * Tc-99m * Tc96m+g * Tc-95m * thick target yields * U-120M cyclotron Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 1.109, year: 2016

  5. Gamma-ray emission cross section from proton-incident spallation reaction

    International Nuclear Information System (INIS)

    Iga, Kiminori; Ishibashi, Kenji; Shigyo, Nobuhiro

    1996-01-01

    Gamma-ray emission double differential cross sections from proton-incident spallation reaction have been measured at incident energies of 0.8, 1.5 and 3.0 GeV with Al, Fe, In and Pb targets. The experimental results have been compared with calculate values of HETC-KFA2. The measured cross sections disagree with the calculated results in the gamma ray energies above 10 MeV. (author)

  6. Study of the reaction. gamma. p. --> delta. /sup + +/. pi. /sup -/ on polarized protons

    Energy Technology Data Exchange (ETDEWEB)

    Belyaev, A.; Get' man, V.; Gorbenko, V.; Gushchin, V.; Derkach, A.; Zhebrovskii, Y.; Zayats, A.; Karnaukhov, I.; Kolesnikov, L.; Lukhanin, A.; Rubashkin, A.; Sobol' , M.; Sorokin, P.; Sporov, E.; Telegin, Y.

    1982-02-01

    We have measured for the first time the asymmetry of the cross section for the reaction ..gamma..p..--> delta../sup + +/..pi../sup -/ on polarized protons. The measurements were made at E/sub ..gamma../ = 660 MeV in the range of pion emission angles 45--120/sup 0/ c.m.s. The experimental data obtained are compared with the theoretical predictions.

  7. Stereochemistry of 1,2-elimination and proton-transfer reactions: toward a unified understanding.

    Science.gov (United States)

    Mohrig, Jerry R

    2013-07-16

    Many mechanistic and stereochemical studies have focused on the breaking of the C-H bond through base-catalyzed elimination reactions. When we began our research, however, chemists knew almost nothing about the stereospecificity of addition-elimination reactions involving conjugated acyclic carbonyl compounds, even though the carbonyl group is a pivotal functional group in organic chemistry. Over the last 25 years, we have studied the addition-elimination reactions of β-substituted acyclic esters, thioesters, and ketones in order to reach a comprehensive understanding of how electronic effects influence their stereochemistry. This Account brings together our understanding of the stereochemistry of 1,2-elimination and proton-transfer reactions, describing how each study has built upon previous work and contributed to our understanding of this field. When we began, chemists thought that anti stereospecificity in base-catalyzed 1,2-elimination reactions occurred via concerted E2 mechanisms, which provide a smooth path for anti elimination. Unexpectedly, we discovered that some E1cBirrev reactions produce the same anti stereospecificity as E2 reactions even though they proceed through diffusionally equilibrated, "free" enolate-anion intermediates. This result calls into question the conventional wisdom that anti stereochemistry must result from a concerted mechanism. While carrying out our research, we developed insights ranging from the role of historical contingency in the evolution of hydratase-dehydratase enzymes to the influence of buffers on the stereochemistry of H/D exchange in D2O. Negative hyperconjugation is the most important concept for understanding our results. This idea provides a unifying view for the largely anti stereochemistry in E1cBirrev elimination reactions and a basis for understanding the stereoelectronic influence of electron-withdrawing β-substituents on proton-transfer reactions.

  8. Proton propagation through nuclei and the quasi-free reaction mechanism studied with (e,e'p) reactions

    International Nuclear Information System (INIS)

    Dutta, D.; Abbott, D.; Amatuni, T.A.

    1997-01-01

    Jefferson Lab experiment E91-013 measured the energy dependence of proton propagation in nuclei, using the quasi-free (e, e'p) reaction. The ratios of the experimental (e, e'p) cross-sections integrated over the quasi-free region to PWIA calculations are presented as a function of momentum transfer, (0.6 2 2 ) and target nucleus (C, Fe and Au). As a first step towards a longitudinal and transverse separation of the quasi-free cross-section, a super ratio of the measured to the calculated cross-sections at forward and backward angles is presented

  9. An experimental study of odd mass promethium isotopes using proton stripping and pickup reactions

    International Nuclear Information System (INIS)

    Straume, O.

    1979-11-01

    Odd Pm isotopes have been studied by one proton pick-up and stripping reactions. Spin assignment and spectroscopic factors have been obtained for a number of energy levels. In the stripping reactions, the relative cross-sections have been measured with an unusually high precision by the use of a target of natural neodymium. The spectroscopic strengths have been extracted using standard distorted wave methods. The nuclear structures of these promethium isotopes fall into three categories. The spherical approach seems valid for 143 Pm and 145 Pm and the deformed regime covers 151 Pm and 153 Pm, while 147 Pm and 149 Pm remain as transitional nuclei. (Auth.)

  10. Field theoretical approach to proton-nucleus reactions. I - One step inelastic scattering

    International Nuclear Information System (INIS)

    Eiras, A.; Kodama, T.; Nemes, M.C.

    1988-01-01

    In this work we obtain a closed form expression to the double differential cross section for one step proton-nucleus reaction within a field theoretical framework. Energy and momentum conservation as well as nuclear structure effects are consistently taken into account within the field theoretical eikonal approximation. In our formulation the kinematics of such reaction is not dominated by the free nucleon-nucleon cross section but a new factor which we call relativistic differential cross section in a Born Approximation. (author) [pt

  11. p-process nucleosynthesis via proton-capture reactions in thermonuclear supernovae explosions

    Directory of Open Access Journals (Sweden)

    Endres Anne

    2015-01-01

    Full Text Available Model calculations within the framework of the so-called γ process show an underproduction of the p nucleus with the highest isotopic abundace 92Mo. This discrepancy can be narrowed by taking into account the alternative production site of a type Ia supernova explosion. Here, the nucleus 92Mo can be produced by a sequence of proton-capture reactions. The amount of 92Mo nuclei produced via this reaction chain is most sensitive to the reactions 90Zr(p,γ and 91Nb(p,γ. Both rates have to be investigated experimentally to study the impact of this nucleosynthesis aspect on the long-standing 92Mo-problem. We have already measured the proton-capture reaction on 90Zr using high-resolution in-beam γ-ray spectroscopy. In this contribution, we will present our preliminary results of the total cross sections as well as the partial cross sections. Furthermore, we plan to measure the 91Nb(p,γ reaction soon. Due to the radioactive target material, the 91Nb nuclei have to be produced prior to the experiment. The current status of this production will be presented in this contribution.

  12. Theoretical modeling of yields for proton-induced reactions on natural and enriched molybdenum targets.

    Science.gov (United States)

    Celler, A; Hou, X; Bénard, F; Ruth, T

    2011-09-07

    Recent acute shortage of medical radioisotopes prompted investigations into alternative methods of production and the use of a cyclotron and ¹⁰⁰Mo(p,2n)(99m)Tc reaction has been considered. In this context, the production yields of (99m)Tc and various other radioactive and stable isotopes which will be created in the process have to be investigated, as these may affect the diagnostic outcome and radiation dosimetry in human studies. Reaction conditions (beam and target characteristics, and irradiation and cooling times) need to be optimized in order to maximize the amount of (99m)Tc and minimize impurities. Although ultimately careful experimental verification of these conditions must be performed, theoretical calculations can provide the initial guidance allowing for extensive investigations at little cost. We report the results of theoretically determined reaction yields for (99m)Tc and other radioactive isotopes created when natural and enriched molybdenum targets are irradiated by protons. The cross-section calculations were performed using a computer program EMPIRE for the proton energy range 6-30 MeV. A computer graphical user interface for automatic calculation of production yields taking into account various reaction channels leading to the same final product has been created. The proposed approach allows us to theoretically estimate the amount of (99m)Tc and its ratio relative to (99g)Tc and other radioisotopes which must be considered reaction contaminants, potentially contributing to additional patient dose in diagnostic studies.

  13. Reaction cross sections for 8He and 14B on proton target for the separation of proton and neutron density distributions

    International Nuclear Information System (INIS)

    Tanaka, Masaomi; Fukuda, Mitsunori; Nishimura, Daiki

    2015-01-01

    We utilized the proton-neutron asymmetry of nucleon–nucleon total cross sections in the intermediate energy region (σ pn ≠σ pp(nn) ) to obtain the information of proton and neutron distributions respectively. We have measured reaction cross sections (σ R ) for 14 B and 8 He on proton targets as isospin asymmetric targets in addition to symmetric ones. Proton and neutron density distributions were derived respectively through the χ 2 -fitting procedure with the modified Glauber calculation. The result suggests a necessity for 14 B of a long tail, and also a necessity for 8 He of a neutron tail. Root-mean-square proton, neutron and matter radii for 14 B and 8 He are also derived. Each radius is consistent with some of the other experimental values and also with some of the several theoretical values. (author)

  14. 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...

  15. 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

  16. Presolvated Electron Reaction with Methylacetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-atom Abstraction

    Science.gov (United States)

    Petrovici, Alex; Adhikary, Amitava; Kumar, Anil; Sevilla, Michael D.

    2015-01-01

    Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methylacetoacetate (MAA, CH3-CO-CH2-CO-OCH3) at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-CO-OCH3) in the temperature range (77 to ca. 170 K) have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR) spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•)OH-CH2-CO-OCH3. The ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylen protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K), CH3-C(•)OH-CH2-CO-OCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-CO-OCH3. Theoretical calculations using density functional theory (DFT) support the radical assignments. PMID:25255751

  17. Inclusive proton spectra and total reaction cross sections for proton-nucleus scattering at 800 MeV

    International Nuclear Information System (INIS)

    McGill, J.A.

    1981-08-01

    Current applications of multiple scattering theory to describe the elastic scattering of medium energy protons from nuclei have been shown to be quite successful in reproducing the experimental cross sections. These calculations use the impulse approximation, wherein the scattering from individual nucleons in the nucleus is described by the scattering amplitude for a free nucleon. Such an approximation restricts the inelastic channels to those initiated by nucleon-nucleon scattering. As a first step in determining the nature of p + nucleus scattering at 800 MeV, both total reaction cross sections and (p,p') inclusive cross sections were measured and compared to the free p + p cross sections for hydrogen, deuterium, calcium 40, carbon 12, and lead 208. It is concluded that as much as 85% of all reactions in a nucleus proceed from interactions with a single nucleon in the nucleus, and that the impulse approximation is a good starting point for a microscopic description of p + nucleus interactions at 800 MeV

  18. 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%)

  19. Cross sections and thermonuclear reaction rates of proton-induced reactions on 37Cl

    International Nuclear Information System (INIS)

    Weber, R.O.; Tingwell, C.I.W.; Mitchell, L.W.; Sevior, M.E.; Sargood, D.G.

    1984-01-01

    The yields of γ-rays from the reactions of 37 Cl(p,γ) 38 Ar and 37 Cl(p,αγ) 34 S have been measured as a of bombarding energy over the ranges 0.65 - 2.15 MeV and 1.25 -2.15 MeV respectively, and the yield of neutrons from 37 Cl(p,n) 37 Ar from threshold to 2.50 MeV. The results are compared with global statistical-model calculations and thermonuclear reaction rates are calculated for the temperature range 5 x 10 8 - 10 10 K. The significance of these thermonuclear reaction rates for stellar nucleosynthesis calculations is discussed

  20. 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.

  1. Production of proton-rich nuclei around Z = 84-90 in fusion-evaporation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Peng-Hui [Chinese Academy of Sciences, Institute of Modern Physics, Lanzhou (China); Lanzhou University, School of Nuclear Science and Technology, Lanzhou (China); University of Chinese Academy of Sciences, Beijing (China); Feng, Zhao-Qing; Li, Jun-Qing; Jin, Gen-Ming [Chinese Academy of Sciences, Institute of Modern Physics, Lanzhou (China); Niu, Fei [Chinese Academy of Sciences, Institute of Modern Physics, Lanzhou (China); Henan Normal University, Institute of Particle and Nuclear Physics, Xinxiang (China); Guo, Ya-Fei [Chinese Academy of Sciences, Institute of Modern Physics, Lanzhou (China); Lanzhou University, School of Nuclear Science and Technology, Lanzhou (China); Zhang, Hong-Fei [Lanzhou University, School of Nuclear Science and Technology, Lanzhou (China)

    2017-05-15

    Within the framework of the dinuclear system model, production cross sections of proton-rich nuclei with charged numbers of Z = 84-90 are investigated systematically. Possible combinations with the {sup 28}Si, {sup 32}S, {sup 40}Ar bombarding the target nuclides {sup 165}Ho, {sup 169}Tm, {sup 170-174}Yb, {sup 175,176}Lu, {sup 174,} {sup 176-180}Hf and {sup 181}Ta are analyzed thoroughly. The optimal excitation energies and evaporation channels are proposed to produce the proton-rich nuclei. The systems are feasible to be constructed in experiments. It is found that the neutron shell closure of N = 126 is of importance during the evaporation of neutrons. The experimental excitation functions in the {sup 40}Ar induced reactions can be nicely reproduced. The charged particle evaporation is comparable with neutrons in cooling the excited proton-rich nuclei, in particular for the channels with α and proton evaporation. The production cross section increases with the mass asymmetry of colliding systems because of the decrease of the inner fusion barrier. The channels with pure neutron evaporation depend on the isotopic targets. But it is different for the channels with charged particles and more sensitive to the odd-even effect. (orig.)

  2. 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.

  3. Hydroxynitrile Lyases with α/β-Hydrolase Fold: Two Enzymes with Almost Identical 3D Structures but Opposite Enantioselectivities and Different Reaction Mechanisms

    Science.gov (United States)

    Andexer, Jennifer N; Staunig, Nicole; Eggert, Thorsten; Kratky, Christoph; Pohl, Martina; Gruber, Karl

    2012-01-01

    Hydroxynitrile lyases (HNLs) catalyze the cleavage of cyanohydrins to yield hydrocyanic acid (HCN) and the respective carbonyl compound and are key enzymes in the process of cyanogenesis in plants. In organic syntheses, HNLs are used as biocatalysts for the formation of enantiopure cyanohydrins. We determined the structure of the recently identified, R-selective HNL from Arabidopsis thaliana (AtHNL) at a crystallographic resolution of 2.5 Å. The structure exhibits an α/β-hydrolase fold, very similar to the homologous, but S-selective, HNL from Hevea brasiliensis (HbHNL). The similarities also extend to the active sites of these enzymes, with a Ser-His-Asp catalytic triad present in all three cases. In order to elucidate the mode of substrate binding and to understand the unexpected opposite enantioselectivity of AtHNL, complexes of the enzyme with both (R)- and (S)-mandelonitrile were modeled using molecular docking simulations. Compared to the complex of HbHNL with (S)-mandelonitrile, the calculations produced an approximate mirror image binding mode of the substrate with the phenyl rings located at very similar positions, but with the cyano groups pointing in opposite directions. A catalytic mechanism for AtHNL is proposed, in which His236 from the catalytic triad acts as a general base and the emerging negative charge on the cyano group is stabilized by main-chain amide groups and an α-helix dipole very similar to α/β-hydrolases. This mechanistic proposal is additionally supported by mutagenesis studies. PMID:22851196

  4. Dynamics of the F(-) + CH3I → HF + CH2I(-) Proton Transfer Reaction.

    Science.gov (United States)

    Zhang, Jiaxu; Xie, Jing; Hase, William L

    2015-12-17

    Direct chemical dynamics simulations, at collision energies Erel of 0.32 and 1.53 eV, were performed to obtain an atomistic understanding of the F(-) + CH3I reaction dynamics. There is only the F(-) + CH3I → CH3F + I(-) bimolecular nucleophilic substitution SN2 product channel at 0.32 eV. Increasing Erel to 1.53 eV opens the endothermic F(-) + CH3I → HF + CH2I(-) proton transfer reaction, which is less competitive than the SN2 reaction. The simulations reveal proton transfer occurs by two direct atomic-level mechanisms, rebound and stripping, and indirect mechanisms, involving formation of the F(-)···HCH2I complex and the roundabout. For the indirect trajectories all of the CH2I(-) is formed with zero-point energy (ZPE), while for the direct trajectories 50% form CH2I(-) without ZPE. Without a ZPE constraint for CH2I(-), the reaction cross sections for the rebound, stripping, and indirect mechanisms are 0.2 ± 0.1, 1.2 ± 0.4, and 0.7 ± 0.2 Å(2), respectively. Discarding trajectories that do not form CH2I(-) with ZPE reduces the rebound and stripping cross sections to 0.1 ± 0.1 and 0.7 ± 0.5 Å(2). The HF product is formed rotationally and vibrationally unexcited. The average value of J is 2.6 and with histogram binning n = 0. CH2I(-) is formed rotationally excited. The partitioning between CH2I(-) vibration and HF + CH2I(-) relative translation energy depends on the treatment of CH2I(-) ZPE. Without a CH2I(-) ZPE constraint the energy partitioning is primarily to relative translation with little CH2I(-) vibration. With a ZPE constraint, energy partitioning to CH2I(-) rotation, CH2I(-) vibration, and relative translation are statistically the same. The overall F(-) + CH3I rate constant at Erel of both 0.32 and 1.53 eV is in good agreement with experiment and negligibly affected by the treatment of CH2I(-) ZPE, since the SN2 reaction is the major contributor to the total reaction rate constant. The potential energy surface and reaction dynamics for F

  5. Excitation functions of radionuclides produced by proton induced reactions on gadolinium targets

    International Nuclear Information System (INIS)

    Challana, M.B.; Comsana, M.N.H.; Moawadb, G.S.; Abou-Zeid, M.A.

    2008-01-01

    Cross section study for proton induced reaction on natural Gadolinium targets were performed. Excitation functions for the reactions n atGd(p,x) 152m+g , 154m,154g Tb from threshold up to E p = 18 MeV have been measured employing the stacked foil activation technique, and using high resolution HPGe gamma spectrometry. Utilizing the simultaneous measurement of the excitation function of n atCu(p,x) 62 Zn, n atCu(p,x) 63 Zn, and n atCu(p,x) 65 Zn as monitor reactions. The theoretical analysis of the excitation functions has been done employing both ALICE-91 and EMPIRE-II codes. In general, theoretical calculations agree well with the experimental data. A significant contribution of pre-equilibrium component has been observed at these energies

  6. Theoretical study of cross sections of proton-induced reactions on cobalt

    Directory of Open Access Journals (Sweden)

    Mustafa Yiğit

    2018-04-01

    Full Text Available Nuclear fusion may be among the strongest sustainable ways to replace fossil fuels because it does not contribute to acid rain or global warming. In this context, activated cobalt materials in corrosion products for fusion energy are significant in determination of dose levels during maintenance after a coolant leak in a nuclear fusion reactor. Therefore, cross-section studies on cobalt material are very important for fusion reactor design. In this article, the excitation functions of some nuclear reaction channels induced by proton particles on 59Co structural material were predicted using different models. The nuclear level densities were calculated using different choices of available level density models in ALICE/ASH code. Finally, the newly calculated cross sections for the investigated nuclear reactions are compared with the experimental values and TENDL data based on TALYS nuclear code. Keywords: Cobalt, Nuclear Structural Materials, Reaction Cross Section, TENDL Database

  7. Exclusive measurements of quasi-free proton scattering reactions in inverse and complete kinematics

    Directory of Open Access Journals (Sweden)

    V. Panin

    2016-02-01

    Full Text Available Quasi-free scattering reactions of the type (p,2p were measured for the first time exclusively in complete and inverse kinematics, using a 12C beam at an energy of ∼400 MeV/u as a benchmark. This new technique has been developed to study the single-particle structure of exotic nuclei in experiments with radioactive-ion beams. The outgoing pair of protons and the fragments were measured simultaneously, enabling an unambiguous identification of the reaction channels and a redundant measurement of the kinematic observables. Both valence and deeply-bound nucleon orbits are probed, including those leading to unbound states of the daughter nucleus. Exclusive (p,2p cross sections of 15.8(18 mb, 1.9(2 mb and 1.5(2 mb to the low-lying 0p-hole states overlapping with the ground state (3/2− and with the bound excited states of 11B at 2.125 MeV (1/2− and 5.02 MeV (3/2−, respectively, were determined via γ-ray spectroscopy. Particle-unstable deep-hole states, corresponding to proton removal from the 0s-orbital, were studied via the invariant-mass technique. Cross sections and momentum distributions were extracted and compared to theoretical calculations employing the eikonal formalism. The obtained results are in a good agreement with this theory and with direct-kinematics experiments. The dependence of the proton–proton scattering kinematics on the internal momentum of the struck proton and on its separation energy was investigated for the first time in inverse kinematics employing a large-acceptance measurement.

  8. From the HINDAS Project: Excitation Functions for Residual Nuclide Production by Proton-Induced Reactions

    International Nuclear Information System (INIS)

    Michel, R.; Gloris, M.; Protoschill, J.; Uosif, M.A.M.; Weug, M.; Herpers, U.; Kuhnhenn, J.; Kubik, P.-W.; Schumann, D.; Synal, H.-A.; Weinreich, R.; Leya, I.; David, J.C.; Leray, S.; Duijvestijn, M.; Koning, A.; Kelic, A.; Schmidt, K.H.; Cugnon, J.

    2005-01-01

    A survey is given about efforts undertaken during the HINDAS project to investigate the energy dependence of residual nuclide production by proton-induced reactions from thresholds up to 2.6 GeV. For proton-induced reactions, our experiments aimed to further develop and complete the cross-section database that was established by our collaboration in recent years. It was extended to the heavy-target elements Ta, W, Pb, and Bi for energies up to 2.6 GeV. In addition, new measurements for the target element iron were performed up to 2.6 GeV and for natural uranium for energies from 21 MeV to 69 MeV. For the target element lead, a comprehensive set of excitation functions published recently was completed by AMS-measurements of cross sections for the production of the long-lived radionuclides Be-10, Al-26, Cl-36, and I-129 and by mass spectrometric measurements for stable and radioactive rare gas isotopes of He, Ne, Ar, Kr, and Xe. Comprehensive tests of the nuclear-reaction codes TALYS and INCL4+ABLA, which were developed within the HINDAS project, were performed with the new experimental results over the entire energy range

  9. Property investigations of proton-proton reaction in dependence of the transverse momentum of a single particle for a beam momentum of 24 GeV/c

    International Nuclear Information System (INIS)

    Geist, W.M.

    1976-01-01

    This study is based on data produced in an experiment for the investigation of proton-proton reactions at a beam momentum of 24 GeV/c. In particular, the dependence of final state properties on the transverse momentum of a chosen secondary particle (trigger particle) is considered. The study has four parts: First, experimental procedures of selection, cleaning and correction of the data are developed and applied for exclusive and inclusive reactions. Then the description of a model with minimum correlation between two particles is given. In the third section, the mean charged multiplicities of inclusive reactions are measured and interpreted as a function of the transverse momentum of the trigger particle. A complete event structure for quasi-inclusive reactions is given in the last section. Much emphasis is placed on the investigation of events comprising the production of a particle with high transverse momentum (more than 1 GeV/c). (orig./WL) [de

  10. Calculation of proton and neutron emission spectra from proton reactions with 90Zr and 208Pb to 160 MeV with the GNASH code

    International Nuclear Information System (INIS)

    Young, P.G.; Chadwick, M.B.

    1994-01-01

    A number of modifications have been made to the reaction theory code GNASH in order the accuracy of calculations at incident particle energies up to 200 MeV. Direct reaction a level density models appropriate for higher energy calculations are now used in the code, and most importantly, improved preequilibrium models have been incorporated into the code system. The code has been used to calculate proton-induced reactions on 90 Zr and 208 Pb for the International Code and Model Intercomparison for Intermediate Energy Reactions organized by the NEA. Calculations were performed with GNASH at incident proton energies of 25, 45, 80, and 160 mev using both the exciton model and Feshbach-Kerman-Koonin theory for the preequilibrium component. The models and procedures used in the GNASH calculations with the exciton model are described here. The results are compared to experimental data and to results from the GNASH calculations with Feshbach-Kerman-Koonin preequilibrium theory

  11. Remeasurement and compilation of excitation function of proton induced reactions on iron for activation techniques

    International Nuclear Information System (INIS)

    Takacs, S.; Vasvary, L.; Tarkanyi, F.

    1994-01-01

    Excitation functions of proton induced reactions on nat Fe(p, xn) 56 Co have been remeasured in the energy region up to 18 MeV using stacked foil technique and standard high resolution gamma-ray spectrometry at the Debrecen MGC-20E cyclotron. Compilation of the available data measured between 1959 and 1993 has been made. The corresponding excitation functions have been reviewed, critical comparison of all the available data was done to obtain the most accurate data set. The feasibility of the evaluated data set was checked by reproducing experimental calibration curves for TLA by calculation. (orig.)

  12. Proton induced nuclear reactions on cadmium up 17 MeV

    International Nuclear Information System (INIS)

    Al-Abyad, M.

    2012-01-01

    The cross-sections of proton induced reactions on nat Cd targets was studied in the energy range from threshold up to 17 MeV, using a stacked-foil irradiation technique and classical gamma-spectroscopy. We measured the formation cross-sections of the radioisotopes 109g,110m,110,111g,113m,114m,115m,116m In The obtained excitation functions were compared with the earlier published data and the theoretical model calculations by the codes ALICE-IPPE, EMPIRE and TALYS .

  13. Proton conduction within the reaction centers of Rhodobacter capsulatus: the electrostatic role of the protein.

    OpenAIRE

    Maróti, P; Hanson, D K; Baciou, L; Schiffer, M; Sebban, P

    1994-01-01

    Light-induced charge separation in the photosynthetic reaction center results in delivery of two electrons and two protons to the terminal quinone acceptor QB. In this paper, we have used flash-induced absorbance spectroscopy to study three strains that share identical amino acid sequences in the QB binding site, all of which lack the protonatable amino acids Glu-L212 and Asp-L213. These strains are the photosynthetically incompetent site-specific mutant Glu-L212/Asp-L213-->Ala-L212/Ala-L213 ...

  14. Theoretical modeling of yields for proton-induced reactions on natural and enriched molybdenum targets

    Energy Technology Data Exchange (ETDEWEB)

    Celler, A; Hou, X [University of British Columbia, Vancouver, BC, Canada, (Canada); Benard, F; Ruth, T, E-mail: aceller@physics.ubc.ca, E-mail: xinchi@phas.ubc.ca, E-mail: fbenard@bccrc.ca, E-mail: truth@triumf.ca [BC Cancer Agency, Vancouver, BC (Canada)

    2011-09-07

    Recent acute shortage of medical radioisotopes prompted investigations into alternative methods of production and the use of a cyclotron and {sup 100}Mo(p,2n){sup 99m}Tc reaction has been considered. In this context, the production yields of {sup 99m}Tc and various other radioactive and stable isotopes which will be created in the process have to be investigated, as these may affect the diagnostic outcome and radiation dosimetry in human studies. Reaction conditions (beam and target characteristics, and irradiation and cooling times) need to be optimized in order to maximize the amount of {sup 99m}Tc and minimize impurities. Although ultimately careful experimental verification of these conditions must be performed, theoretical calculations can provide the initial guidance allowing for extensive investigations at little cost. We report the results of theoretically determined reaction yields for {sup 99m}Tc and other radioactive isotopes created when natural and enriched molybdenum targets are irradiated by protons. The cross-section calculations were performed using a computer program EMPIRE for the proton energy range 6-30 MeV. A computer graphical user interface for automatic calculation of production yields taking into account various reaction channels leading to the same final product has been created. The proposed approach allows us to theoretically estimate the amount of {sup 99m}Tc and its ratio relative to {sup 99g}Tc and other radioisotopes which must be considered reaction contaminants, potentially contributing to additional patient dose in diagnostic studies.

  15. 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.

  16. Estimates of the astrophysical S-factors for proton radiative capture by 10B and 24Mg nuclei using the ANCs from proton transfer reactions

    International Nuclear Information System (INIS)

    Artemov, S.V.; Igamov, S.B.; Karakhodzhaev, A.A.; Nie, G.K.; Yarmukhamedov, R.; Zaparov, E.A.; Burtebaev, N.; Rehm, K.E.

    2010-01-01

    The contribution of the direct radiative capture of protons by 10 B and 24 Mg nuclei at low energies to the astrophysical S-factors in the reactions 10 B(p,γ) 11 C and 24 Mg(p,γ) 25 Al have been calculated within the R-matrix formalism by using empirical proton asymptotical normalization coefficients (ANC). The ANCs for bound proton configurations { 10 B+p} and { 24 Mg+p} were obtained from the analysis of the reactions ( 3 He, d). The ANCs were also estimated from the values of the neutron ANCs in the mirror nucleus 25 Mg following the suggestion that the neutron and the proton in the mirror states have equivalent nuclear potentials. It has been found that the S-factor for the reaction 10 B(p,γ) 11 C extrapolated to zero energy contributes ~100 keV b to the radiative capture to the ground state of 11 C. For the reaction 24 Mg(p,γ) 25 Al the value S(0) gives 58 keV b with a direct capture contribution of 41 keV b. (author)

  17. The investigation of quasi-free scattering reactions with the two-proton-halo nucleus {sup 17}Ne

    Energy Technology Data Exchange (ETDEWEB)

    Lehr, Christopher; Aumann, Thomas; Marganiec, Justyna [TU Darmstadt (Germany); Wamers, Felix [GSI Helmholtzzentrum (Germany)

    2016-07-01

    {sup 17}Ne is a Borromean two-proton-halo nucleus located at the proton-dripline and therefore an interesting candidate for nuclear-structure studies. Reactions of the nucleus {sup 17}Ne have been measured in complete kinematics at the R3B/LAND setup at GSI in Darmstadt. It was studied in exclusive measurements of one-proton-removal reactions. Polyethylene (CH{sub 2}) and carbon (C) were used as targets. Thus it is possible to reconstruct the pure H contribution of the CH{sub 2} data by subtracting the carbon background. The resulting events are clean (p,2p) reactions showing the typical angular correlations known from p-p scattering. Thereby quasi-free (p,2p) and carbon-induced one-proton removal reactions are studied separately. Quasi-free scattering reactions are compared with carbon-induced one-proton removal reactions and shown to be a clean tool for nuclear-structure studies.

  18. Cross section measurements of proton capture reactions on Se isotopes relevant to the astrophysical p process

    Science.gov (United States)

    Foteinou, V.; Harissopulos, S.; Axiotis, M.; Lagoyannis, A.; Provatas, G.; Spyrou, A.; Perdikakis, G.; Zarkadas, Ch.; Demetriou, P.

    2018-03-01

    Cross sections of proton capture reactions on 74Se, 78Se, and 80Se have been measured at incident beam energies from 2 to 6 MeV, 1.7 to 3 MeV, and 1.5 to 3.5 MeV, respectively. In the case of Se,8078, cross sections were obtained from in-beam γ -angular distribution measurements, whereas for the 74Se isotope they were derived from off-beam activity measurements. The measured cross sections were compared with calculations performed with the nuclear reaction code talys (version 1.6). A good agreement between theory and experiment was found. Astrophysical S factors and reaction rates deduced from the experimental and calculated cross sections were also compared and the impact of different nuclear ingredients in the calculations on the reaction rates was investigated. It was found that, for certain combinations of nuclear input models, the reaction rates obtained at temperatures relevant to p -process nucleosynthesis differ by a factor 2 at the most, differences that are well within the acceptable deviations of calculated p -nuclei abundances and observations.

  19. Two-proton pickup studies with the (6Li,8B) reaction

    Energy Technology Data Exchange (ETDEWEB)

    Weisenmiller, R.B.

    1976-12-03

    The (/sup 6/Li,/sup 8/B) reaction has been investigated on targets of /sup 26/Mg, /sup 24/Mg, /sup 16/O, /sup 13/C, /sup 12/C, /sup 11/B, /sup 10/B, and /sup 9/Be at a bombarding energy of 80.0 MeV, and on targets of /sup 16/O, /sup 12/C, /sup 9/Be, /sup 7/Li, and /sup 6/Li at a bombarding energy of 93.3 MeV. Only levels consistent with direct, single-step two-proton pickup reaction mechanisms were observed to be strongly populated. On T/sub z/ = 0 targets, the spectroscopic selectivity of this reaction resembles that of the analogous (p,t) reaction. Additionally, these data demonstrate the dominance of spatially symmetric transfer of the two protons. On T/sub z/ greater than 0 targets the (/sup 6/Li,/sup 8/B) reaction was employed to locate two previously unreported levels (at 7.47 +- 0.05 MeV and 8.86 +- 0.07 MeV) in the T/sub z/ = 2 nuclide /sup 24/Ne and to establish the low-lying 1p-shell states in the T/sub z/ = /sup 3///sub 2/ nuclei /sup 11/Be, /sup 9/Li, and /sup 7/He. However, no evidence was seen for any narrow levels in the T/sub z/ = /sup 3///sub 2/ nuclide /sup 5/H nor for any narrow excited states in /sup 7/He. The angular distributions reported here are rather featureless and decrease monotonically with increasing angle. This behavior can be shown by a semi-classical reaction theory to be a consequence of the reaction kinematics. A semi-classical approach also suggests that the kinematic term in the transition matrix element is only weakly dependent upon the angular momentum transfer (which is consistent with simple Distorted Wave Born Approximation calculations). However, only qualitative agreement was obtained between the observed relative transition yields and semi-classical predictions, using the two-nucleon coefficients of fractional parentage of Cohen and Kurath, probably due to the limitations of the semi-classical reaction theory.

  20. Two-proton pickup studies with the (6Li,8B) reaction

    International Nuclear Information System (INIS)

    Weisenmiller, R.B.

    1976-01-01

    The ( 6 Li, 8 B) reaction has been investigated on targets of 26 Mg, 24 Mg, 16 O, 13 C, 12 C, 11 B, 10 B, and 9 Be at a bombarding energy of 80.0 MeV, and on targets of 16 O, 12 C, 9 Be, 7 Li, and 6 Li at a bombarding energy of 93.3 MeV. Only levels consistent with direct, single-step two-proton pickup reaction mechanisms were observed to be strongly populated. On T/sub z/ = 0 targets, the spectroscopic selectivity of this reaction resembles that of the analogous (p,t) reaction. Additionally, these data demonstrate the dominance of spatially symmetric transfer of the two protons. On T/sub z/ greater than 0 targets the ( 6 Li, 8 B) reaction was employed to locate two previously unreported levels (at 7.47 +- 0.05 MeV and 8.86 +- 0.07 MeV) in the T/sub z/ = 2 nuclide 24 Ne and to establish the low-lying 1p-shell states in the T/sub z/ = 3 / 2 nuclei 11 Be, 9 Li, and 7 He. However, no evidence was seen for any narrow levels in the T/sub z/ = 3 / 2 nuclide 5 H nor for any narrow excited states in 7 He. The angular distributions reported here are rather featureless and decrease monotonically with increasing angle. This behavior can be shown by a semi-classical reaction theory to be a consequence of the reaction kinematics. A semi-classical approach also suggests that the kinematic term in the transition matrix element is only weakly dependent upon the angular momentum transfer (which is consistent with simple Distorted Wave Born Approximation calculations). However, only qualitative agreement was obtained between the observed relative transition yields and semi-classical predictions, using the two-nucleon coefficients of fractional parentage of Cohen and Kurath, probably due to the limitations of the semi-classical reaction theory

  1. Experimental studies on excitation functions of the proton-induced activation reactions on silver

    International Nuclear Information System (INIS)

    Uddin, M.S.; Hagiwara, M.; Baba, M.; Tarkanyi, F.; Ditroi, F.

    2005-01-01

    Excitation functions were measured for the production of 106m,105 Ag, 103,101,100 Pd, 105,102,101m,100,99 Rh and 97 Ru via proton-induced activation reactions on natural silver using a stacked foil technique in the energy range 11-80 MeV. The residual activity measurements were carried out nondestructively by the high-resolution HPGe γ-ray spectroscopy. Thick target integral yields were deduced using the measured cross-sections from the respective threshold energies of the investigated reactions up to 80 MeV. The present work gives new results for the investigated radionuclides. The data in MENDL-2P deduced with the theoretical model code ALICE-IPPE are consistent in shape with the measured values, but show disagreement in magnitude

  2. Effect of free-particle collisions in high energy proton and pion-induced nuclear reactions

    International Nuclear Information System (INIS)

    Jacob, N.P. Jr.

    1975-07-01

    The effect of free-particle collisions in simple ''knockout'' reactions of the form (a,aN) and in more complex nuclear reactions of the form (a,X) was investigated by using protons and pions. Cross sections for the 48 Ti(p,2p) 47 Sc and the 74 Ge(p,2p) 73 Ga reactions were measured from 0.3 to 4.6 GeV incident energy. The results indicate a rise in (p,2p) cross section for each reaction of about (25 +- 3) percent between the energies 0.3 and 1.0 GeV, and are correlated to a large increase in the total free-particle pp scattering cross sections over the same energy region. Results are compared to previous (p,2p) excitation functions in the GeV energy region and to (p,2p) cross section calculations based on a Monte Carlo intranuclear cascade-evaporation model. Cross section measurements for (π/sup +-/, πN) and other more complex pion-induced spallation reactions were measured for the light target nuclei 14 N, 16 O, and 19 F from 45 to 550 MeV incident pion energy. These measurements indicate a broad peak in the excitation functions for both (π,πN) and (π,X) reactions near 180 MeV incident energy. This corresponds to the large resonances observed in the free-particle π + p and π - p cross sections at the same energy. Striking differences in (π,πN) cross section magnitudes are observed among the light nuclei targets. The experimental cross section ratio sigma(π - ,π - n)/sigma(π + ,πN) at 180 MeV is 1.7 +- 0.2 for all three targets. The experimental results are compared to previous pion and analogous proton-induced reactions, to Monte Carlo intranuclear cascade-evaporation calculations, and to a semi-classical nucleon charge exchange model. (108 references) (auth)

  3. 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.

  4. 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.

  5. Proton-gamma coincidence experiment on medium mass nuclei at 400MeV and study of reaction mechanisms

    International Nuclear Information System (INIS)

    Baldit, Alain.

    1981-01-01

    Previous γ ray production experiments produced by proton on nuclei show important cross sections for residual nuclei corresponding to a four nucleon (2p + 2n) removal. With our (p - γ) coincidence experiment the forward emitted proton reflects the primary interaction and the γ spectra characterizes the final state of the reaction. Protons are detected with a magnetic spectrometer and γ rays are selected with a Ge(Li) diode. Angular and momentum analysis of scattered protons demonstrate a primary quasi free process on nucleons. No indication of knock out reactions on clusters has been seen. The residual nuclei are mainly produced by evaporation processes. A theoretical calculation involving intranuclear cascades and evaporation processes has been performed. The nucleus model is based upon a Fermi gas and nuclear density agrees with diffusion electron experiments. Residual nuclei far from target are well described with a such model. Residual nuclei near the target are sensitive to the nuclear structure [fr

  6. Enantioselective organocatalyzed Oxa-Michael-Aldol cascade reactions: Construction of chiral 4H-chromenes with a trifluoromethylated tetrasubstituted carbon stereocenter

    KAUST Repository

    Zhang, Jing; Ajitha, Manjaly John; He, Lin; Liu, Kai; Dai, Bin; Huang, Kuo-Wei

    2015-01-01

    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

  7. Impact Parameter Dependence of the Double Neutron/Proton Ratio of Nucleon Emissions in Isotopic Reaction Systems

    International Nuclear Information System (INIS)

    Xun-Chao, Zhang; Gao-Chan, Yong; Bao-An, Li; Lie-Wen, Chen

    2009-01-01

    Within the transport model IBUU04, we investigate the double neutron/proton ratio of free nucleons taken from two reaction systems using two Sn isotopes at a beam energy of 50 MeV/nucleon and with impact parameters 2 fm, 4 fm and 8 fm, respectively. It is found that the double neutron/proton ratio from peripheral collisions is more sensitive to the density dependence of the symmetry energy than those from mid-central and central collisions. (nuclear physics)

  8. Study of proton-deuteron break-up reaction in exclusive experiment at 1 GeV

    International Nuclear Information System (INIS)

    Aleshin, N.P.; Belostotskij, S.L.; Dotsenko, Yu.V.

    1987-07-01

    The exclusive proton-deuteron break-up reaction pD yields ppn was studied at 1 GeV. Differential cross sections and polarizations of the final protons were measured in the range of neutron-spectator momenta 0 3 3 <0.2 GeV/c, respectively. The data obtained are well described within the framework of impulse approximation with the Paris wave function of the deuteron. (author)

  9. Gas phase reactions of protonated 1,3-diphenylpropyne and some isomeric [C15H13]+ ions

    OpenAIRE

    Bäther, Wolfgang; Kuck, Dietmar; Grützmacher, Hans-Friedrich

    1985-01-01

    Metastable (3-phenyl-2-propynyl)benzenium ions, generated by electron impact induced fragmentation from the appropriately substituted 1,4-dihydrobenzoic acid, react by loss of ·CH3 and C6H6. The study of deuterated derivatives reveals that hydrogen/deuterium exchanges involving all hydrogen and deuterium atoms precede the fragmentations. The results suggest a skeletal rearrangement by electrophilic ring-closure reactions giving rise to protonated phenylindene and protonated 9,10-methano-9,10-...

  10. Extension of PENELOPE to protons: Simulation of nuclear reactions and benchmark with Geant4

    International Nuclear Information System (INIS)

    Sterpin, E.; Sorriaux, J.; Vynckier, S.

    2013-01-01

    Purpose: Describing the implementation of nuclear reactions in the extension of the Monte Carlo code (MC) PENELOPE to protons (PENH) and benchmarking with Geant4.Methods: PENH is based on mixed-simulation mechanics for both elastic and inelastic electromagnetic collisions (EM). The adopted differential cross sections for EM elastic collisions are calculated using the eikonal approximation with the Dirac–Hartree–Fock–Slater atomic potential. Cross sections for EM inelastic collisions are computed within the relativistic Born approximation, using the Sternheimer–Liljequist model of the generalized oscillator strength. Nuclear elastic and inelastic collisions were simulated using explicitly the scattering analysis interactive dialin database for 1 H and ICRU 63 data for 12 C, 14 N, 16 O, 31 P, and 40 Ca. Secondary protons, alphas, and deuterons were all simulated as protons, with the energy adapted to ensure consistent range. Prompt gamma emission can also be simulated upon user request. Simulations were performed in a water phantom with nuclear interactions switched off or on and integral depth–dose distributions were compared. Binary-cascade and precompound models were used for Geant4. Initial energies of 100 and 250 MeV were considered. For cases with no nuclear interactions simulated, additional simulations in a water phantom with tight resolution (1 mm in all directions) were performed with FLUKA. Finally, integral depth–dose distributions for a 250 MeV energy were computed with Geant4 and PENH in a homogeneous phantom with, first, ICRU striated muscle and, second, ICRU compact bone.Results: For simulations with EM collisions only, integral depth–dose distributions were within 1%/1 mm for doses higher than 10% of the Bragg-peak dose. For central-axis depth–dose and lateral profiles in a phantom with tight resolution, there are significant deviations between Geant4 and PENH (up to 60%/1 cm for depth–dose distributions). The agreement is much

  11. Extension of PENELOPE to protons: simulation of nuclear reactions and benchmark with Geant4.

    Science.gov (United States)

    Sterpin, E; Sorriaux, J; Vynckier, S

    2013-11-01

    Describing the implementation of nuclear reactions in the extension of the Monte Carlo code (MC) PENELOPE to protons (PENH) and benchmarking with Geant4. PENH is based on mixed-simulation mechanics for both elastic and inelastic electromagnetic collisions (EM). The adopted differential cross sections for EM elastic collisions are calculated using the eikonal approximation with the Dirac-Hartree-Fock-Slater atomic potential. Cross sections for EM inelastic collisions are computed within the relativistic Born approximation, using the Sternheimer-Liljequist model of the generalized oscillator strength. Nuclear elastic and inelastic collisions were simulated using explicitly the scattering analysis interactive dialin database for (1)H and ICRU 63 data for (12)C, (14)N, (16)O, (31)P, and (40)Ca. Secondary protons, alphas, and deuterons were all simulated as protons, with the energy adapted to ensure consistent range. Prompt gamma emission can also be simulated upon user request. Simulations were performed in a water phantom with nuclear interactions switched off or on and integral depth-dose distributions were compared. Binary-cascade and precompound models were used for Geant4. Initial energies of 100 and 250 MeV were considered. For cases with no nuclear interactions simulated, additional simulations in a water phantom with tight resolution (1 mm in all directions) were performed with FLUKA. Finally, integral depth-dose distributions for a 250 MeV energy were computed with Geant4 and PENH in a homogeneous phantom with, first, ICRU striated muscle and, second, ICRU compact bone. For simulations with EM collisions only, integral depth-dose distributions were within 1%/1 mm for doses higher than 10% of the Bragg-peak dose. For central-axis depth-dose and lateral profiles in a phantom with tight resolution, there are significant deviations between Geant4 and PENH (up to 60%/1 cm for depth-dose distributions). The agreement is much better with FLUKA, with deviations within

  12. Proton conduction within the reaction centers of Rhodobacter capsulatus: the electrostatic role of the protein.

    Science.gov (United States)

    Maróti, P; Hanson, D K; Baciou, L; Schiffer, M; Sebban, P

    1994-06-07

    Light-induced charge separation in the photosynthetic reaction center results in delivery of two electrons and two protons to the terminal quinone acceptor QB. In this paper, we have used flash-induced absorbance spectroscopy to study three strains that share identical amino acid sequences in the QB binding site, all of which lack the protonatable amino acids Glu-L212 and Asp-L213. These strains are the photosynthetically incompetent site-specific mutant Glu-L212/Asp-L213-->Ala-L212/Ala-L213 and two different photocompetent derivatives that carry both alanine substitutions and an intergenic suppressor mutation located far from QB (class 3 strain, Ala-Ala + Arg-M231-->Leu; class 4 strain, Ala-Ala + Asn-M43-->Asp). At pH 8 in the double mutant, we observe a concomitant decrease of nearly 4 orders of magnitude in the rate constants of second electron and proton transfer to QB compared to the wild type. Surprisingly, these rates are increased to about the same extent in both types of suppressor strains but remain > 2 orders of magnitude smaller than those of the wild type. In the double mutant, at pH 8, the loss of Asp-L213 and Glu-L212 leads to a substantial stabilization (> or = 60 meV) of the semiquinone energy level. Both types of compensatory mutations partially restore, to nearly the same level, the original free energy difference for electron transfer from primary quinone QA to QB. The pH dependence of the electron and proton transfer processes in the double-mutant and the suppressor strains suggests that when reaction centers of the double mutant are shifted to lower pH (1.5-2 units), they function like those of the suppressor strains at physiological pH. Our data suggest that the main effect of the compensatory mutations is to partially restore the negative electrostatic environment of QB and to increase an apparent "functional" pK of the system for efficient proton transfer to the active site. This emphasizes the role of the protein in tuning the

  13. A Simulation Study for Radiation Treatment Planning Based on the Atomic Physics of the Proton-Boron Fusion Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sunmi; Yoon, Do-Kun; Shin, Han-Back; Jung, Joo-Young; Kim, Moo-Sub; Kim, Kyeong-Hyeon; Jang, Hong-Seok; Suh, Tae Suk [the Catholic University of Korea, Seoul (Korea, Republic of)

    2017-03-15

    The purpose of this research is to demonstrate, based on a Monte Carlo simulation code, the procedure of radiation treatment planning for proton-boron fusion therapy (PBFT). A discrete proton beam (60 - 120 MeV) relevant to the Bragg peak was simulated using a Monte Carlo particle extended (MCNPX, Ver. 2.6.0, National Laboratory, Los Alamos NM, USA) simulation code. After computed tomography (CT) scanning of a virtual water phantom including air cavities, the acquired CT images were converted using the simulation source code. We set the boron uptake regions (BURs) in the simulated water phantom to achieve the proton-boron fusion reaction. Proton sources irradiated the BUR, in the phantom. The acquired dose maps were overlapped with the original CT image of the phantom to analyze the dose volume histogram (DVH). We successfully confirmed amplifications of the proton doses (average: 130%) at the target regions. From the DVH result for each simulation, we acquired a relatively accurate dose map for the treatment. A simulation was conducted to characterize the dose distribution and verify the feasibility of proton boron fusion therapy (PBFT). We observed a variation in proton range and developed a tumor targeting technique for treatment that was more accurate and powerful than both conventional proton therapy and boron-neutron capture therapy.

  14. Activation cross-section measurements of some proton induced reactions on Ni, Co and Mo for proton activation analysis (PAA) purposes

    International Nuclear Information System (INIS)

    Alharbi, A.A.; Alzahrani, J.; Azzam, A.; Nuclear Research Center, Cairo

    2011-01-01

    The experimental proton induced reaction cross sections on some elements of the Havar alloy were measured using the activation method and the well established stacked-foil technique combined with high resolution gamma-ray spectroscopy. They included the reactions nat Ni(p,x) 57 Ni, nat Co(p,x) 58(m+g) Co and nat Mo(p,x) 94g,95g,96(m+g) Tc, the aim being to obtain reliable data in the proton energy range up to 26 MeV for some important reactions to be used in the proton activation analysis of steel or other alloys. Irradiations were performed using the CS-30 Cyclotron at KFSH and RC, Riyadh, Saudi Arabia. The activity measurements were carried out in PNU laboratories, Riyadh, Saudi Arabia. The experimental excitation functions for the investigated reactions were constructed and compared with the performed computed theoretical nuclear model calculations using two different codes: ALICE-IPPE and TALYS. A comparison between our measured cross-section values and the available published data is also presented, with a view to checking the consistency of the reported experimental work from various laboratories.

  15. The Generation of Dehydroalanine Residues in Protonated Polypeptides: Ion/Ion Reactions for Introducing Selective Cleavages

    Science.gov (United States)

    Peng, Zhou; Bu, Jiexun; McLuckey, Scott A.

    2017-09-01

    We examine a gas-phase approach for converting a subset of amino acid residues in polypeptide cations to dehydroalanine (Dha). Subsequent activation of the modified polypeptide ions gives rise to specific cleavage N-terminal to the Dha residue. This process allows for the incorporation of selective cleavages in the structural characterization of polypeptide ions. An ion/ion reaction within the mass spectrometer between a multiply protonated polypeptide and the sulfate radical anion introduces a radical site into the multiply protonated polypeptide reactant. Subsequent collisional activation of the polypeptide radical cation gives rise to radical side chain loss from one of several particular amino acid side chains (e.g., leucine, asparagine, lysine, glutamine, and glutamic acid) to yield a Dha residue. The Dha residues facilitate preferential backbone cleavages to produce signature c- and z-ions, demonstrated with cations derived from melittin, mechano growth factor (MGF), and ubiquitin. The efficiencies for radical side chain loss and for subsequent generation of specific c- and z-ions have been examined as functions of precursor ion charge state and activation conditions using cations of ubiquitin as a model for a small protein. It is noted that these efficiencies are not strongly dependent on ion trap collisional activation conditions but are sensitive to precursor ion charge state. Moderate to low charge states show the greatest overall yields for the specific Dha cleavages, whereas small molecule losses (e.g., water/ammonia) dominate at the lowest charge states and proton catalyzed amide bond cleavages that give rise to b- and y-ions tend to dominate at high charge states. [Figure not available: see fulltext.

  16. 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

  17. Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction.

    Science.gov (United States)

    Zhu, Hongying; Huang, Guangming

    2015-03-31

    In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m(-3), ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. The use of low energy, ion induced nuclear reactions for proton radiotherapy applications

    International Nuclear Information System (INIS)

    Horn, K.M.; Doyle, B.; Segal, M.N.; Adler, R.J.; Glatstein, E.

    1995-01-01

    Medical radiotherapy has traditionally relied upon the use of external photon beams and internally implanted radioisotopes as the chief means of irradiating tumors. However, advances in accelerator technology and the exploitation of novel means of producing radiation may provide useful alternatives to some current modes of medical radiation delivery with reduced total dose to surrounding healthy tissue, reduced expense, or increased treatment accessibility. This paper will briefly overview currently established modes of radiation therapy, techniques still considered experimental but in clinical use, innovative concepts under study that may enable new forms of treatment or enhance existing ones. The potential role of low energy, ion-induced nuclear reactions in radiotherapy applications is examined specifically for the 650 keV d( 3 He,p) 4 He nuclear reaction. This examination will describe the basic physics associated with this reaction's production of 17.4 MeV protons and the processes used to fabricate the necessary materials used in the technique. Calculations of the delivered radiation dose, heat generation, and required exposure times are presented. Experimental data are also presented validating the dose calculations. The design of small, lower cost ion accelerators, as embodied in 'nested'-tandem and radio frequency quadrupole accelerators is examined, as is the potential use of high-output 3 He and deuterium ion sources. Finally, potential clinical applications are discussed in terms of the advantages and disadvantages of this technique with respect to current radiotherapy methods and equipment

  19. The use of low energy, ion induced nuclear reactions for proton radiotherapy applications

    Science.gov (United States)

    Horn, K. M.; Doyle, B.; Segal, M. N.; Hamm, R. W.; Adler, R. J.; Glatstein, E.

    1995-12-01

    Medical radiotherapy has traditionally relied upon the use of external photon beams and internally implanted radioisotopes as the chief means of irradiating tumors. However, advances in accelerator technology and the exploitation of novel means of producing radiation may provide useful alternatives to some current modes of medical radiation delivery — with reduced total dose to surrounding healthy tissue, reduced expense, or increased treatment accessibility. This paper will briefly overview currently established modes of radiation therapy, techniques still considered experimental but in clinical use and innovative concepts under study that may enable new forms of treatment or enhance existing ones. The potential role of low energy, ion-induced nuclear reactions in radiotherapy applications is examined specifically for the 650 keV d( 3He,p) 4 He nuclear reaction. This examination will describe the basic physics associated with this reaction's production of 17.4 MeV protons and the processes used to fabricate the necessary materials used in the technique. Calculations of the delivered radiation dose, heat generation, and required exposure times are presented. Experimental data is also presented validating the dose calculations. The design of small, lower cost ion accelerators, as embodied in "nested"-tandem and radio frequency quadrupole accelerators is examined, as is the potential use of high-output 3He and deuterium ion sources. Finally, potential clinical applications are discussed in terms of the advantages and disadvantages of this technique with respect to current radiotherapy methods and equipment.

  20. Demonstration of Synaptic Behaviors and Resistive Switching Characterizations by Proton Exchange Reactions in Silicon Oxide

    Science.gov (United States)

    Chang, Yao-Feng; Fowler, Burt; Chen, Ying-Chen; Zhou, Fei; Pan, Chih-Hung; Chang, Ting-Chang; Lee, Jack C.

    2016-02-01

    We realize a device with biological synaptic behaviors by integrating silicon oxide (SiOx) resistive switching memory with Si diodes. Minimal synaptic power consumption due to sneak-path current is achieved and the capability for spike-induced synaptic behaviors is demonstrated, representing critical milestones for the use of SiO2-based materials in future neuromorphic computing applications. Biological synaptic behaviors such as long-term potentiation (LTP), long-term depression (LTD) and spike-timing dependent plasticity (STDP) are demonstrated systematically using a comprehensive analysis of spike-induced waveforms, and represent interesting potential applications for SiOx-based resistive switching materials. The resistive switching SET transition is modeled as hydrogen (proton) release from (SiH)2 to generate the hydrogen bridge defect, and the RESET transition is modeled as an electrochemical reaction (proton capture) that re-forms (SiH)2. The experimental results suggest a simple, robust approach to realize programmable neuromorphic chips compatible with large-scale CMOS manufacturing technology.

  1. Measurement of the Induced Proton Polarization Pn in the 12C(e, e', p) reaction

    International Nuclear Information System (INIS)

    Woo, R.J.; Barkhuff, David; Bertozzi, William; Jian-ping Chen; Dan Dale; G. Dodson; K.A. Dow; Marty Epstein; Manouchehr Farkhondeh; Mike Finn; Shalev Gilad; Mark K. Jones; Kyungseon Joo; James Kelly; Stanley Kowalski; Bob Lourie; Richard Madey; Dimitri Margaziotis; Pete Markowitz; Justin McIntyre; Christoph Mertz; Brian Milbrath; Joseph Mitchell; Charles F. Perdrisat; Vina Punjabi; Paul Rutt; Adam Sarty; D. Tieger; C. Tschalaer; William Turchinetz; Paul E. Ulmer; S.P. Van Verst; C. Vellidis; Glen Warren; Lawrence Weinstein

    1998-01-01

    The first measurements of the induced proton polarization Pn for the 12C(e,e',p) reaction are reported. The experiment was performed at quasifree kinematics for energy and momentum transfer (w,q) = (294 MeV, 765 MeV/c) and sampled a missing momentum range of 0-250 MeV/c. The induced polarization arises from final-state interactions and for these kinematics is dominated by the real part of the spin-orbit optical potential. The distorted-wave impulse approximation provides good agreement with data for the 1 p3/2 shell. The data for the continuum suggest that both the 1s1/2 shell and underlying l > 1 configurations contribute

  2. Development of a system of measuring double-differential cross sections for proton-induced reactions

    Energy Technology Data Exchange (ETDEWEB)

    Harada, M.; Watanabe, Y.; Sato, K. [Kyushu Univ., Fukuoka (Japan); Meigo, S.

    1997-03-01

    We report the present status of a counter telescope and a data acquisition system which are being developed for the measurement of double-differential cross sections of all light-charged particles emitted from proton-induced reactions on {sup 12}C at incident energies less than 90 MeV. The counter telescope consists of an active collimator made of a plastic scintillator, two thin silicon {Delta}E-detectors and a CsI(Tl) E-detectors with photo-diode readout. Signals from each detector are processed using the data acquisition system consisting of the front-end electronics (CAMAC) and two computers connected with the ethernet LAN: a personal computer as the data collector and server, and a UNIX workstation as the monitor and analyzer. (author)

  3. Fragment formation in GeV-energy proton and light heavy-ion induced reactions

    International Nuclear Information System (INIS)

    Murakami, T.; Haga, M.; Haseno, M.

    2002-01-01

    We have investigated similarities and differences among the fragment formation processes in GeV-energy light-ion and light heavy-ion induced reactions. We have newly measured inclusive and exclusive energy spectra of intermediate mass fragments (3 ≤ Z ≤ 30; IMFs) for 8-GeV 16 O and 20 Ne and 12-GeV 20 Ne induced target multifragmentations (TMFs) in order to compare them with those previously measured for 8- and 12-GeV proton induced TMFs. We fond noticeable difference in their spectrum shapes and magnitudes but all of them clearly indicate the existence of sideward-peaked components, indicating fragment formations are mainly dictated not by a incident energy per nucleon but by a total energy of the projectile. (author)

  4. New calculations of cyclotron production cross sections of some positron emitting radioisotopes in proton induced reactions

    International Nuclear Information System (INIS)

    Tel, E.; Aydin, E.G.; Kaplan, A.; Aydin, A.

    2009-01-01

    In this study, new calculations on the excitation functions of 13 C(p, n) 13 N, 14 N (p, α) 11 C, 15 N(p, n) 15 O, 16 O(p, α) 13 N, 18 O(p, n) 18 F, 62 Ni(p, n) 62 Cu, 68 Zn(p, n) 68 Ga and 72 Ge(p, n) 72 As reactions have been carried out in the 5-40 MeV incident proton energy range. In these calculations, the pre-equilibrium and equilibrium effects have been investigated. The pre-equilibrium calculations involve hybrid model, geometry dependent hybrid model, the cascade exciton model and full exciton model. Equilibrium effects were calculated according to Weisskopf-Ewing model. The calculated results have been compared with experimental data taken from literature. (author)

  5. The isolation of 139Ce after production by a proton-induced nuclear reaction on praseodymium

    International Nuclear Information System (INIS)

    Van der Walt, T.N.; Vermeulen, C.

    2004-01-01

    A method, based on anion exchange chromatography, is presented for the isolation of 139 Ce after production by a proton-induced nuclear reaction on a thick praseodymium target. After bombardment the target is dissolved in nitric acid and 139 Ce oxidised to the Ce(IV) oxidation state with bromic acid. 139 Ce is then separated form the praseodymium by anion exchange chromatography on a Ag MP-1 resin column in a nitric acid - bromic acid mixture. 139 Ce is sorbed onto the resin column and praseodymium eluted with the acid mixture. The bromic acid is washed out of the column with nitric acid and 139 Ce finally eluted with dilute nitric acid containing sulphur dioxide

  6. Formaldehyde measurements by Proton transfer reaction – Mass Spectrometry (PTR-MS: correction for humidity effects

    Directory of Open Access Journals (Sweden)

    A. Vlasenko

    2010-08-01

    Full Text Available Formaldehyde measurements can provide useful information about photochemical activity in ambient air, given that HCHO is formed via numerous oxidation processes. Proton transfer reaction mass spectrometry (PTR-MS is an online technique that allows measurement of VOCs at the sub-ppbv level with good time resolution. PTR-MS quantification of HCHO is hampered by the humidity dependence of the instrument sensitivity, with higher humidity leading to loss of PTR-MS signal. In this study we present an analytical, first principles approach to correct the PTR-MS HCHO signal according to the concentration of water vapor in sampled air. The results of the correction are validated by comparison of the PTR-MS results to those from a Hantzsch fluorescence monitor which does not have the same humidity dependence. Results are presented for an intercomparison made during a field campaign in rural Ontario at Environment Canada's Centre for Atmospheric Research Experiments.

  7. 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

  8. Reaction Coordinate, Free Energy, and Rate of Intramolecular Proton Transfer in Human Carbonic Anhydrase II.

    Science.gov (United States)

    Paul, Sanjib; Paul, Tanmoy Kumar; Taraphder, Srabani

    2018-03-22

    The role of structure and dynamics of an enzyme has been investigated at three different stages of its function including the chemical event it catalyzes. A one-pot computational method has been designed for each of these stages on the basis of classical and/or quantum mechanical-molecular mechanical molecular dynamics and transition path sampling simulations. For a pair of initial and final states A and B separated by a high free-energy barrier, using a two-stage selection process, several collective variables (CVs) are identified that can delineate A and B. However, these CVs are found to exhibit strong cross-coupling over the transition paths. A set of mutually orthogonal order parameters is then derived from these CVs and an optimal reaction coordinate, r, determined applying half-trajectory likelihood maximization along with a Bayesian information criterion. The transition paths are also used to project the multidimensional free energy surface and barrier crossing dynamics along r. The proposed scheme has been applied to the rate-determining intramolecular proton transfer reaction of the well-known enzyme human carbonic anhydrase II. The potential of mean force, F( r), in the absence of the chemical step is found to reproduce earlier results on the equilibrium population of two side-chain orientations of key residue His-64. Estimation of rate constants, k, from mean first passage times for the three different stages of catalysis shows that the rate-determining step of intramolecular proton transfer occurs with k ≃ 1.0 × 10 6 s -1 , in close agreement with known experimental results.

  9. Transverse-momentum scaling in pi /sup +or-/, K/sup +or-/, p, p production in proton-proton inclusive reactions at very high energies

    CERN Document Server

    Misra, R C

    1975-01-01

    Experimental measurements made on pp reactions at CERN ISR are discussed. The dependence on transverse momentum is approximately exponential for pi /sup +or-/ and K/sup +or-/ production, while for antiprotons and protons in the fragmentation region the dependence is better represented by a Gaussian form. It is shown that a generalised formalism can be set up, similar to KNO scaling, for the transverse momentum distribution of the produced particles and the production process can be either exponential or Gaussian. (11 refs).

  10. Calculation of rate coefficients of some proton-transfer ion-molecule reactions in weakly ionized gases

    International Nuclear Information System (INIS)

    Stiller, W.

    1985-01-01

    A classical collision theory is used to describe thermal bimolecular rate coefficeints for reaction between positive and negative ions and polar molecules in a carrier gas. Special attention is paid to ion-molecule reaction in which proton transfer occurs. These reactions play an important role in terrestrial plasma devices, in ionosphere, in planetary atmospheres and in interstellar matter. The equilibrium rate coefficients of the reactions are calculated based on a microscopic reactive cross section derived from a long distance polar molecule-ion potential. The results are compared with experimental values of afterglow measurements. (D.Gy.)

  11. On the idea of low-energy nuclear reactions in metallic lattices by producing neutrons from protons capturing "heavy" electrons

    Science.gov (United States)

    Tennfors, Einar

    2013-02-01

    The present article is a critical comment on Widom and Larsens speculations concerning low-energy nuclear reactions (LENR) based on spontaneous collective motion of protons in a room temperature metallic hydride lattice producing oscillating electric fields that renormalize the electron self-energy, adding significantly to the effective electron mass and enabling production of low-energy neutrons. The frequency and mean proton displacement estimated on the basis of neutron scattering from protons in palladium and applied to the Widom and Larsens model of the proton oscillations yield an electron mass enhancement less than one percent, far below the threshold for the proposed neutron production and even farther below the mass enhancement obtained by Widom and Larsen assuming a high charge density. Neutrons are not stopped by the Coulomb barrier, but the energy required for the neutron production is not low.

  12. Determination of the proton spectral function of 3He with the (e,e'p) reaction

    International Nuclear Information System (INIS)

    Jans, E.

    1982-01-01

    Cross sections of the 3 He(e,e'p) reaction have been measured with the 600 MeV linear accelerator at Saclay and the two-spectrometer set-up of the experimental hall HE1. The data cover the following region for the missing energy Esub(m) and the proton recoil momentum k: 0 3 He target are described in chapter IV. The experimental procedure, the data analysis, and the corrections which have been applied to the data, are discussed in chapter V. The results of the experiment are presented in chapter VI. The (e,e'p) reaction has proven its capabilities in obtaining detailed information on nuclear structure properties as nucleon momentum density distributions and separation energies, although corrections due to FSI and MEC have to be considered. In the case of 3 He, the results can be compared to predictions of various calculational techniques, using realistic NN-potentials and thus serve as a test for NN-potential models. (Auth.)

  13. Recent progress in the development of a polarized proton target for reactions with radioactive ion beams

    International Nuclear Information System (INIS)

    Urrego-Blanco, J.P.; Bingham, C.R.; Brandt, B. van den; Galindo-Uribarri, A.; Gomez del Campo, J.; Hautle, P.; Konter, J.A.; Padilla-Rodal, E.; Schmelzbach, P.A.

    2007-01-01

    Polarization observables in nuclear reactions with stable beams have provided important information concerning structural properties of nuclei and reaction mechanisms and hold great promise in the context of exotic nuclei. We report on the development of a polarized target based on plastic foils of 20-200 μm thickness to be used with radioactive ion beams. The operation of such a target requires a moderately high magnetic field and very low temperatures. The plastic foil is placed inside a chamber attached to the mixing chamber of a 3 He- 4 He dilution refrigerator. Cooling of the foil is achieved via a superfluid film of 4 He that can be supplied through two capillaries. The chamber has two thin, highly uniform silicon nitride windows. An NMR coil is attached to the target to monitor the polarization. Results of a first test to characterize the target system, using the elastic scattering of 38 MeV 12 C by protons in inverse kinematics are presented

  14. Production of noble gas isotopes by proton-induced reactions on bismuth

    International Nuclear Information System (INIS)

    Leya, I.; David, J.-C.; Leray, S.; Wieler, R.; Michel, R.

    2008-01-01

    We measured integral thin target cross sections for the proton-induced production of He-, Ne-, Ar-, Kr- and Xe-isotopes from bismuth (Bi) from the respective reaction thresholds up to 2.6 GeV. Here we present 275 cross sections for 23 nuclear reactions. The production of noble gas isotopes from Bi is of special importance for design studies of accelerator driven systems (EA/ADS) and nuclear spallation sources. For experiments with proton energies above 200 MeV the mini-stack approach was used instead of the stacked-foil technique in order to minimise the influences of secondary particles on the residual nuclide production. Comparing the cross sections for Bi to the data published recently for Pb indicates that for 4 He the cross sections for Bi below 200 MeV are up to a factor of 2-3 higher than the Pb data, which can be explained by the production of α-decaying Po-isotopes from Bi but not from Pb. Some of the cross sections for the production of 21 Ne from Bi are affected by recoil effects from neighboured Al-foils, which compromises a study of a possible lowering of the effective Coulomb-barrier. The differences in the excitation functions between Pb and Bi for Kr- and Xe-isotopes can be explained by energy-dependent higher fission cross sections for Bi compared to Pb. The experimental data are compared to results from the theoretical nuclear model codes INCL4/ABLA and TALYS. The INCL4/ABLA system describes the cross sections for the production of 4 He-, Kr- and Xe-isotopes reasonably well, i.e. mostly within a factor of a few. In contrast, the model completely fails describing 21 Ne, 22 Ne, 36 Ar and 38 Ar, which are produced via spallation and/or multifragmentation. The TALYS code is only able to accurately predict reaction thresholds. The absolute values are either significantly over- or underestimated. Consequently, the comparison of measured and modelled thin target cross sections clearly indicates that experimental data are still needed because the

  15. Thresholds and Q values of nuclear reactions induced by neutrons, protons, deuterons, tritons, 3He ions, alpha particles, and photons

    International Nuclear Information System (INIS)

    Howerton, R.J.

    1981-01-01

    The 1977 Wapstra and Bos nuclear mass data tables were used to derive tables for thresholds and Q values of nuclear reactions induced by neutrons, protons, deuterons, tritons, 3 He ions, alpha particles, and photons. The tables are displayed on microfiche included with the report

  16. In vitro and in vivo volatile flavour analysis of red kidney beans by proton transfer reaction-mass spectrometry

    NARCIS (Netherlands)

    Ruth, van S.M.; Dings, L.; Buhr, K.; Posthumus, M.A.

    2004-01-01

    The volatile flavour released from red kidney beans was evaluated in vitro (in a model mouth system) and in vivo (in-nose). The dynamic release of the volatile flavour compounds was analysed by proton transfer reaction¿mass spectrometry. The flavour compounds were identified by gas

  17. Measurement and calculation of cross section for (p,x) reactions on natural Fe for 650 MeV protons

    International Nuclear Information System (INIS)

    Janczyszyn, J.; Pohorecki, W.; Domanska, G.; Loska, L.; Taczanowski, S.; Shvetsov, V.

    2006-01-01

    Cross sections for production of radionuclides in (p,x) reactions on natural iron were measured for protons of 650 ± 4 MeV with the use of HPGe gamma spectrometry and calculated with the MCNPX code. The determined cross section values were compared with the computed and other experimental ones

  18. Comparison between proton transfer reaction mass spectrometry and near infrared spectroscopy for the authentication of Brazilian coffee

    NARCIS (Netherlands)

    Monteiro, Pablo Inocêncio; Santos, Jânio Sousa; Alvarenga Brizola, Vitor Rafael; Pasini Deolindo, Carolina Turnes; Koot, Alex; Boerrigter-Eenling, Rita; Ruth, van Saskia; Georgouli, Konstantia; Koidis, Anastasios; Granato, Daniel

    2018-01-01

    In this study, proton-transfer reaction mass spectrometry (PTR-MS) and near-infrared spectroscopy (NIRS) were compared for the authentication of geographical and farming system origins of Brazilian coffees. For this purpose, n = 19 organic (ORG) and n = 26 conventional (CONV) coffees from

  19. Characterisation of the semi-volatile component of Dissolved Organic Matter by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry

    NARCIS (Netherlands)

    Materić, Dušan; Peacock, Mike; Kent, Matthew; Cook, Sarah; Gauci, Vincent; Röckmann, Thomas; Holzinger, Rupert

    2017-01-01

    Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a sensitive, soft ionisation method suitable for qualitative and quantitative analysis of volatile and semi-volatile organic vapours. PTR-MS is used for various environmental applications including monitoring of volatile organic compounds

  20. Proton transfer reaction-mass spectrometry volatile organic compound fingerprinting for monovarietal extra virgin olive oil identification

    NARCIS (Netherlands)

    Ruiz-Samblas, C.; Tres, A.; Koot, A.H.; Ruth, van S.M.; Gonzalez-Casado, A.; Cuadros-Rodriguez, L.

    2012-01-01

    Proton transfer reaction-mass spectrometry (PTR-MS) is a relatively new technique that allows the fast and accurate qualification of the volatile organic compound (VOC) fingerprint. This paper describes the analysis of thirty samples of extra virgin olive oil, of five different varieties of olive

  1. Geographical provenancing of purple grape juices from different farming systems by proton transfer reaction mass spectrometry using supervised statistical techniques

    NARCIS (Netherlands)

    Granato, Daniel; Koot, Alex; Ruth, van S.M.

    2015-01-01

    BACKGROUND: Organic, biodynamic and conventional purple grape juices (PGJ; n = 79) produced in Brazil and Europe were characterized by volatile organic compounds (m/z 20-160) measured by proton transfer reaction mass spectrometry (PTR-MS), and classification models were built using supervised

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solution based upon a mixed quantum-classical approximation. II. Proton transfer reaction in non-polar solvent

    Science.gov (United States)

    Kojima, H.; Yamada, A.; Okazaki, S.

    2015-05-01

    The intramolecular proton transfer reaction of malonaldehyde in neon solvent has been investigated by mixed quantum-classical molecular dynamics (QCMD) calculations and fully classical molecular dynamics (FCMD) calculations. Comparing these calculated results with those for malonaldehyde in water reported in Part I [A. Yamada, H. Kojima, and S. Okazaki, J. Chem. Phys. 141, 084509 (2014)], the solvent dependence of the reaction rate, the reaction mechanism involved, and the quantum effect therein have been investigated. With FCMD, the reaction rate in weakly interacting neon is lower than that in strongly interacting water. However, with QCMD, the order of the reaction rates is reversed. To investigate the mechanisms in detail, the reactions were categorized into three mechanisms: tunneling, thermal activation, and barrier vanishing. Then, the quantum and solvent effects were analyzed from the viewpoint of the reaction mechanism focusing on the shape of potential energy curve and its fluctuations. The higher reaction rate that was found for neon in QCMD compared with that found for water solvent arises from the tunneling reactions because of the nearly symmetric double-well shape of the potential curve in neon. The thermal activation and barrier vanishing reactions were also accelerated by the zero-point energy. The number of reactions based on these two mechanisms in water was greater than that in neon in both QCMD and FCMD because these reactions are dominated by the strength of solute-solvent interactions.

  8. Theoretical calculations of the reaction cross-sections for proton-induced reactions on natural copper using ALICE-IPPE code

    International Nuclear Information System (INIS)

    Alharbi, A.A.; Azzam, A.

    2012-01-01

    A theoretical study of the nuclear-reaction cross sections for proton-induced reactions on 63 Cu and 65 Cu was performed in the proton energy range from threshold values up to 50 MeV. The produced nuclei were different isotopes of Zn, Cu, Ni, Co and Mn, some of which have important applications. The reaction cross-section calculations were performed using the ALICE-IPPE code, which depends on the pre-equilibrium compound nucleus model. This code is suitable for the studied energy and isotopic mass ranges. Approximately 14 excitation functions for the different reactions have been constructed from the calculated cross-section values. The excitation function curves for the proton reactions with natural copper targets have been constructed from those for enriched targets using the natural abundance of the copper isotopes. Comparisons between the calculated excitation functions with those previously experimentally measured are given whenever the experimental values were available. Some statistical parameters were introduced to control the quality of the fitting between both the experimental and the theoretical calculated cross-section values. - Highlights: ► We performed reaction cross section calculations using ALICE-IPPE code. ► We constructed 14 excitation functions for nat Cu(p,xn)Zn,Cu,Ni,Co,Mn reactions. ► The available experimental data were fitted to the performed ALICE-IPPE calculations. ► Statistical parameters were introduced to control the quality of the fitting. ► The code failed to fit the experimental data for reactions with large nucleon emissions.

  9. Measurements of activation reaction rate distributions on a mercury target bombarded with high-energy protons at AGS

    Energy Technology Data Exchange (ETDEWEB)

    Takada, Hiroshi; Kasugai, Yoshimi; Nakashima, Hiroshi; Ikeda, Yujiro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Ino, Takashi; Kawai, Masayoshi [High Energy Accelerator Research Organization, Tsukuba, Ibaraki (Japan); Jerde, Eric; Glasgow, David [Oak Ridge National Laboratory, Oak Ridge, TN (United States)

    2000-02-01

    A neutronics experiment was carried out using a thick mercury target at the Alternating Gradient Synchrotron (AGS) facility of Brookhaven National Laboratory in a framework of the ASTE (AGS Spallation Target Experiment) collaboration. Reaction rate distributions around the target were measured by the activation technique at incident proton energies of 1.6, 12 and 24 GeV. Various activation detectors such as the {sup 115}In(n,n'){sup 115m}In, {sup 93}Nb(n,2n){sup 92m}Nb, and {sup 209}Bi(n,xn) reactions with threshold energies ranging from 0.3 to 70.5 MeV were employed to obtain the reaction rate data for estimating spallation source neutron characteristics of the mercury target. It was found from the measured {sup 115}In(n,n'){sup 115m}In reaction rate distribution that the number of leakage neutrons becomes maximum at about 11 cm from the top of hemisphere of the mercury target for the 1.6-GeV proton incidence and the peak position moves towards forward direction with increase of the incident proton energy. The similar result was observed in the reaction rate distributions of other activation detectors. The experimental procedures and a full set of experimental data in numerical form are summarized in this report. (author)

  10. Measurements of activation reaction rate distributions on a mercury target bombarded with high-energy protons at AGS

    International Nuclear Information System (INIS)

    Takada, Hiroshi; Kasugai, Yoshimi; Nakashima, Hiroshi; Ikeda, Yujiro; Jerde, Eric; Glasgow, David

    2000-02-01

    A neutronics experiment was carried out using a thick mercury target at the Alternating Gradient Synchrotron (AGS) facility of Brookhaven National Laboratory in a framework of the ASTE (AGS Spallation Target Experiment) collaboration. Reaction rate distributions around the target were measured by the activation technique at incident proton energies of 1.6, 12 and 24 GeV. Various activation detectors such as the 115 In(n,n') 115m In, 93 Nb(n,2n) 92m Nb, and 209 Bi(n,xn) reactions with threshold energies ranging from 0.3 to 70.5 MeV were employed to obtain the reaction rate data for estimating spallation source neutron characteristics of the mercury target. It was found from the measured 115 In(n,n') 115m In reaction rate distribution that the number of leakage neutrons becomes maximum at about 11 cm from the top of hemisphere of the mercury target for the 1.6-GeV proton incidence and the peak position moves towards forward direction with increase of the incident proton energy. The similar result was observed in the reaction rate distributions of other activation detectors. The experimental procedures and a full set of experimental data in numerical form are summarized in this report. (author)

  11. The two-proton halo nucleus {sup 17}Ne studied in high-energy nuclear breakup reactions

    Energy Technology Data Exchange (ETDEWEB)

    Wamers, Felix [EMMI, GSI, Darmstadt (Germany); FIAS, Frankfurt (Germany); IKP, TU Darmstadt, Darmstadt (Germany); GSI, Darmstadt (Germany); Marganiec, Justyna [IKP, TU Darmstadt, Darmstadt (Germany); EMMI, GSI, Darmstadt (Germany); GSI, Darmstadt (Germany); Aumann, Thomas [IKP, TU Darmstadt, Darmstadt (Germany); GSI, Darmstadt (Germany); Bertulani, Carlos [Texas A and M University-Commerce, Commerce (United States); Chulkov, Leonid [GSI, Darmstadt (Germany); NRC Kurchatov Institute, Moscow (Russian Federation); Heil, Michael; Simon, Haik [GSI, Darmstadt (Germany); Plag, Ralf [GSI, Darmstadt (Germany); Goethe Universitaet, Frankfurt (Germany); Savran, Deniz [EMMI, GSI, Darmstadt (Germany); FIAS, Frankfurt (Germany); Collaboration: R3B-Collaboration

    2014-07-01

    We report on exclusive measurements of nuclear breakup reactions of highly-energetic (500 MeV) unstable {sup 17}Ne beams impinging on light targets in an experiment at the R{sup 3}B-LAND complete-kinematics reaction setup at GSI. Focusing on the properties of beam-like {sup 15}O-p (={sup 16}F) systems produced in one-proton-removal reactions, we are presenting a comprehensive analysis of the s-/d-wave configuration mixing of the {sup 17}Ne valence-proton pair that is used to quantify its halo-nature. The results include the {sup 15}O-p relative-energy spectrum, {sup 16}F momentum distributions, and their corresponding momentum profile.

  12. Study on the properties of leading protons and antiprotons from exclusive anti pp reactions at 32 GeV/c

    International Nuclear Information System (INIS)

    Bogolyubskij, M.Yu.; Borovikov, A.A.; Boos, Eh.G.

    1986-01-01

    The leading properties of protons and antiprotons from the nondiffractive events are studied for p-barp-exclusive reactions at 32 GeV/c. It is found that the relative leading effect of protons and antiprotons does not depend on the final-state multiplicity and that the longitudinal moments of the leading hadrons are uncorrelated, but a significant part of the transverse momentum of a leading hadron is compensated by the transverse momentum of another leading hadron. It is shown that these experimental facts are described well by a statistical jet-independent model but contradict the Lund string-fragmentation model

  13. Excitation functions for the formation of some short-lived products in proton-induced reactions on silver

    OpenAIRE

    Uddin, M. S.; Baba, M.; Hagiwara, M.; Latif, S. K. A.; Qaim, S. M.

    2008-01-01

    Excitation functions of the Ag-nat(p, xn)Cd-104,Cd-105 and Ag-nat(p, pxn) Ag-103,Ag-104m.g,Ag- 1049 reactions were measured for the first time over the proton energy range of 32 to about 60 MeV. The data were compared with the results of precompound-hybrid model calculations, whereby only partial agreement was obtained. The contribution of the Ag-103 precursor decay to the total formation of the therapeutic radionuclide Pd-103 in proton activation of silver was estimated: it amounted to about...

  14. An abnormally slow proton transfer reaction in a simple HBO derivative due to ultrafast intramolecular-charge transfer events.

    Science.gov (United States)

    Alarcos, Noemí; Gutierrez, Mario; Liras, Marta; Sánchez, Félix; Douhal, Abderrazzak

    2015-07-07

    We report on the steady-state, picosecond and femtosecond time-resolved studies of a charge and proton transfer dye 6-amino-2-(2'-hydroxyphenyl)benzoxazole (6A-HBO) and its methylated derivative 6-amino-2-(2'-methoxyphenyl)benzoxazole (6A-MBO), in different solvents. With femtosecond resolution and comparison with the photobehaviour of 6A-MBO, we demonstrate for 6A-HBO in solution, the photoproduction of an intramolecular charge-transfer (ICT) process at S1 taking place in ∼140 fs or shorter, followed by solvent relaxation in the charge transferred species. The generated structure (syn-enol charge transfer conformer) experiences an excited-state intramolecular proton-transfer (ESIPT) reaction to produce a keto-type tautomer. This subsequent proton motion occurs in 1.2 ps (n-heptane), 14 ps (DCM) and 35 ps (MeOH). In MeOH, it is assisted by the solvent molecules and occurs through tunneling for which we got a large kinetic isotope effect (KIE) of about 13. For the 6A-DBO (deuterated sample in CD3OD) the global proton-transfer reaction takes place in 200 ps, showing a remarkable slow KIE regime. The slow ESIPT reaction in DCM (14 ps), not through tunnelling as it is not sensitive to OH/OD exchange, has however to overcome an energy barrier using intramolecular as well as solvent coordinates. The rich ESIPT dynamics of 6A-HBO in the used solutions is governed by an ICT reaction, triggered by the amino group, and it is solvent dependent. Thus, the charge injection to a 6A-HBO molecular frame makes the ICT species more stable, and the phenol group less acidic, slowing down the subsequent ESIPT reaction. Our findings bring new insights into the coupling between ICT and ESIPT reactions on the potential-energy surfaces of several barriers.

  15. 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.

  16. Monitoring benzene formation from benzoate in model systems by proton transfer reaction-mass spectrometry

    Science.gov (United States)

    Aprea, Eugenio; Biasioli, Franco; Carlin, Silvia; Märk, Tilmann D.; Gasperi, Flavia

    2008-08-01

    The presence of benzene in food and in particular in soft drinks has been reported in several studies and should be considered in fundamental investigations about formation of this carcinogen compound as well as in quality control. Proton transfer reaction-mass spectrometry (PTR-MS) has been used here for rapid, direct quantification of benzene and to monitor its formation in model systems related to the use of benzoate, a common preservative, in presence of ascorbic acid: a widespread situation that yields benzene in, e.g., soft drinks and fruit juices. Firstly, we demonstrate here that PTR-MS allows a rapid determination of benzene that is in quantitative agreement with independent solid phase micro-extraction/gas chromatography (SPME/GC) analysis. Secondly, as a case study, the effect of different sugars (sucrose, fructose and glucose) on benzene formation is investigated indicating that they inhibit its formation and that this effect is enhanced for reducing sugars. The sugar-induced inhibition of benzene formation depends on several parameters (type and concentration of sugar, temperature, time) but can be more than 80% in situations that can be expected in the storage of commercial soft drinks. This is consistent with the reported observations of higher benzene concentrations in sugar-free soft drinks.

  17. Production of residual nuclides by proton-induced reactions on target W at the energy of 72 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Miah, Moazzem Hossain [Univ. of Chittagong, Dept. of Physics, Chittagong (Bangladesh); Kuhnhenn, Jochen; Herpers, Ulrich [Univ. of Cologne, Dept. of Nuclear Chemistry, Cologne (Germany); Michel, Rolf [University of Hannover, Centre for Radiation Protection and Radioecology (Germany); Kubik, Peter [Paul Scherrer Inst., c/o Institute for Particle Physics, ETH Hoenggerberg, Zuerich (Switzerland)

    2002-08-01

    Investigations of cross-sections for residual nuclide production on the target element W by proton-induced reactions were performed by irradiating the target with 72 MeV protons using the cyclotron facilities at Paul-Scherrer Institute, Zurich, Switzerland. Residual nuclides were measured by gamma-spectrometry of HpGe detectors calibrated with standard gamma sources. The measured data contains 104 individual cross-sections for 20 identified nuclides in the proton energies between 52.5 - 68.9 MeV. These nuclear data is important in the study of spallation neutron source and in accelerator driven technologies such as waste transmutation and energy amplification. The present data are compared with the shape of the excitation functions of earlier only one measurement at higher energies and they are in good agreement to each other. (author)

  18. 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.

  19. Production of He-, Ne-, Ar-, Kr-, and Xe-isotopes by proton-induced reactions on lead

    International Nuclear Information System (INIS)

    Leya, I.; Michel, R.

    2003-01-01

    We measured integral thin target cross sections for the proton-induced production of He-, Ne-, Ar-, Kr-, and Xe-isotopes from lead from the respective reaction thresholds up to 2.6 GeV. The production of noble gas isotopes in lead by proton-induced reactions is of special importance for design studies of accelerator driven systems and energy amplifiers. In order to minimise the influences of secondary particles on the production of residual nuclides a new Mini-Stack approach was used instead of the well-known stacked-foil techniques for all experiments with proton energies above 200 MeV. With some exceptions our database for the proton-induced production of noble gas isotopes from lead is consistent and nearly complete. In contradistinction to the production of He from Al and Fe, where the cross sections obtained by thin-target irradiation experiments are up to a factor of 2 higher than the NESSI data, both datasets agree for the He production from lead. (orig.)

  20. Proton conductive Pt-Co nanoparticles anchoring on citric acid functionalized graphene for efficient oxygen reduction reaction

    Science.gov (United States)

    Zhao, Yige; Liu, Jingjun; Wu, Yijun; Wang, Feng

    2017-08-01

    Designing highly efficient electro-catalysts for the oxygen reduction reaction (ORR) has been regarded as a demanding task in the development of renewable energy sources. However, little attention has been paid on improving Pt-based catalysts by promoting proton transfer from the electrolyte solutions to the catalyst layer at the cathode. Herein, we design proton conductive Pt-Co alloy nanoparticles anchoring on citric acid functionalized graphene (Pt-Co/CA-G) catalysts for efficient ORR. The facile modification approach for graphene can introduce oxygenated functional groups on the graphene surface to promote proton transfer as well as keeping the high electron conductivity without destroying the graphene original structure. The electrochemical results show that the Pt-Co/CA-G catalyst exhibits more excellent ORR activity and stability than the commercial Pt/C catalyst, which can be attributed to its improved proton transfer ability. The fast proton transfer comes from the hydrogen-bonding networks formed by the interaction between the oxygenated functional groups and water molecules. This work provides not only a novel and simple approach to modify graphene but also an effective strategy to improve Pt-based catalysts for the ORR.

  1. 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.

  2. Percolation-fission model study of the fragment mass distribution for the 1 GeV proton induced reaction

    International Nuclear Information System (INIS)

    Katsuma, Masahiko; Kobayashi, Hiroshi; Sawada, Tetsuo; Sasa, Toshinobu

    2005-01-01

    The 1 GeV proton induced reaction on 208 Pb targets is analyzed by using the percolation model combined with the Atchison fission model. The fragment mass distribution and the isotopic production cross sections obtained from our model are compared with the experimental data. The trends of the fragment mass distribution for the 1 GeV proton induced reaction can be reproduced by our calculation in some degree. The order of magnitude for the calculated isotopic production cross sections at the calculated peak positions is similar to that of the experimental peak values. The calculated peak positions of the isotopic production cross sections are shifted to the heavier region than those of the experimental data. (author)

  3. Tensor analyzing powers in deuteron--proton elastic scattering and the breakup reaction at 45.4 MeV

    International Nuclear Information System (INIS)

    Conzett, H.E.

    1978-08-01

    Recently the tensor analyzing powers in vector d + p elastic scattering and in the breakup reaction at E/sub d/ = 45.4 MeV were measured. The elastic results now establish a rather complete set of polarization data in nucleon--deuteron scattering at E/sub N/ = 22.7 MeV, which consists of the proton analyzing power, the deuteron vector and tensor analyzing powers, and vector polarization transfer measurements, as well. 8 references

  4. Leading coordinate analysis of reaction pathways in proton chain transfer: Application to a two-proton transfer model for the green fluorescent protein

    International Nuclear Information System (INIS)

    Wang Sufan; Smith, Sean C.

    2006-01-01

    The 'leading coordinate' approach to computing an approximate reaction pathway, with subsequent determination of the true minimum energy profile, is applied to a two-proton chain transfer model based on the chromophore and its surrounding moieties within the green fluorescent protein (GFP). Using an ab initio quantum chemical method, a number of different relaxed energy profiles are found for several plausible guesses at leading coordinates. The results obtained for different trial leading coordinates are rationalized through the calculation of a two-dimensional relaxed potential energy surface (PES) for the system. Analysis of the 2-D relaxed PES reveals that two of the trial pathways are entirely spurious, while two others contain useful information and can be used to furnish starting points for successful saddle-point searches. Implications for selection of trial leading coordinates in this class of proton chain transfer reactions are discussed, and a simple diagnostic function is proposed for revealing whether or not a relaxed pathway based on a trial leading coordinate is likely to furnish useful information

  5. 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.

  6. Target fragmentation in proton-nucleus and /sup 16/O-nucleus reactions at 60 and 200 GeVnucleon

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, H R; Albrecht, R; Awes, T C; Baktash, C; Beckmann, P; Claesson, G; Berger, F; Bock, R; Dragon, L; Ferguson, R L; Franz, A; Garpman, S; Glasow, R; Gustafsson, H A; Gutbrod, H H; Kampert, K H; Kolb, B W; Kristiansson, P; Lee, I Y; Loehner, H; Lund, I; Obenshain, F E; Oskarsson, A; Otterlund, I; Peitzmann, T; Persson, S; Plasil, F; Poskanzer, A M; Purschke, M; Ritter, H G; Santo, R; Siemiarczuk, T; Sorensen, S P; Stenlund, E; Young, G R

    1987-01-01

    Target remnants with Z<3 from proton-nucleus and /sup 16/O-nulceus reactions at 60 and 200 GeVnucleon were measured in the angular range from 30)degree) to 160)degree) (-1.7<)eta)1.3) employing the Plastic Ball detector. The excitation energy of the target spectator matter in central oxygen-induced collisions is found to be high enough to allow for complete disintegration of the target nucelus into fragments with Z<3. The average longtitudinal momentum transfer per proton to the target in central collisions is considerably higher in the case of /sup 16/O-induced reactions (approx.300 MeVc) than in proton-induced reactions (approx.130 MeVc). The baryon rapidity distributions are roughly in agreement with one-fluid hydrodynamical calcualtions at 60 GeVnucleon /sup 16/O)plus)Au but are in disagreement at 200 GeVnucleon, indicating the higher degree of transparency at the higher bombarding energy. Both, the transverse moments of target spectators and the entropy produced in the target gfragmentation region are compared to those attained in head-on collisions of two heavy nuclei at Bevalac energies. They are found to be comparable or do even exceed the values for the participant matter at beam energies of about 1-2 GeVnucleon. 18 refs., 112 figs

  7. Disjunct eddy covariance measurements of volatile organic compound fluxes using proton transfer reaction mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Taipale, R.

    2011-07-01

    Volatile organic compounds (VOCs) are emitted into the atmosphere from natural and anthropogenic sources, vegetation being the dominant source on a global scale. Some of these reactive compounds are deemed major contributors or inhibitors to aerosol particle formation and growth, thus making VOC measurements essential for current climate change research. This thesis discusses ecosystem scale VOC fluxes measured above a boreal Scots pine dominated forest in southern Finland. The flux measurements were performed using the micrometeorological disjunct eddy covariance (DEC) method combined with proton transfer reaction mass spectrometry (PTR-MS), which is an online technique for measuring VOC concentrations. The measurement, calibration, and calculation procedures developed in this work proved to be well suited to long-term VOC concentration and flux measurements with PTR-MS. A new averaging approach based on running averaged covariance functions improved the determination of the lag time between wind and concentration measurements, which is a common challenge in DEC when measuring fluxes near the detection limit. The ecosystem scale emissions of methanol, acetaldehyde, and acetone were substantial. These three oxygenated VOCs made up about half of the total emissions, with the rest comprised of monoterpenes. Contrary to the traditional assumption that monoterpene emissions from Scots pine originate mainly as evaporation from specialized storage pools, the DEC measurements indicated a significant contribution from de novo biosynthesis to the ecosystem scale monoterpene emissions. This thesis offers practical guidelines for long-term DEC measurements with PTR-MS. In particular, the new averaging approach to the lag time determination seems useful in the automation of DEC flux calculations. Seasonal variation in the monoterpene biosynthesis and the detailed structure of a revised hybrid algorithm, describing both de novo and pool emissions, should be determined in

  8. Investigation of coulomb and pairing effects using new developed empirical formulas for proton-induced reaction cross sections

    International Nuclear Information System (INIS)

    Tel, E.; Aydin, E. G.; Aydin, A.; Kaplan, A.; Boeluekdemir, M. H.; Okuducu, S.

    2010-01-01

    We have investigated Coulomb and pairing effects by using new empirical formulas including the new coefficients for (p, α) at 17.9 MeV, (p, np) at 22.3 MeV, and (p, nα) at 24.8 and 28.5 MeV energies. A new formula is obtained by adjusting Levkovskii's original asymmetry parameter formula and also Tel et al. formula for proton-induced reactions. The new coefficients by using least-squares fitting method for the reactions are determined. In addition, the findings of the present study are compared with the available experimental data.

  9. Measurement of the proton screening correction in a deuteron for reactions π-+p(d)→π++X

    International Nuclear Information System (INIS)

    Abramov, B.M.; Dukhovskoj, I.A.; Fedoretz, V.S.; Kishkurno, V.V.; Kondratyuk, L.A.; Krutenkova, A.P.; Kulikov, V.V.; Matsyuk, M.A.; Radkevich, I.A.; Turdakina, E.N.

    1979-01-01

    The proton screening correction deltasub(p) in a deuteron has been measured by comparative investigation of reactions π - d→π + X - and π - P→π + X - at π 0 =2.6 GeV/c and πsub(perpendicular)sup(2)=0.0025+-0.0025(GeV/c) 2 . In the region under investigation the reaction π - n → π + X - - is kinematically forbidden. On the basis of the value deltasub(p)=0.177+-0.019 the Glauber parameter was found to be 2 >=0.37+-0.05fm

  10. Presolvated Electron Reactions with Methyl Acetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-Atom Abstraction

    Directory of Open Access Journals (Sweden)

    Alex Petrovici

    2014-09-01

    Full Text Available Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methyl acetoacetate (MAA, CH3-CO-CH2-COOCH3 at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-COOCH3 in the 77 to ca. 170 K temperature range have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•OH-CH2-COOCH3. The ESR spectrum of CH3-C(•OH-CH2-COOCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•OH-CH2-COOCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylene protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K, CH3-C(•OH-CH2-COOCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-COOCH3. Theoretical calculations using density functional theory (DFT support the radical assignments.

  11. Presolvated electron reactions with methyl acetoacetate: electron localization, proton-deuteron exchange, and H-atom abstraction.

    Science.gov (United States)

    Petrovici, Alex; Adhikary, Amitava; Kumar, Anil; Sevilla, Michael D

    2014-09-01

    Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methyl acetoacetate (MAA, CH3-CO-CH2-COOCH3) at 77 K and subsequent reactions of the anion radical (CH3-CO•--CH2-COOCH3) in the 77 to ca. 170 K temperature range have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR) spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•)OH-CH2-COOCH3. The ESR spectrum of CH3-C(•)OH-CH2-COOCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•)OH-CH2-COOCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylene protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K), CH3-C(•)OH-CH2-COOCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-COOCH3. Theoretical calculations using density functional theory (DFT) support the radical assignments.

  12. Hadron correlations in nuclear reactions with production of cumulative protons induced by π- mesons with momentum of 6.0 GeV/c

    International Nuclear Information System (INIS)

    Bayukov, Yu.D.; Vlasov, A.V.; Gavrilov, V.B.

    1981-01-01

    Hardonic correlations were investigated in reactions with the proton backward production induced by 6.0-GeV/c π - mesons on nuclei Be, C, Al, Cu, Cd, Pb, U. The studied correlations indicate an essential role of multiple interactions of the incident particle in production of cumulative protons [ru

  13. Optimization of the pion beam for the HADES detector and determination of the η form factor in proton-proton reactions at 2.2 GeV

    International Nuclear Information System (INIS)

    Spruck, Bjoern

    2008-01-01

    This thesis contains two tasks. The first part focuses on the development and optimization of the pion beam facility for the HADES experiment. The second part describes the measurement of the electromagnetic transition form factor of the η meson in proton-proton reactions. To investigate pion-nucleon reaction, a secondary pion beam is required. The pions are produced by a heavy ion beam impinging on a beryllium target. In order to determine the profile of the beam focus, two scintillating fiber detectors have been built as part of this thesis and are read out with recently developed electronics. The measured size of the beam focus appeared to be not acceptable, which can be attributed to the achromatic magnetic focusing in the beam line. Simulations have shown, that an additional quadrupole magnet directly in front of HADES would solve this problem and improve the beam quality. A test experiment including this new quadrupole has been performed and the analysis is still in progress. Preliminary results show a significant reduction of the momentum dependency of the focus. The size of the actual beam spot has been deduced to 14 mm by using an indirect tracking approach. For deducing the electromagnetic structure of hadrons, a first step has been done by analyzing the η Dalitz decay in p+p reactions at 2.2 GeV kinetic energy to determine the electromagnetic transition form factor of the η meson. A fit to the data leads to a form factor slope of b=2.2 -1.4 +1.2 GeV -2 . This corresponds to a pole mass of λ=680 -130 +460 MeV/c 2 . It has been shown, that a semi-exclusive analysis of the η Dalitz decay within the event hypothesis framework including a kinematical fit is feasible. (orig.)

  14. Kinetic isotope effects and tunnelling in the proton-transfer reaction between 4-nitrophenylnitromethane and tetramethylguanidine in various aprotic solvents

    International Nuclear Information System (INIS)

    Caldin, E.F.; Mateo, S.

    1975-01-01

    Rates and equilibrium constants have been determined for the proton-transfer reaction of 4-nitrophenylnitromethane, NO 2 C 6 H 4 CH 2 NO 2 , and its αα-deuterated analogue NO 2 C 6 H 4 CD 2 NO 2 , with the strong base tetramethylguanidine [HN=C(NMe 2 ) 2 ), at temperatures between -60 0 C and +65 0 in a range of aprotic solvents. Spectrophotometry and the stopped-flow technique were used. The reaction is a simple proton-transfer process leading to an ion-pair. The kinetic isotope effects are correlated with the polarity of the solvents, as measured by the dielectric constant or by the empirical parameter Esub(T). In the less polar solvents they are exceptionally large. In toluene, for example, at 25 0 C the rate ratio ksup(H)/ksup(D) = 45 +- 2, the activation energy difference Esub(a)sup(D) - Esub(a)sup(H) =4.3 +- 0.3 kcal molsup(-1) (16 kJ molsup(-1), and the ratio of the pre-exponential factors logsub(10) (Asup(D)/Asup(H)) = 1.5 +- 0.2+ and even larger values of logsub(10)(Asup(D)/Asup(H)) are found for mesitylene (1.94 +- 0.06) and cyclohexane (2.4 +- 0.2). Positive deviations from linear Arrhenius plots are found for these solvents. Tunnelling is the only interpretation that cannot account for these results. For the more polar solvents (dielectric constant 7 to 37), the isotope effects are closer to the range predicted by semi-classical theory. The isotope effects in all solvents have been fitted to Bell's equation for a parabolic barrier, and the barrier dimensions calculated for each solvent. The suggested interpretation of the results is that the solvent-solute interactions affect the height of the barrier and that motions of solvent molecules are coupled with the motion of the proton in the more polar solvents but not in the less polar ones; reorganization of solvent molecules accompanies the proton-transfer in the more polar solvents, but only electron-polarization in the less polar. Tunnelling has large effects in the less polar solvents, where the

  15. Proton transfer in malonaldehyde: From reaction path to Schrödinger's Cat

    Science.gov (United States)

    Fillaux, François; Nicolaï, Béatrice

    2005-11-01

    Proton transfer in the chelated form of malonaldehyde is commonly supposed to occur between two tautomers, across a transition state involving changes of the chemical bonding. We show that this view is in conflict with rotational spectra. The molecule is better thought of as a superposition of indistinguishable and non-separable C s tautomers and proton tunneling is totally decoupled from the other degrees of freedom. Double minimum potential functions are determined from experiments and ab initio calculations.

  16. Contribution to the analysis of dileptons production reactions in proton-proton collision with HADES; Contribution a l'analyse de reactions de production de dileptons en collision proton-proton avec HADES

    Energy Technology Data Exchange (ETDEWEB)

    Moriniere, E

    2008-03-15

    The most recent analysis of dilepton spectra, produced in heavy ion collisions, have shown the need for a precise knowledge of all dilepton production channels. The experimental HADES facility, installed on the GSI accelerator site, is appropriate for that goal. Thus, the Dalitz decay branching ratio of {delta} resonance ({delta} {yields} Ne{sup +}e{sup -}), which has never been measured, is studied in this work. Moreover, the pp {yields} p/ {delta}{sup +} {yields} ppe{sup +-} reaction could allow to provide some information about the internal resonance structure and more precisely, about the electromagnetic transition N - A form factors. The analysis of simulations shows the feasibility of this experiment, estimates the counting yield as well as the Signal over Background ratio. This analysis shows also the great importance of the momentum resolution of the detector for the success of this experiment. The momentum resolution must be investigated. In this work, an attempt to find out the most important contributions to the measured resolution is presented. The calibration step, which provides the relation between electronic time and physical time, the detector alignment (global, relative or internal) as well as the tracking method are studied. Some methods for improvement of these different contributions are proposed in order to reach the optimal resolution. (author)

  17. Analysis of the proton-induced reactions at 150 MeV - 24 GeV by high energy nuclear reaction code JAM

    International Nuclear Information System (INIS)

    Niita, Koji; Nara, Yasushi; Takada, Hiroshi; Nakashima, Hiroshi; Chiba, Satoshi; Ikeda, Yujiro

    1999-09-01

    We are developing a nucleon-meson transport code NMTC/JAM, which is an upgraded version of NMTC/JAERI. NMTC/JAM implements the high energy nuclear reaction code JAM for the infra-nuclear cascade part. By using JAM, the upper limits of the incident energies in NMTC/JAERI, 3.5 GeV for nucleons and 2.5 GeV for mesons, are increased drastically up to several hundreds GeV. We have modified the original JAM code in order to estimate the residual nucleus and its excitation energy for nucleon or pion induced reactions by assuming a simple model for target nucleus. As a result, we have succeeded in lowering the applicable energies of JAM down to about 150 MeV. In this report, we describe the main components of JAM code, which should be implemented in NMTC/JAM, and compare the results calculated by JAM code with the experimental data and with those by LAHET2.7 code for proton induced reactions from 150 MeV to several 10 GeV. It has been found that the results of JAM can reproduce quite well the experimental double differential cross sections of neutrons and pions emitted from the proton induced reactions from 150 MeV to several 10 GeV. On the other hand, the results of LAHET2.7 show the strange behavior of the angular distribution of nucleons and pions from the reactions above 4 GeV. (author)

  18. 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.

  19. Target fragmentation in proton-nucleus and 16O-nucleus reactions at 60 and 200 GeV/nucleon

    International Nuclear Information System (INIS)

    Schmidt, H.R.; Albrecht, R.; Claesson, G.; Bock, R.; Gutbrod, H.H.; Kolb, B.W.; Lund, I.; Siemiarczuk, T.; Awes, T.C.; Baktash, C.; Ferguson, R.L.; Lee, I.Y.; Obenshain, F.E.; Plasil, F.; Sorensen, S.P.; Young, G.R.; Beckmann, P.; Berger, F.; Dragon, L.; Glasow, R.; Kampert, K.H.; Loehner, H.; Peitzmann, T.; Purschke, M.; Santo, R.; Franz, A.; Kristiansson, P.; Poskanzer, A.M.; Ritter, H.G.; Garpman, S.; Gustafsson, H.A.; Oskarsson, A.; Otterlund, I.; Persson, S.; Stenlund, E.

    1988-01-01

    Target remnants with Z 16 O-nucleus reactions at 60 and 200 GeV/nucleon were measured in the angular range from 30 0 to 160 0 (-1.7 16 O-induced reactions (≅ 300 MeV/c) than in proton-induced reactions (≅ 130 MeV/c). The baryon rapidity distributions are roughly in agreement with one-fluid hydrodynamical calculations at 60 GeV/nucleon 16 O+Au but are in disagreement at 200 GeV/nucleon, indicating the higher degree of transparency at the higher bombarding energy. Both, the transverse momenta of target spectators and the entropy produced in the target fragmentation region are compared to those attained in head-on collisions of two heavy nuclei at Bevalac energies. They are found to be comparable or do even exceed the values for the participant matter at beam energies of about 1-2 GeV/nucleon. (orig.)

  20. Target fragmentation in proton-nucleus and 16O-nucleus reactions at 60 and 200 GeV/nucleon

    International Nuclear Information System (INIS)

    Schmidt, H.R.; Albrecht, R.; Claesson, G.; Bock, R.; Gutbrod, H.H.; Kolb, B.W.; Lund, I.; Siemiarczuk, T.; Awes, T.C.; Baktash, C.; Ferguson, R.L.; Lee, I.Y.; Obenshain, F.E.; Plasil, F.; Sorensen, S.P.; Young, G.R.; Beckmann, P.; Berger, F.; Dragon, L.; Glasow, R.; Kampert, K.H.; Loehner, H.; Peitzmann, T.; Purschke, M.; Santo, R.; Franz, A.; Kristiansson, P.; Poskanzer, A.M.; Ritter, H.G.; Garpman, S.; Gustafsson, H.A.; Oskarsson, A.; Otterlund, I.; Persson, S.; Stenlund, E.

    1988-01-01

    Target remnants with Z 16 O-nucleus reactions at 60 and 200 GeV/nucleon were measured in the angular range from 30 0 to 160 0 (-1.7 16 O-induced reactions (= 300 MeV/c) than in proton-induced reactions (= 130 MeV/c). The baryon rapidity distributions are roughly in agreement with one-fluid hydrodynamical calculations at 60 GeV/nucleon 16 O+Au but are in disagreement at 200 GeV/nucleon, indicating the higher degree of transparency at the higher bombarding energy. Both, the transverse momenta of target spectators and the entropy produced in the target fragmentation region are compared to those attained in head-on collisions of two heavy nuclei at Bevalac energies. They are found to be comparable or do even exceed the values for the participant matter at beam energies of about 1-2 GeV/nucleon. (orig.)

  1. Excitation functions for the formation of some short-lived products in proton-induced reactions on silver

    International Nuclear Information System (INIS)

    Uddin, M.S.; Latif, S.K.A.; Baba, M.; Hagiwara, M.; Qaim, S.M.

    2008-01-01

    Excitation functions of the nat Ag(p, xn) 104, 105 Cd and nat Ag(p, pxn) 103, 104m,g, 104g Ag reactions were measured for the first time over the proton energy range of 32 to about 60 MeV. The data were compared with the results of precompound-hybrid model calculations, whereby only partial agreement was obtained. The contribution of the 103 Ag precursor decay to the total formation of the therapeutic radionuclide 103 Pd in proton activation of silver was estimated: it amounted to about 70%. The various possible routes for the production of 103 Pd were also considered: the nat Ag(p, x) 103 Pd and 103 Rh(p, n) 103 Pd processes were found to be most interesting. Despite its somewhat lower yield, the latter process is preferred because it can be applied at a low-energy cyclotron. (orig.)

  2. The future plan for the applications of RI produced in the proton-induced spallation-reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ikezoe, Hiroshi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1997-07-01

    A plan of research facilities (transmutations of minor actinides and neutron scattering for material and life sciences) has been proposed in JAERI. This plan is based on a proton lineac with an energy of 1.5 GeV and a beam current of several mA. Among these facilities, we are planning to accelerate neutron-rich radioactive nuclei (RI) produced in the fission and spallation reactions of thorium or uranium bombarded by the intense high energy proton beams. The RI produced in an ion source are separated by a high resolution isotope separator and their charge states are changed to be negative to inject into the existing tandem-booster accelerator. Main purpose of this plan is to study the nuclear and chemical properties of neutron rich transactinium elements not yet synthesized and the nuclear structures of neutron rich nuclei far from the nuclear stability line. (author)

  3. 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...

  4. 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

  5. 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....

  6. 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.

  7. An efficient catalyst for asymmetric Reformatsky reaction

    Indian Academy of Sciences (India)

    rate enantioselectivity using N,N-dialkylnorephedrines as chiral ligands. ..... temperatures also, there was no product conversion. ... Optimization of reaction conditions for asymmetric Reformatsky reaction between benzaldehyde and α-.

  8. Reaction Mechanism and Structure Interplay for Proton Elastic Scattering from Halo Nuclei

    International Nuclear Information System (INIS)

    Crespo, R.; Johnson, R.C.

    1999-01-01

    The aim of this work is to clarify what properties of the projectile w.f. are relevant to describe elastic scattering of halo nuclei from stable nuclei. In particular, we examine how far elastic scattering observables probe correlation effects among projectile nucleons. Our treatment is based on a multiple scattering expansion of the proton-projectile transition amplitude in a form which is well adapted to the weakly bound cluster picture of halo nuclei. In the specific case of 11 Li scattering from protons at 800 MeV/u we show that because core recoil effects are significant, scattering cross sections can not, in general, be deduced from knowledge of the total matter density alone. We advocate that the optical potential concept for the scattering of halo nuclei on protons should be avoided and that the multiple scattering series for the full transition amplitude should be used instead

  9. Reaction mechanism and structure interplay for proton elastic scattering from halo nuclei

    International Nuclear Information System (INIS)

    Crespo, R.; Johnson, R. C.

    1999-01-01

    The aim of this work is to clarify what properties of the projectile w.f. are relevant to describe elastic scattering of halo nuclei from stable nuclei. In particular, we examine how far elastic scattering observables probe correlation effects among projectile nucleons. Our treatment is based on a multiple scattering expansion of the proton-projectile transition amplitude in a form which is well adapted to the weakly bound cluster picture of halo nuclei. In the specific case of 11 Li scattering from protons at 800 MeV/u we show that because core recoil effects are significant, scattering crosssections cannot, in general, be deduced from knowledge of the total matter density alone. We advocate that the optical potential concept for the scattering of halo nuclei on protons should be avoided and that the multiple scattering series for the full transition amplitude should be used instead

  10. Semi-classical approaches for the proton emission in intermediate energy heavy ion reactions

    International Nuclear Information System (INIS)

    Gregoire, C.; Scheuter, F.; Remaud, B.; Sebille, F.

    1984-05-01

    Semi-classical approaches are proposed to study the transition between the one- and two-body processes in intermediate energy heavy ion collisions. The Landau-Vlasov equation is used as a transport equation for nucleons in the nuclear matter. We apply our formalism to the fast proton ejection. On the one hand, the effects of the nucleon-nucleon collisions are studied for the particles which travel through the nucleus cores. On the other hand, the inertial emission turns out to be an important proton emission mechanism. Our results conflict the interpretation of the proton spectra in terms of moving sources. Reasonable agreements with the experimental data are found without reference to any thermal equilibrium

  11. Proton transfer and unimolecular decay in the low-energy-reaction dynamics of H3O+ with acetone

    International Nuclear Information System (INIS)

    Creasy, W.R.; Farrar, J.M.

    1983-01-01

    The title reaction has been studied at collision energies of 0.83 and 2.41 eV. Direct reaction dynamics have been observed at both energies and an increasingly high fraction of the total energy appears in product translation as the collision energy increases. This result is consistent with the concept of induced repulsive energy release, which becomes more effective as trajectories sample the corner of the potential energy surface. At the higher collision energy, the protonated acetone cation undergoes two unimolecular decay channels: C-C bond cleavage to CH 3 CO + and CH 4 , and C-O bond cleavagto C 3 H 5 + (presumably to allyl cation) and H 2 O. The CH 3 CO + channel, endothermic relative to ground state protonated acetone cations by 0.74 eV, appears to liberate 0.4 eV in relative product translation while the C 3 H 5 + channel, endothermic by 2.17 eV, liberates only 0.07 eV in relative translation. These results are discussed in terms of the location on the reaction coordinate and magnitudes of potential energy barriers to 1,3-hydrogen atoms shifts which must precede the bond cleavage processes

  12. Dynamics of excited-state intramolecular proton transfer reactions in piroxicam. Role of triplet states

    Science.gov (United States)

    Cho, Dae Won; Kim, Yong Hee; Yoon, Minjoong; Jeoung, Sae Chae; Kim, Dongho

    1994-08-01

    The picosecond time-resolved fluorescence and transient absorption behavior of piroxicam at room temperature are reported. The keto tautomer in the excited singlet state ( 1K*) formed via the fast intramolecular proton transfer (≈ 20 ps) is observed. The short-lived (7.5 ns) triplet state of keto tauomer ( 3K*) is generated from 1K * in toluene whereas it is hardly observed in ethanol. Consequently, rapid reverse proton transfer takes place from 3K * to the enol triplet state ( 3E *.

  13. Direct nuclear reactions with polarized protons: an experimental study of Ge and Se

    International Nuclear Information System (INIS)

    Moonen, W.H.L.

    1986-01-01

    The present investigation, is concerned with excited states of some transitional nuclides, which, through the experimental improvements, became accessible for polarized proton experiments. The aim was to see how nuclei behave when they have a proton and/or neutron number inbetween 28 and 50. Another aim was the completion of the picture of even-even nuclei in general where the research started with the nuclei Fe (Z=26) and Ni (Z=28). Therefore some nuclei were chosen which follow this series: Ge, Z=32, N=38,40,42,44; Se, Z=34, N=42,44,46. (Auth.)

  14. Cross-sections of spallation residues produced in 1A GeV 208Pb on proton reactions

    International Nuclear Information System (INIS)

    Wlazlo, W.; Uniwersytet Jagiellonski, Cracow; Enqvist, T.; Armbruster, P.

    2000-02-01

    Spallation residues produced in 1 GeV per nucleon 208 Pb on proton reactions have been studied using the fragment separator facility at GSI. Isotopic production cross-sections of elements from 61 Pm to 82 Pb have been measured down to 0.1 mb with a high accuracy. The recoil kinetic energies of the produced fragments were also determined. The obtained cross-sections agree with most of the few existing gamma-spectroscopy data. Data are compared with different intranuclear-cascade and evaporation-fission models. Drastic deviations were found for a standard code used in technical applications. (orig.)

  15. New excitation functions for proton induced reactions on natural titanium, nickel and copper up to 70 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Garrido, E. [SUBATECH, Ecole des Mines de Nantes, Université de Nantes, CNRS/IN2P3, Nantes (France); Duchemin, C., E-mail: Charlotte.Duchemin@subatech.in2p3.fr [SUBATECH, Ecole des Mines de Nantes, Université de Nantes, CNRS/IN2P3, Nantes (France); Guertin, A. [SUBATECH, Ecole des Mines de Nantes, Université de Nantes, CNRS/IN2P3, Nantes (France); Haddad, F.; Michel, N. [SUBATECH, Ecole des Mines de Nantes, Université de Nantes, CNRS/IN2P3, Nantes (France); GIP Arronax, 1 rue Aronnax, 44817 Saint-Herblain (France); Métivier, V. [SUBATECH, Ecole des Mines de Nantes, Université de Nantes, CNRS/IN2P3, Nantes (France)

    2016-09-15

    Highlights: • Natural titanium, nickel and copper targets. • 70 MeV ARRONAX cyclotron proton beam. • Stacked-foil technique and monitor reactions. • Experimental cross section values. • TALYS code version 1.6. - Abstract: New excitation functions for proton induced nuclear reactions on natural titanium, nickel and copper were measured, using the stacked-foil technique and gamma spectrometry, up to 70 MeV. The experimental cross sections were measured using the Ti-nat(p,x) V-48, Ni-nat(p,x) Ni-57 and Cu-nat(p,x) Zn-62,Co-56 monitor reactions recommended by the International Atomic Energy Agency (IAEA), depending on the investigated energy range. Data have been extracted for the Ti-nat(p,x) Sc-43,44m,46,47,48, V-48, K-42,43, Ni-nat(p,x) Ni-56,57, Co-55,56,57,58, Mn-52,54, Cu-nat(p,x) Cu-61,64, Ni-57, Co-56,57,58,60, Zn-62,65, Mn-54 reactions. Our results are discussed and compared to the existing ones as well as with the TALYS code version 1.6 calculations using default models. Our experimental data are in overall good agreement with the literature. TALYS is able to reproduce, in most cases, the experimental trend. Our new experimental results allow to expand our knowledge on these excitation functions, to confirm the existing trends and to give additional values on a large energy range. This work is in line with the new Coordinated Research Project (CRP) launched by the IAEA to expand the database of monitor reactions.

  16. A beam detector for pion experiments and analysis of the inclusive Λ production in proton-proton reactions with HADES

    Energy Technology Data Exchange (ETDEWEB)

    Lalik, Rafal Tomasz

    2016-06-02

    This thesis presents the work focused on two topics related to the physics performed at the HADES detector. In the first part, the development of the tracking detector playing an important role of online beam monitoring and the momentum reconstruction device in the secondary pion beam experiment is presented. Such a detector must fulfill various requirements regarding the operation in the vacuum, with accelerator beams and high count rates. Two detection stations employing double sided silicons strip sensors with an active area of 10 cm x 10 cm and position resolution of 780 μm, providing momentum resolution below 0.5 % and capable for operating with beams up to 32 x 10{sup 6} particles/s total and 2 x 10{sup 6} particles/s in a single channel have been constructed, tested and used in the pion beam experiments. In the first chapter, general information about the production of the secondary, in particular, pion beams is presented. Further, description how the momentum is reconstructed using the information obtained from the tracking detector, and description of most important components of the system, namely the silicon sensor and front end electronics used for its readout is presented. In the second chapter, development of the detector, including all the components used or constructed for this particular purpose is presented. This section also includes description of the laboratory tests and calibrations performed to characterize the detector. In the end of the section, results from two of the beam runs employed for the tests of the detector are presented and discussed. The last third chapter presents results from the commissioning of the tracking detector in the final configuration. Momentum reconstruction feasibility is presented. The second part of the thesis focuses on the analysis of inclusive production of the Λ hyperons in the nuclear reactions at the HADES energies. The aims of the analysis are to extract the differential cross-section of Λ production in

  17. Calculation of A (x) for the Proton-Deuteron Breakup Reaction at 135 MeV

    NARCIS (Netherlands)

    Eslami-Kalantari, M.; Mehmandoost-Khajeh-Dad, A. A.; Shafaei, M. A.; Amir-Ahmadi, H. R.; Biegun, A.; Gasparic, I.; Joulaeizadeh, L.; Kalantar-Nayestanaki, N.; Kistryn, St.; Kozela, A.; Mardanpour, H.; Messchendorp, J. G.; Moeini, H.; Ramazani Moghaddam Arani, Ahmad; Shende, S. V.; Stephan, E.; Sworst, R.

    Observables in proton-deuteron scattering are sensitive probes of the nucleon-nucleon interaction and three-nucleon force effects (3NF). Several facilities in the world, including Kernfysisch Versneller Instituut (KVI), allow a detailed study a few-nucleon interaction below the pion-production

  18. Deamidation reactions of protonated asparagine and glutamine investigated by ion spectroscopy

    NARCIS (Netherlands)

    Kempkes, L.J.M.; Martens, J.K.; Grzetic, J.; Berden, G.; Oomens, J.

    2016-01-01

    RATIONALE: Deamidation of Asn and Gln residues is a primary route for spontaneous post-translational protein modification. Several structures have been proposed for the deamidation products of the protonated amino acids. Here we verify these structures by ion spectroscopy, as well as the structures

  19. Time resolved investigations on biogenic trace gases exchanges using proton-transfer-reaction mass spectrometry

    International Nuclear Information System (INIS)

    Karl, T.

    2000-02-01

    Volatile organic compounds (VOCs) released from vegetation, including wound-induced VOCs, can have important effects on atmospheric chemistry. The analytical methods for measuring wound-induced VOCs, especially the hexenal family of VOCs (hexenals, hexenols and hexenyl esters) but also compounds like acetaldehyde, are complicated by their chemical instability and the transient nature of their formation after leaf and stem wounding. The goal of this thesis was to assess, quantify and complement our understanding on the origin of tropospheric VOCs. This thesis demonstrates that formation and emission of hexenal family compounds can be monitored on-line using proton-transfer-reaction mass spectrometry (PTR-MS), avoiding the need for preconcentration or chromatography. These measurements revealed the rapid emission of the parent compound, (Z)-3-hexenal, within 1-2 seconds of wounding of leaves from various woody and nonwoody plants, and its metabolites including (E)-2-hexenal, hexenols and hexenyl acetates. Emission of (Z)-3-hexenal from detached, drying leaves averaged 500 μg (gram dry weight)-1. PTR-MS showed to be a useful tool for the analysis of VOC emissions resulting from grazing, herbivory, harvesting and senescing leaves. The release of reactive VOCs during lawn mowing was observed in on-line ambient air measurements in July and August 1998 in the outskirts of Innsbruck. Also obtained were data on emission rates of reactive aldehydes (hexenyl compounds) and other abundant VOCs such as methanol, acetaldehyde and acetone from drying grass in various chamber experiments. Fluxes were measured after cutting of grass using eddy covariance measurements and the micrometeorological gradient method (Obhukov-Similarity-Method). Comparison of data obtained by these different methods showed satisfactory agreement. The highest fluxes for methanol during drying were 5 mg/m2h, for (Z)-3-hexenal 1.5 mg/m2h. Experiments conducted on the Sonnblick Observatory in Fall and Winter

  20. Characterisation of Dissolved Organic Carbon by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry

    Science.gov (United States)

    Materić, Dušan; Peacock, Mike; Kent, Matthew; Cook, Sarah; Gauci, Vincent; Röckmann, Thomas; Holzinger, Rupert

    2017-04-01

    Dissolved organic carbon (DOC) is an integral component of the global carbon cycle. DOC represents an important terrestrial carbon loss as it is broken down both biologically and photochemically, resulting in the release of carbon dioxide (CO2) to the atmosphere. The magnitude of this carbon loss can be affected by land management (e.g. drainage). Furthermore, DOC affects autotrophic and heterotrophic processes in aquatic ecosystems, and, when chlorinated during water treatment, can lead to the release of harmful trihalomethanes. Numerous methods have been used to characterise DOC. The most accessible of these use absorbance and fluorescence properties to make inferences about chemical composition, whilst high-performance size exclusion chromatography can be used to determine apparent molecular weight. XAD fractionation has been extensively used to separate out hydrophilic and hydrophobic components. Thermochemolysis or pyrolysis Gas Chromatography - Mass Spectrometry (GC-MS) give information on molecular properties of DOC, and 13C NMR spectroscopy can provide an insight into the degree of aromaticity. Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a sensitive, soft ionisation method suitable for qualitative and quantitative analysis of volatile and semi-volatile organic vapours. So far, PTR-MS has been used in various environmental applications such as real-time monitoring of volatile organic compounds (VOCs) emitted from natural and anthropogenic sources, chemical composition measurements of aerosols etc. However, as the method is not compatible with water, it has not been used for analysis of organic traces present in natural water samples. The aim of this work was to develop a method based on thermal desorption PTR-MS to analyse water samples in order to characterise chemical composition of dissolved organic carbon. We developed a clean low-pressure evaporation/sublimation system to remove water from samples and thermal desorption system to introduce

  1. 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.

  2. 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 ...

  3. Analysis for fragmentation products of proton-induced reactions on Pb with energy up to GeV

    International Nuclear Information System (INIS)

    Fan Sheng; Li Zhuxia; Zhao Zhixiang; Ding Dazhao

    2002-01-01

    The mass and charge distribution of residual products produced in the spallation reaction needs to be studied because it can provide useful information for the disposal of nuclear and the radiation damage in the spallation target. The mass and charge distribution of the spallation products is studied by using quantum molecular dynamic (QMD) models. The simulation results are well agreed with the experimental data of the spallation fragment and empirical formula. However, QMD model does not include the fission process; the calculations can not reproduce the fission fragment. The fission model is introduced into QMD model to investigate the fragment products from proton-induced reactions on Pb. The results are in good agreement with the experimental data

  4. The H2 + + He proton transfer reaction: quantum reactive differential cross sections to be linked with future velocity mapping experiments

    Science.gov (United States)

    Hernández Vera, Mario; Wester, Roland; Gianturco, Francesco Antonio

    2018-01-01

    We construct the velocity map images of the proton transfer reaction between helium and molecular hydrogen ion {{{H}}}2+. We perform simulations of imaging experiments at one representative total collision energy taking into account the inherent aberrations of the velocity mapping in order to explore the feasibility of direct comparisons between theory and future experiments planned in our laboratory. The asymptotic angular distributions of the fragments in a 3D velocity space is determined from the quantum state-to-state differential reactive cross sections and reaction probabilities which are computed by using the time-independent coupled channel hyperspherical coordinate method. The calculations employ an earlier ab initio potential energy surface computed at the FCI/cc-pVQZ level of theory. The present simulations indicate that the planned experiments would be selective enough to differentiate between product distributions resulting from different initial internal states of the reactants.

  5. Neutronigen target study and realization for medical cyclotron using proton reactions on lithium deuteride

    International Nuclear Information System (INIS)

    Filhol, J.M.

    1984-02-01

    The new idea, used for this source realization, consists of replacing the classical beryllium targets (usuals in neutronotherapy cyclotrons) by a half-thick lithium deuteride target. The target is bombarded by high energy 150 MeV) protons which are beyond the target, deviated out of the neutron beam by a permanent magnet, before to be stopped in a graphite block. Target cooling conditions study and optimisation is presented, followed by the proton deflection block study and realization. The permanent magnet used (SmCo 5 ) is adapted to this target use conditions. Many series of neutronic and dosimetric characteristics measurements allow to verify the theoretical predictions concerning the neutron flux obtained [fr

  6. Proton-induced knockout reactions with netron-rich oxygen isotopes at R{sup 3}B

    Energy Technology Data Exchange (ETDEWEB)

    Atar, Leyla [IKP, TU Darmstadt (Germany); GSI (Germany); Collaboration: R3B-Collaboration

    2014-07-01

    Proton-induced knockout reactions are one of the main goal of the experimental program at the future R{sup 3}B (Reactions with Relativistic Radioactive Beams) Experiment at FAIR. It allows us to obtain spectroscopic information about valence and deeply bound single-nucleon states and to study their evolution over a large variation in isospin. Recent studies have shown that the occupancies of loosely bound valence nucleons in neutron- or proton-rich nuclei have a spectroscopic factor close to unity, whereas single-particle strength for deeply bound nucleons is suppressed in isospin asymmetric systems compared to the predictions of the many-body shell model. Further experimental and theoretical studies are needed for a qualitative and quantitative understanding. For this aim a series of measurements have been performed on the complete oxygen isotopic chain using the existing experimental setup LAND/R{sup 3}B at GSI. We present the main scientific goals, the concepts of the experiment and the preliminary results.

  7. Analysis of Native-Like Proteins and Protein Complexes Using Cation to Anion Proton Transfer Reactions (CAPTR)

    Science.gov (United States)

    Laszlo, Kenneth J.; Bush, Matthew F.

    2015-12-01

    Mass spectra of native-like protein complexes often exhibit narrow charge-state distributions, broad peaks, and contributions from multiple, coexisting species. These factors can make it challenging to interpret those spectra, particularly for mixtures with significant heterogeneity. Here we demonstrate the use of ion/ion proton transfer reactions to reduce the charge states of m/ z-selected, native-like ions of proteins and protein complexes, a technique that we refer to as cation to anion proton transfer reactions (CAPTR). We then demonstrate that CAPTR can increase the accuracy of charge state assignments and the resolution of interfering species in native mass spectrometry. The CAPTR product ion spectra for pyruvate kinase exhibit ~30 peaks and enable unambiguous determination of the charge state of each peak, whereas the corresponding precursor spectra exhibit ~6 peaks and the assigned charge states have an uncertainty of ±3%. 15+ bovine serum albumin and 21+ yeast enolase dimer both appear near m/ z 4450 and are completely unresolved in a mixture. After a single CAPTR event, the resulting product ions are baseline resolved. The separation of the product ions increases dramatically after each subsequent CAPTR event; 12 events resulted in a 3000-fold improvement in separation relative to the precursor ions. Finally, we introduce a framework for interpreting and predicting the figures of merit for CAPTR experiments. More generally, these results suggest that CAPTR strongly complements other mass spectrometry tools for analyzing proteins and protein complexes, particularly those in mixtures.

  8. Target fragmentation in proton-nucleus and16O-nucleus reactions at 60 and 200 GeV/nucleon

    Science.gov (United States)

    Albrecht, R.; Awes, T. C.; Baktash, C.; Beckmann, P.; Claesson, G.; Berger, F.; Bock, R.; Dragon, L.; Ferguson, R. L.; Franz, A.; Garpman, S.; Glasow, R.; Gustafsson, H. Å.; Gutbrod, H. H.; Kampert, K. H.; Kolb, B. W.; Kristiansson, P.; Lee, I. Y.; Löhner, H.; Lund, I.; Obenshain, F. E.; Oskarsson, A.; Otterlund, I.; Peitzmann, T.; Persson, S.; Plasil, F.; Poskanzer, A. M.; Purschke, M.; Ritter, H. G.; Santo, R.; Schmidt, H. R.; Siemiarczuk, T.; Sorensen, S. P.; Stenlund, E.; Young, G. R.

    1988-03-01

    Target remnants with ZPlastic Ball detector. The excitation energy of the target spectator matter in central oxygen-induced collisions is found to be high enough to allow for complete disintegration of the target nucleus into fragments with Z<3. The average longitudinal momentum transfer per proton to the target in central collisions is considerably higher in the case of16O-induced reactions (≈300 MeV/c) than in proton-induced reactions (≈130 MeV/c). The baryon rapidity distributions are roughly in agreement with one-fluid hydrodynamical calculations at 60 GeV/nucleon16O+Au but are in disagreement at 200 GeV/nucleon, indicating the higher degree of transparency at the higher bombarding energy. Both, the transverse momenta of target spectators and the entropy produced in the target fragmentation region are compared to those attained in head-on collisions of two heavy nuclei at Bevalac energies. They are found to be comparable or do even exceed the values for the participant matter at beam energies of about 1 2 GeV/nucleon.

  9. Field theoretical approach to proton-nucleus reactions: II-Multiple-step excitation process

    International Nuclear Information System (INIS)

    Eiras, A.; Kodama, T.; Nemes, M.

    1989-01-01

    A field theoretical formulation to multiple step excitation process in proton-nucleus collision within the context of a relativistic eikonal approach is presented. A closed form expression for the double differential cross section can be obtained whose structure is very simple and makes the physics transparent. Glauber's formulation of the same process is obtained as a limit of ours and the necessary approximations are studied and discussed. (author) [pt

  10. High energy nuclear data evaluations for neutron-, proton-, and photon-induced reactions at KAERI

    International Nuclear Information System (INIS)

    Lee, Young Ouk; Chang, Jong Hwa; Kim, Doo Hwan; Lee, Jeong Yeon; Han, Yinlu; Sukhovitski, Efrem Sh.

    2001-01-01

    The Korea Atomic Energy Research Institute (KAERI) is building high energy neutron-, proton-, and photon-induced nuclear data libraries for energies up to hundreds MeV in response to nuclear data needs from various R and Ds and applications. The librares provide nuclear data needed for the accelerator-driven transmutation of nuclear waste and radiation transport simulations of cancer radiotherapy. The neutron library currently has 10 isotopes such as C-12, N-14, O-16, Al-27, Si-28, Ca-40, Fe-56, Ni-58, Zr-90, Sn-120, and Pb-208 for energies from 20 up to 400 MeV. The proton nuclear data were evaluated in a consistent manner with the neutron case, using the same nuclear model parameters. In addition to the same isotopes included in the neutron library, the proton library has 70 extra isotopes of 24 elements ranging from nitrogen to lead up to 150 MeV for which the evaluations are focused on the medical and activation analyses applications. The photonuclear data library has been built along with international collaboration by participating in the IAEA's Coordinated Research Project (CRP) which ended last year. Currently the KAERI photonuclear library includes 143 isotopes of 39 elements

  11. Intramolecular kinetic isotope effect in gas-phase proton-transfer reactions

    International Nuclear Information System (INIS)

    Wellman, K.M.; Victoriano, M.E.; Isolani, P.C.; Riveros, J.M.

    1979-01-01

    The k/sub H//k/sub D/ isotope effects were determined by ICR for the reaction of substituted toluenes with several alkoxides. The results showed a definite trend for k/sub H//k/sub D/ starting as a normal isotope effect for appreciably exothermic reaction (> 3 kcal mol -1 ) and proceeding smoothly toward an inverse isotope effect as the reaction approached thermoneutrality or becomes endothermic. These observations were explained by a reaction which involved a double minima potential with a central energy barrier

  12. Protective effect of transparent film dressing on proton therapy induced skin reactions

    International Nuclear Information System (INIS)

    Whaley, Jonathan T; Kirk, Maura; Cengel, Keith; McDonough, James; Bekelman, Justin; Christodouleas, John P

    2013-01-01

    Proton therapy can result in clinically significant radiation dermatitis. In some clinical scenarios, such as lung or breast cancer, the risk of severe radiation dermatitis may limit beam arrangement and prescription doses. Patients undergoing proton therapy for prostate cancer commonly develop mild radiation dermatitis. Herein, we report the outcomes of two prostate cancer patients whose radiation dermatitis appears to have been substantially diminished by transparent film dressings (Beekley stickers). This is a descriptive report of the skin toxicity observed in two patients undergoing proton therapy for prostate cancer at a single institution in 2011. A phantom dosimetric study was performed to evaluate the impact of a transparent film dressing on a beam’s spread out Bragg peak (SOBP). Two patients with low risk prostate cancer were treated with proton therapy to a total dose of 79.2Gy (RBE) in 1.8 Gy (RBE) fractions using two opposed lateral beams daily. Both patients had small circular (2.5 cm diameter) transparent adhesive markers placed on their skin to assist with daily alignment. Patient 1 had markers in place bilaterally for the entirety of treatment. Patient 2 had a marker in place for three weeks on one side and six weeks on the other. Over the course of therapy, both men developed typical Grade 1 radiation dermatitis (asymptomatic erythema) on their hips; however, in both patients, the erythema was substantially decreased beneath the markers. Patient 2 demonstrated less attenuation and thus greater erythema in the skin covered for three weeks compared to the skin covered for six weeks. The difference in skin changes between the covered and uncovered skin persisted for at least 1 month. A phantom study of double scattered beam SOBP with and without the marker in the beam path showed no gross dosimetric effect. Transparent adhesive markers appear to have attenuated radiation dermatitis in these two patients without affecting the SOBP. One patient may

  13. Modeling of the symmetry factor of electrochemical proton discharge via the Volmer reaction

    DEFF Research Database (Denmark)

    Björketun, Mårten E.; Tripkovic, Vladimir; Skúlason, Egill

    2013-01-01

    A scheme for evaluating symmetry factors of elementary electrode reactions using a density functional theory (DFT) based model of the electrochemical double layer is presented. As an illustration, the symmetry factor is determined for hydrogen adsorption via the electrochemical Volmer reaction...

  14. Low-lying states and structure of the exotic 8He via direct reactions on the proton

    International Nuclear Information System (INIS)

    Skaza, F.; Lapoux, V.; Keeley, N.; Alamanos, N.; Auger, F.; Beaumel, D.; Becheva, E.; Blumenfeld, Y.; Delaunay, F.; Drouart, A.; Gillibert, A.; Giot, L.; Khan, E.; Nalpas, L.; Pakou, A.; Pollacco, E.; Raabe, R.; Roussel-Chomaz, P.; Rusek, K.; Scarpaci, J.-A.; Sida, J.-L.; Stepantsov, S.; Wolski, R.

    2007-01-01

    The structure of the light exotic nucleus 8 He was investigated using direct reactions of the 8 He SPIRAL beam on a proton-rich target. The (p,p') scattering to the 2 1 + state, the (p,d) 7 He and (p,t) 6 He transfer reactions, were measured at the energy E lab =15.7 A.MeV. The light charged particles (p,d,t) were detected in the MUST Si-strip telescope array. The excitation spectrum of 8 He was extracted from the (p,p') reaction. Above the known 2 1 + excited state at 3.6 MeV, a second resonance was found around 5.4 MeV. The cross sections were analyzed within the coupled-reaction channels framework, using microscopic potentials. It is inferred that the 8 He ground state has a more complex neutron-skin structure than suggested by previous α+4n models assuming a pure (1p 3/2 ) 4 configuration

  15. Investigation of the reaction mechanism by means of polarized proton scattering at 30 Si in the range of Ericson fluctuations

    International Nuclear Information System (INIS)

    Wangler, M.

    1978-01-01

    By measuring cross section fluctuations in the area of heavily overlapping resonances (Ericson-fluctuations) one is able to extract nuclear properties like level width and level distance. For the elastic scattering case of polarized spin 1/2-particles at nuclei with zero spin one is able to determine the direct reaction part independently from the model by evaluating the polarized and unpolarized cross sections. For this reason the reaction 30 Si(p,p 0 ) and 30 Si(p,p 1 ) was measured with polarized protons in the angular range 50 0 0 , ΔTHETA = 10 0 . The bombarding energy was varied between 8.500 MeV and 10.680 MeV with 20 keV steps. A mean value of (18.5 +- 2.9) keV resulted for the coherence width that was in agreement for the measurements with polarized and unpolarized particles. To define a final value of the reaction mechanism in elastic scattering the direct part of reaction was determined for all angles. (orig.) [de

  16. Neutron-proton bremsstrahlung from intermediate energy heavy-ion reactions as a probe of the nuclear symmetry energy?

    International Nuclear Information System (INIS)

    Yong, G.-C.; Li Baoan; Chen Liewen

    2008-01-01

    Hard photons from neutron-proton bremsstrahlung in intermediate energy heavy-ion reactions are examined as a potential probe of the nuclear symmetry energy within a transport model. Effects of the symmetry energy on the yields and spectra of hard photons are found to be generally smaller than those due to the currently existing uncertainties of both the in-medium nucleon-nucleon cross sections and the photon production probability in the elementary process pn→pnγ. Very interestingly, nevertheless, the ratio of hard photon spectra R 1/2 (γ) from two reactions using isotopes of the same element is not only approximately independent of these uncertainties but also quite sensitive to the symmetry energy. For the head-on reactions of 132 Sn + 124 Sn and 112 Sn + 112 Sn at E beam /A=50 MeV, for example, the R 1/2 (γ) displays a rise up to 15% when the symmetry energy is reduced by about 20% at ρ=1.3ρ 0 which is the maximum density reached in these reactions

  17. Computing the cross sections of nuclear reactions with nuclear clusters emission for proton energies between 30 MeV and 2.6 GeV

    Energy Technology Data Exchange (ETDEWEB)

    Korovin, Yu. A.; Maksimushkina, A. V., E-mail: AVMaksimushkina@mephi.ru; Frolova, T. A. [Obninsk Institute for Nuclear Power Engineering, National Research Nuclear University MEPhI (Moscow Engineering Physics Institute) (Russian Federation)

    2016-12-15

    The cross sections of nuclear reactions involving emission of clusters of light nuclei in proton collisions with a heavy-metal target are computed for incident-proton energies between 30 MeV and 2.6 GeV. The calculation relies on the ALICE/ASH and CASCADE/INPE computer codes. The parameters determining the pre-equilibrium cluster emission are varied in the computation.

  18. 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.

  19. Calculation of proton total reaction cross sections for some target nuclei in incident energy range of 10-600 MeV

    International Nuclear Information System (INIS)

    Bueyuekuslu, H.; Kaplan, A.; Aydin, A.; Tel, E.; Yildirim, G.

    2010-01-01

    In this study, proton total reaction cross sections have been investigated for some isotopes such as 12 C, 27 Al, 9 Be, 16 O, 181 Ta, 197 Au, 6 Li, and 14 N by a proton beam up to 600 MeV. Calculation of the proton total cross sections has been carried out by the analytic expression formulated by M.A. Alvi by using Coulomb-modified Glauber theory with the Helm model nuclear form factor. The obtained results have been discussed and compared with the available experimental data and found to be in agreement with each other.

  20. Neutron and Proton Diffusion in Fusion Reactions for the Synthesis of Superheavy Nuclei

    International Nuclear Information System (INIS)

    Ming-Hui, Huang; Zai-Guo, Gan; Zhao-Qing, Feng; Xiao-Hong, Zhou; Jun-Qing, Li

    2008-01-01

    The restriction of the one dimensional (1D) master equation (ME) with the mass number of the projectile-like fragment as a variable is studied, and a two-dimensional (2D) master equation with the neutron and proton numbers as independent variables is set up, and solved numerically. Our study showed that the 2D ME can describe the fusion process well in all projectile-target combinations. Therefore the possible channels to synthesize super-heavy nuclei can be studied correctly in wider possibilities. The available condition for employing 1D ME is pointed out

  1. Neutron pair and proton pair transfer reactions between identical cores in the sulfur region

    International Nuclear Information System (INIS)

    Mermaz, M.C.

    1995-12-01

    Optical model and exact finite range distorted-wave Born approximation analyses were performed on neutron pair exchange between identical cores for 32 S and 34 S nuclei and on proton pair exchange between identical cores for 30 Si and 32 S. The extracted spectroscopic factors were compared with theoretical ones deduced from Hartree-Fock calculations on these pair of nuclei. The enhancement of the experimental cross sections with respect to the theoretical ones strongly suggests evidence for a nuclear Josephson effect. (author). 15 refs., 5 figs., 3 tabs

  2. Integral excitation functions for proton and alpha induced reactions on target elements 22 <= Z <= 28

    International Nuclear Information System (INIS)

    Brinkmann, G.

    1979-01-01

    In the framework of a systematic study which is also important for certain cosmological questions a series of integral excitation functions of p- and α-induced nuclear reactions on target elements 22 [de

  3. Detection of forward-scattered protons in photon-induced reactions on the nucleon

    International Nuclear Information System (INIS)

    Koop, Karsten

    2015-01-01

    The study of excitation spectra of hadrons can contribute to a better understanding of the strong interaction. A method is the photoproduction of mesons on the nucleon. Because of the width of the excited states a consideration of polarization observables is helpful in order to be abble to separate overlapping states. In this thesis an experiment for the study of the polarization of the recoil proton is presented. The setup presented here is part of the BGO-OD experiment at the ELSA electron accelerator of the Bonn university. BGO-OD consists of an electromagnetic calorimeter, which surrounds the target, several track detectors in forward direction, and a dipole magnet for the momentum measurement of charged particles. The presented detector is located immediately behind the liquid hydrogen target. In order to be able to determine the polarization of the recoil proton these are scattered on an analyzer, whereby the distribution of the scattering angles is polarization dependent. In this thesis a detector was developed in order to determine the track of the charged particles before and behind the target and by this the scattering angle. Furthermore simulations were performed, which show the realizability of the experiment.

  4. Reaction channel coupling effects for nucleons on 16O: Induced undularity and proton-neutron potential differences

    Science.gov (United States)

    Keeley, N.; Mackintosh, R. S.

    2018-01-01

    Background: Precise fitting of scattering observables suggests that the nucleon-nucleus interaction is l dependent. Such l dependence has been shown to be S -matrix equivalent to an undulatory l -independent potential. The undulations include radial regions where the imaginary term is emissive. Purpose: To study the dynamical polarization potential (DPP) generated in proton-16O and neutron-16O interaction potentials by coupling to pickup channels. Undulatory features occurring in these DPPs can be compared with corresponding features of empirical optical model potentials (OMPs). Furthermore, the additional inclusion of coupling to vibrational states of the target will provide evidence for dynamically generated nonlocality. Methods: The fresco code provides the elastic channel S -matrix Sl j for chosen channel couplings. Inversion, Sl j→V (r ) +l .s VSO(r ) , followed by subtraction of the bare potential, yields an l -independent and local representation of the DPP due to the chosen couplings. Results: The DPPs have strongly undulatory features, including radial regions of emissivity. Certain features of empirical DPPs appear, e.g., the full inverted potential has emissive regions. The DPPs for different collective states are additive except near the nuclear center, whereas the collective and reaction channel DPPs are distinctly nonadditive over a considerable radial range, indicating dynamical nonlocality. Substantial differences between the DPPs due to pickup coupling for protons and neutrons occur; these imply a greater difference between proton and neutron OMPs than the standard phenomenological prescription. Conclusions: The onus is on those who object to undularity in the local and l -independent representation of nucleon elastic scattering to show why such undulations do not occur. This work suggests that it is not legitimate to halt model-independent fits to high-quality data at the appearance of undularity.

  5. cis-chlorobenzene dihydrodiol dehydrogenase (TcbB) from Pseudomonas sp. strain P51, expressed in Escherichia coli DH5alpha(pTCB149), catalyzes enantioselective dehydrogenase reactions.

    Science.gov (United States)

    Raschke, H; Fleischmann, T; Van Der Meer, J R; Kohler, H P

    1999-12-01

    cis-Chlorobenzene dihydrodiol dehydrogenase (CDD) from Pseudomonas sp. strain P51, cloned into Escherichia coli DH5alpha(pTCB149) was able to oxidize cis-dihydrodihydroxy derivatives (cis-dihydrodiols) of dihydronaphthalene, indene, and four para-substituted toluenes to the corresponding catechols. During the incubation of a nonracemic mixture of cis-1,2-indandiol, only the (+)-cis-(1R,2S) enantiomer was oxidized; the (-)-cis-(S,2R) enantiomer remained unchanged. CDD oxidized both enantiomers of cis-1,2-dihydroxy-1,2,3, 4-tetrahydronaphthalene, but oxidation of the (+)-cis-(1S,2R) enantiomer was delayed until the (-)-cis-(1R,2S) enantiomer was completely depleted. When incubated with nonracemic mixtures of para-substituted cis-toluene dihydrodiols, CDD always oxidized the major enantiomer at a higher rate than the minor enantiomer. When incubated with racemic 1-indanol, CDD enantioselectively transformed the (+)-(1S) enantiomer to 1-indanone. This stereoselective transformation shows that CDD also acted as an alcohol dehydrogenase. Additionally, CDD was able to oxidize (+)-cis-(1R,2S)-dihydroxy-1, 2-dihydronaphthalene, (+)-cis-monochlorobiphenyl dihydrodiols, and (+)-cis-toluene dihydrodiol to the corresponding catechols.

  6. cis-Chlorobenzene Dihydrodiol Dehydrogenase (TcbB) from Pseudomonas sp. Strain P51, Expressed in Escherichia coli DH5α(pTCB149), Catalyzes Enantioselective Dehydrogenase Reactions

    Science.gov (United States)

    Raschke, Henning; Fleischmann, Thomas; Van Der Meer, Jan Roelof; Kohler, Hans-Peter E.

    1999-01-01

    cis-Chlorobenzene dihydrodiol dehydrogenase (CDD) from Pseudomonas sp. strain P51, cloned into Escherichia coli DH5α(pTCB149) was able to oxidize cis-dihydrodihydroxy derivatives (cis-dihydrodiols) of dihydronaphthalene, indene, and four para-substituted toluenes to the corresponding catechols. During the incubation of a nonracemic mixture of cis-1,2-indandiol, only the (+)-cis-(1R,2S) enantiomer was oxidized; the (−)-cis-(S,2R) enantiomer remained unchanged. CDD oxidized both enantiomers of cis-1,2-dihydroxy-1,2,3,4-tetrahydronaphthalene, but oxidation of the (+)-cis-(1S,2R) enantiomer was delayed until the (−)-cis-(1R,2S) enantiomer was completely depleted. When incubated with nonracemic mixtures of para-substituted cis-toluene dihydrodiols, CDD always oxidized the major enantiomer at a higher rate than the minor enantiomer. When incubated with racemic 1-indanol, CDD enantioselectively transformed the (+)-(1S) enantiomer to 1-indanone. This stereoselective transformation shows that CDD also acted as an alcohol dehydrogenase. Additionally, CDD was able to oxidize (+)-cis-(1R,2S)-dihydroxy-1,2-dihydronaphthalene, (+)-cis-monochlorobiphenyl dihydrodiols, and (+)-cis-toluene dihydrodiol to the corresponding catechols. PMID:10583971

  7. Cis-Chlorobenzene dihydrodiol dehydrogenase (TcbB) from Pseudomonas sp. strain P51, expressed in Escherichia coli DH5{alpha}(pTCB149), catalyzes enantioselective dehydrogenase reactions

    Energy Technology Data Exchange (ETDEWEB)

    Raschke, H.; Fleischmann, T.; Meer, J.R. van der; Kohler, H.P.E.

    1999-12-01

    cis-Chlorobenzene dihydrodiol dehydrogenase (CDD) from Pseudomonas sp. strain P51, cloned into Escherichia coli DH5{alpha}(pTCB149) was able to oxidize cis-dihydrodihydroxy derivatives (cis-dihydrodiols) of dihydronaphthalene, indene, and four para-substituted toluenes to the corresponding catechols. During the incubation of a nonracemic mixture of cis-1,2-indandiol, only the (+)-cis-(1R,2S) enantiomer was oxidized; the (-)-cis-(S,2R) enantiomer remained unchanged, CDD oxidized both enantiomers of cis-1,2-dihydroxy-1,2,3,4-tetrahydronaphthalene, but oxidation of the (+)-cis-(1S,2R) enantiomer was delayed until the (-)-cis-(1R,2S) enantiomer was completely depleted. When incubated with nonracemic mixtures of para-substituted cis-toluene dihydrodiols, CDD always oxidized the major enantiomer at a higher rate than the minor enantiomer. When incubated with racemic 1-indanol, CDD enantioselectively transformed the (+)-(1S) enatiomer to 1-indanone. This stereoselective transformation shows that CDD also acted as an alcohol dehydrogenase. Additionally, CDD was able to oxidize (+)-cis-(1R,2S)-dihydroxy-1,2-dihydronaphthalene, (+)-cis-monochlorobiphenyl dihydrodiols, and (+)-cis-toluene dihydrodiol to the corresponding catechols.

  8. Measurement of activation reaction rate distributions in a lead assembly bombarded with 500-MeV protons

    CERN Document Server

    Takada, H; Sasa, T; Tsujimoto, K; Yasuda, H

    2000-01-01

    Reaction rate distributions of various activation detectors such as the /sup nat/Ni(n, x)/sup 58/Co, /sup 197/Au(n,2n)/sup 196/Au, and /sup 197/Au(n,4n)/sup 194/Au reactions were measured to study the production and the transport of spallation neutrons in a lead assembly bombarded with protons of 500 MeV. The measured data were analyzed with the nucleon-meson transport code NMTC/JAERI combined with the MCNP4A code using the nuclide production cross sections based on the JENDL Dosimetry File and those calculated with the ALICE-F code. It was found that the NMTC/JAERI-MCNP4A calculations agreed well with the experiments for the low-energy-threshold reaction of /sup nat/Ni(n, x)/sup 58/Co. With the increase of threshold energy, however, the calculation underestimated the experiments, especially above 20 MeV. The reason for the disagreement can be attributed to the underestimation of the neutron yield in the tens of mega-electron-volt regions by the NMTC/JAERI code. (32 refs).

  9. Cross-sections of (p, xn) nuclear reactions on Pb and Bi by 100 MeV protons

    Energy Technology Data Exchange (ETDEWEB)

    Oranj, Leila Mokhtari; Jung, Nam Suk; Oh, Joo Hee; Lee, Arim; Kim, Dong Hyun; Bae, Oryun; Lee, Hee Seock [POSTECH, Pohang (Korea, Republic of)

    2016-04-15

    The development of high-intensity and high-energy accelerator is gaining interest in Korea, in recent years. Rare Isotope Science Project (RISP), Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL), Korea Heavy Ion Medical Accelerator (KHIMA) facilities are being designed. In the frame of above projects, for the safety issue and shielding analysis of the accelerator facility, extensive studies including experimental and simulation on the production yields of residual nuclei induced in the accelerator materials such as Pb, Cu and Bi by protons and heavy ions are in progress. In this work, we measured cross-sections of {sup na}'tPb(p,xn){sup 206,205,204,20{sup ,202}}Bi and {sup 209}Bi(p, xn){sup 207,206,205,204},{sup 203}Po nuclear reactions by the 100-MeV protons. The present experimental data are in good agreement with the results of Titarenkoet al. and Gloris et al.. Experimental data were higher than theoretical data. In other words, results of TALYS code and data in TENDL library underestimated the measured crosss sections and library of TALYS code and TENDL need to be improved.

  10. Study of proton-induced reactions and correlation with fast-neutron scattering

    International Nuclear Information System (INIS)

    Hansen, L.F.

    1982-01-01

    The generation of cross sections for fast neutron-nucleon interactions obtained from elastic and charge-exchange proton data is discussed in terms of the Lane model formalism. A general description of the interaction of nucleons with nuclei is presented in terms of the optical model and the extended (or coupled-channel) optical model, together with the relation of these models to microscopic calculations of the nucleon-nucleon interaction. Comparisons between neutron elastic data and calculations carried out with optical model potentials obtained from (p,p) and (p,n) data are presented for a large number of nuclei. The validity of the Lane model and the importance of coupled effects in the actinide region are shown in a detailed comparison of calculations for elastic and inelastic neutron differential cross sections and measurements for 232 Th and 238 U

  11. Plasma Deposited Thin Iron Oxide Films as Electrocatalyst for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells

    Directory of Open Access Journals (Sweden)

    Lukasz JOZWIAK

    2017-02-01

    Full Text Available The possibility of using plasma deposited thin films of iron oxides as electrocatalyst for oxygen reduction reaction (ORR in proton exchange membrane fuel cells (PEMFC was examined. Results of energy-dispersive X-ray spectroscopy (EDX and X-ray photoelectron spectroscopy (XPS analysis indicated that the plasma deposit consisted mainly of FeOX structures with the X parameter close to 1.5. For as deposited material iron atoms are almost exclusively in the Fe3+ oxidation state without annealing in oxygen containing atmosphere. However, the annealing procedure can be used to remove the remains of carbon deposit from surface. The single cell test (SCT was performed to determine the suitability of the produced material for ORR. Preliminary results showed that power density of 0.23 mW/cm2 could be reached in the tested cell.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14406

  12. Cross Sections for the Production of Residual Nuclides by Proton-Induced Reactions with Uranium at Medium Energies

    International Nuclear Information System (INIS)

    Issa, S.A.M.; Michel, R.; Uosif, M.A.M.; Issa, S.A.M.; Flamentc, J.L.; David, J.C.; Leray, S.

    2009-01-01

    The production of residual nuclides by proton-induced reactions on uranium is investigated using activated targets from irradiation experiments at Saturne II synchrocyclotron at the Laboratory National Saturne/Saclay. These investigations contribute to the European research project NUDATRA within the IP EUROTRANS in which the feasibility of accelerator-driven transmutation of nuclear waste is evaluated. Experimental cross sections are derived from gamma-spectrometric measurements. A total of 1894 cross-section was deter-mined covering 44 residual nuclides in the energy range from 211 MeV to 2530 MeV. The experimental data together with those of earlier work of our group are discussed in the context of theoretical excitation functions calculated by the newly developed INCL4 + ABLA and the TALYS codes

  13. Study of the excited levels of 11C and 12C by the analysis of protons induced reactions

    International Nuclear Information System (INIS)

    Rihet, Y.

    1984-07-01

    The present work is a study of 11 and 12 C excited states by reactions of non polarised protons on 10 B and 11 B. R-matrix analysis of the 10 B excitation curves in the range E p = 0 to 8 MeV was used to establish parameters of 41 levels in 11 C. Isobaric multiplets of T = 1/2 and T = 3/2 states in A = 11 nuclei are deduced. Analysis of 11 B excitation curves in the E p = 0.5 to 7.4 MeV range led to parameter values of 60 levels in 12 C. T = 1 states in A = 12 isobaric nuclei are discussed [fr

  14. Monte Carlo FLUKA code simulation for study of {sup 68}Ga production by direct proton-induced reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mokhtari Oranj, Leila; Kakavand, Tayeb [Physics Faculty, Zanjan University, P.O. Box 451-313, Zanjan (Iran, Islamic Republic of); Sadeghi, Mahdi, E-mail: msadeghi@nrcam.org [Agricultural, Medical and Industrial Research School, Nuclear Science and Technology Research Institute, P.O. Box 31485-498, Karaj (Iran, Islamic Republic of); Aboudzadeh Rovias, Mohammadreza [Agricultural, Medical and Industrial Research School, Nuclear Science and Technology Research Institute, P.O. Box 31485-498, Karaj (Iran, Islamic Republic of)

    2012-06-11

    {sup 68}Ga is an important radionuclide for positron emission tomography. {sup 68}Ga can be produced by the {sup 68}Zn(p,n){sup 68}Ga reaction in a common biomedical cyclotrons. To facilitate optimization of target design and study activation of materials, Monte Carlo code can be used to simulate the irradiation of the target materials with charged hadrons. In this paper, FLUKA code simulation was employed to prototype a Zn target for the production of {sup 68}Ga by proton irradiation. Furthermore, the experimental data were compared with the estimated values for the thick target yield produced in the irradiation time according to FLUKA code. In conclusion, FLUKA code can be used for estimation of the production yield.

  15. Measurement of the Induced Proton Polarization Pn in the 12C(e,e'rvec p) Reaction

    International Nuclear Information System (INIS)

    Woo, R.J.; Finn, J.M.; Jones, M.K.; McIntyre, J.I.; Perdrisat, C.F.; Barkhuff, D.H.; Lourie, R.W.; Milbrath, B.D.; Van Verst, S.P.; Bertozzi, W.; Dale, D.; Dodson, G.; Dow, K.A.; Farkhondeh, M.; Gilad, S.; Joo, K.; Kowalski, S.; Sarty, A.J.; Tieger, D.; Tschalaer, C.; Turchinetz, W.; Van Verst, S.P.; Warren, G.A.; Chen, J.P.; Mitchell, J.; Epstein, M.B.; Margaziotis, D.J.; Kelly, J.J.; Markowitz, P.; Madey, R.; Mertz, C.; Punjabi, V.; Rutt, P.M.; Ulmer, P.E.; Weinstein, L.; Vellidis, C.

    1998-01-01

    The first measurements of the induced proton polarization P n for the 12 C( e,e ' rvec p) reaction are reported. The experiment was performed at quasifree kinematics for energy and momentum transfer (ω,q)∼ (294 MeV, 756 MeV/c) and sampled a missing momentum range of 0 - 250 MeV/c. The induced polarization arises from final-state interactions and for these kinematics is dominated by the real part of the spin-orbit optical potential. The distorted-wave impulse approximation provides good agreement with data for the 1p 3/2 shell. The data for the continuum suggest that both the 1s 1/2 shell and underlying scr(l)>1 configurations contribute. copyright 1998 The American Physical Society

  16. Search for proton emission in {sup 54}Ni and multi-nucleon transfer reactions in the actinide region

    Energy Technology Data Exchange (ETDEWEB)

    Geibel, Kerstin

    2012-06-15

    The first part of the thesis presents the investigation of fusion-evaporation reactions in order to verify one-proton emission from the isomeric 10{sup +} state in the proton rich nucleus {sup 54}Ni. Between the years 2006 and 2009 a series of experimental studies were performed at the Tandem accelerator in the Institut fuer Kernphysik (IKP), University of Cologne. These experiments used fusion-evaporation reactions to populate {sup 54}Ni via the two-neutron-evaporation channel of the compound nucleus {sup 56}Ni. The cross section for the population of the ground state of {sup 54}Ni was predicted to be in orders of microbarn. This required special care with respect to the sensitivity of the experimental setup, which consisted of a double-sided silicon-strip detector (DSSSD), a neutron-detector array and HPGe detectors. In two experiments the excitation functions of the reactions ({sup 32}S+{sup 24}Mg) and ({sup 28}Si+{sup 28}Si) were determined to find the optimal experimental conditions for the population of {sup 54}Ni. A final experiment employed a {sup 28}Si beam at an energy of 70 MeV, impinging on a {sup 28}Si target. With a complex analysis it is possible to obtain a background-free energy spectrum of the DSSSD. An upper cross section limit for the population of the 10{sup +} state in {sup 54}Ni is established at σ({sup 54}Ni(10{sup +})) ≤ (13.9 ± 7.8) nbarn. In the second part of the thesis the population of actinide nuclei by multi-nucleon transfer reactions is investigated. Two experiments, performed in 2007 and 2008 at the CLARA-PRISMA setup at the Laboratori Nazionali di Legnaro, are analyzed with respect to the target-like reaction products. In both experiments {sup 238}U was used as target. A {sup 70}Zn beam with 460 MeV and a {sup 136}Xe beam with 926 MeV, respectively, impinged on the target, inducing transfer reactions. Kinematic correlations between the reaction partners are used to obtain information on the unobserved target-like reaction

  17. Proton transfer and isotope-induced reaction in aniline cluster ions

    Czech Academy of Sciences Publication Activity Database

    Lengyel, Jozef; Poterya, Viktoriya; Fárník, Michal

    2015-01-01

    Roč. 50, č. 3 (2015), s. 643-649 ISSN 1076-5174 R&D Projects: GA ČR GA14-14082S Institutional support: RVO:61388955 Keywords : isotope effect * intracluster reaction * Electron ionization Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.541, year: 2015

  18. Proton, deuteron and triton emission in 14N + Ag reaction at 52 MeV/nucleon

    International Nuclear Information System (INIS)

    Aleksakhin, V.Yu.; Gostkin, M.I.; Gudima, K.K.

    1998-01-01

    Inclusive energy spectra of p, d, t and multiplicities from the reaction 14 N(Ag, X), X = p, d, t at E/A = 52 MeV were measured. The experimental data are compared with Dubna version of the Cascade Model (DCM) and are analyzed in the framework of the moving source model

  19. Nuclear bremsstrahlung in proton induced reactions at 190 MeV (first experiments at AGOR)

    NARCIS (Netherlands)

    Wilschut, HW

    1998-01-01

    An overview is given of the first experiments with the new KVI cyclotron AGOR. First experiments have focused on nuclear bremsstrahlung in few-and many-body reactions. A classical introduction to nuclear bremsstrahlung is given. First results on coherent bremsstrahlung are discussed.

  20. Fragment production in 12-GeV proton-induced reactions

    International Nuclear Information System (INIS)

    Hirata, Yuichi; Ohnishi, Akira; Ohtsuka, Naohiko; Nara, Yasushi; Niida, Koji; Chiba, Satoshi; Takada, Hiroshi

    2000-01-01

    We study mass and angular distribution of Intermediate Mass Fragment (IMF) produced from p(12 GeV)+ 197 Au reaction by using JAM cascade model combined with percolation model. Although the mass distribution of IMF is well reproduced, the experimentally observed sideward peak of IMF angular distribution is not explained within present JAM + percolation model. (author)

  1. 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.

  2. Competitive cation binding computations of proton balance for reactions of the phosphagen and glycolytic energy systems within skeletal muscle

    Science.gov (United States)

    2017-01-01

    Limited research and data has been published for the H+ coefficients for the metabolites and reactions involved in non-mitochondrial energy metabolism. The purpose of this investigation was to compute the fractional binding of H+, K+, Na+ and Mg2+ to 21 metabolites of skeletal muscle non-mitochondrial energy metabolism, resulting in 104 different metabolite-cation complexes. Fractional binding of H+ to these metabolite-cation complexes were applied to 17 reactions of skeletal muscle non-mitochondrial energy metabolism, and 8 conditions of the glycolytic pathway based on the source of substrate (glycogen vs. glucose), completeness of glycolytic flux, and the end-point of pyruvate vs. lactate. For pH conditions of 6.0 and 7.0, respectively, H+ coefficients (-‘ve values = H+ release) for the creatine kinase, adenylate kinase, AMP deaminase and ATPase reactions were 0.8 and 0.97, -0.13 and -0.02, 1.2 and 1.09, and -0.01 and -0.66, respectively. The glycolytic pathway is net H+ releasing, regardless of lactate production, which consumes 1 H+. For glycolysis fueled by glycogen and ending in either pyruvate or lactate, H+ coefficients for pH 6.0 and 7.0 were -3.97 and -2.01 (pyruvate), and -1.96 and -0.01 (lactate), respectively. When starting with glucose, the same conditions result in H+ coefficients of -3.98 and -2.67, and -1.97 and –0.67, respectively. The most H+ releasing reaction of glycolysis is the glyceraldehyde-3-phosphate dehydrogenase reaction, with H+ coefficients for pH 6.0 and 7.0 of -1.58 and -0.76, respectively. Incomplete flux of substrate through glycolysis would increase net H+ release due to the absence of the pyruvate kinase and lactate dehydrogenase reactions, which collectively result in H+ coefficients for pH 6.0 and 7.0 of 1.35 and 1.88, respectively. The data presented provide an extensive reference source for academics and researchers to accurately profile the balance of protons for all metabolites and reactions of non-mitochondrial energy

  3. Competitive cation binding computations of proton balance for reactions of the phosphagen and glycolytic energy systems within skeletal muscle.

    Science.gov (United States)

    Robergs, Robert Andrew

    2017-01-01

    Limited research and data has been published for the H+ coefficients for the metabolites and reactions involved in non-mitochondrial energy metabolism. The purpose of this investigation was to compute the fractional binding of H+, K+, Na+ and Mg2+ to 21 metabolites of skeletal muscle non-mitochondrial energy metabolism, resulting in 104 different metabolite-cation complexes. Fractional binding of H+ to these metabolite-cation complexes were applied to 17 reactions of skeletal muscle non-mitochondrial energy metabolism, and 8 conditions of the glycolytic pathway based on the source of substrate (glycogen vs. glucose), completeness of glycolytic flux, and the end-point of pyruvate vs. lactate. For pH conditions of 6.0 and 7.0, respectively, H+ coefficients (-'ve values = H+ release) for the creatine kinase, adenylate kinase, AMP deaminase and ATPase reactions were 0.8 and 0.97, -0.13 and -0.02, 1.2 and 1.09, and -0.01 and -0.66, respectively. The glycolytic pathway is net H+ releasing, regardless of lactate production, which consumes 1 H+. For glycolysis fueled by glycogen and ending in either pyruvate or lactate, H+ coefficients for pH 6.0 and 7.0 were -3.97 and -2.01 (pyruvate), and -1.96 and -0.01 (lactate), respectively. When starting with glucose, the same conditions result in H+ coefficients of -3.98 and -2.67, and -1.97 and -0.67, respectively. The most H+ releasing reaction of glycolysis is the glyceraldehyde-3-phosphate dehydrogenase reaction, with H+ coefficients for pH 6.0 and 7.0 of -1.58 and -0.76, respectively. Incomplete flux of substrate through glycolysis would increase net H+ release due to the absence of the pyruvate kinase and lactate dehydrogenase reactions, which collectively result in H+ coefficients for pH 6.0 and 7.0 of 1.35 and 1.88, respectively. The data presented provide an extensive reference source for academics and researchers to accurately profile the balance of protons for all metabolites and reactions of non-mitochondrial energy

  4. Competitive cation binding computations of proton balance for reactions of the phosphagen and glycolytic energy systems within skeletal muscle.

    Directory of Open Access Journals (Sweden)

    Robert Andrew Robergs

    Full Text Available Limited research and data has been published for the H+ coefficients for the metabolites and reactions involved in non-mitochondrial energy metabolism. The purpose of this investigation was to compute the fractional binding of H+, K+, Na+ and Mg2+ to 21 metabolites of skeletal muscle non-mitochondrial energy metabolism, resulting in 104 different metabolite-cation complexes. Fractional binding of H+ to these metabolite-cation complexes were applied to 17 reactions of skeletal muscle non-mitochondrial energy metabolism, and 8 conditions of the glycolytic pathway based on the source of substrate (glycogen vs. glucose, completeness of glycolytic flux, and the end-point of pyruvate vs. lactate. For pH conditions of 6.0 and 7.0, respectively, H+ coefficients (-'ve values = H+ release for the creatine kinase, adenylate kinase, AMP deaminase and ATPase reactions were 0.8 and 0.97, -0.13 and -0.02, 1.2 and 1.09, and -0.01 and -0.66, respectively. The glycolytic pathway is net H+ releasing, regardless of lactate production, which consumes 1 H+. For glycolysis fueled by glycogen and ending in either pyruvate or lactate, H+ coefficients for pH 6.0 and 7.0 were -3.97 and -2.01 (pyruvate, and -1.96 and -0.01 (lactate, respectively. When starting with glucose, the same conditions result in H+ coefficients of -3.98 and -2.67, and -1.97 and -0.67, respectively. The most H+ releasing reaction of glycolysis is the glyceraldehyde-3-phosphate dehydrogenase reaction, with H+ coefficients for pH 6.0 and 7.0 of -1.58 and -0.76, respectively. Incomplete flux of substrate through glycolysis would increase net H+ release due to the absence of the pyruvate kinase and lactate dehydrogenase reactions, which collectively result in H+ coefficients for pH 6.0 and 7.0 of 1.35 and 1.88, respectively. The data presented provide an extensive reference source for academics and researchers to accurately profile the balance of protons for all metabolites and reactions of non

  5. 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

  6. 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.

  7. 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.

  8. Dissipative effects in fission investigated with proton-on-lead reactions

    Directory of Open Access Journals (Sweden)

    Rodríguez-Sánchez J. L.

    2016-01-01

    Full Text Available The complete kinematic measurement of the two fission fragments permitted us to investigate dissipative effects at large deformations, between the saddle-point and the corresponding scission configurations. Up to now, this kind of study has only been performed with fusionfission reactions using a limited number of observables, such as the mass distribution of the fission fragments or the neutron multiplicities. However, the large angular momenta gained by the compound nucleus could affect the conclusions drawn from such experiments. In this work, the use of spallation reactions, where the fissioning systems are produced with low angular momentum, small deformations and high excitation energies, favors the study of dissipation, and allowed us to define new observables, such as postscission neutron multiplicities and the neutron excess of the final fission fragments as a function of the atomic number of the fissioning system. These new observables are used to investigate the dissipation at large deformations.

  9. On the nucleon effective mass role to the high energy proton spallation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Santos, B.M., E-mail: biank_ce@if.uff.br [Instituto de Física, Universidade Federal Fluminense, Av. Gal. Milton Tavares de Souza, 24210-346 Niterói, RJ (Brazil); Instituto Militar de Engenharia, Praça General Tibúrcio 80, 22290-270 Rio de Janeiro, RJ (Brazil); Pinheiro, A.R.C. [Centro Brasileiro de Pesquisas Físicas, Rua Dr. Xavier Sigaud 150, 22290-180 Rio de Janeiro, RJ (Brazil); Universidade Federal do Acre, BR 364 km 04, 69920-900 Rio Branco, AC (Brazil); Gonçalves, M. [Comissão Nacional de Energia Nuclear, Rua General Severiano 90, 22290-901 Rio de Janeiro, RJ (Brazil); Duarte, S.B. [Centro Brasileiro de Pesquisas Físicas, Rua Dr. Xavier Sigaud 150, 22290-180 Rio de Janeiro, RJ (Brazil); Cabral, R.G. [Instituto Militar de Engenharia, Praça General Tibúrcio 80, 22290-270 Rio de Janeiro, RJ (Brazil)

    2016-04-15

    We explore the effect of the nucleon effective mass to the dynamic evolution of the rapid phase of proton–nucleus spallation reactions. The analysis of the relaxation time for the non-equilibrium phase is studied by variations in the effective mass parameter. We determine the final excitation energy of the hot residual nucleus at the end of cascade phase and the de-excitation of the nuclear system is carried out considering the competition of particle evaporation and fission processes. It was shown that the excitation energy depends of the hot compound residual nucleus at the end of the rapid phase on the changing effective mass. The multiplicity of particles was also analyzed in cascade and evaporation phase of the reaction. The use of nucleon effective mass during cascade phase can be considered as an effect of the many-body nuclear interactions not included explicitly in a treatment to the nucleon–nucleon interaction inside the nucleus. This procedure represents a more realistic scenario to obtain the neutron multiplicity generated in this reaction, which is a benchmark for the calculation of the neutronic in the ADS reactors.

  10. Neutron to proton ratios of quasiprojectile and midrapidity emission in the 58Ni+58Ni reaction at 52 MeV/nucleon

    International Nuclear Information System (INIS)

    Theriault, D.; Vallee, A.; Gingras, L.; Larochelle, Y.; Roy, R.; April, A.; Beaulieu, L.; Grenier, F.; Lemieux, F.; Moisan, J.; St-Pierre, C.; Turbide, S.; Samri, M.; Borderie, B.; Rivet, M. F.; Bougault, R.; Colin, J.; Cussol, D.; Durand, D.; Lecolley, J.F.

    2005-01-01

    By combining data from a charged particle 58 Ni+ 58 Ni experiment at 52 MeV/nucleon with an 36 Ar+ 58 Ni experiment at 50 MeV/nucleon for which free neutrons have been detected, an increase in the neutron to proton ratio of the whole nuclear material at midrapidity has been experimentally observed in the reaction 58 Ni+ 58 Ni at 52 MeV/nucleon. The neutron-to-proton ratio of the quasi-projectile emission is analyzed for the same reactions and is seen to decrease below the ratio of the initial system. Those observations suggest that an asymmetric exchange of neutrons and protons between the quasiprojectile and the midrapidity region exists

  11. Spallation reaction study for fission products in nuclear waste: Cross section measurements for {sup 137}Cs and {sup 90}Sr on proton and deuteron

    Energy Technology Data Exchange (ETDEWEB)

    Wang, H., E-mail: wanghe@ribf.riken.jp [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Otsu, H.; Sakurai, H.; Ahn, D.S. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Aikawa, M. [Faculty of Science, Hokkaido University, Sapporo 060-0810 (Japan); Doornenbal, P.; Fukuda, N.; Isobe, T. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Kawakami, S. [Department of Applied Physics, University of Miyazaki, Miyazaki 889-2192 (Japan); Koyama, S. [Department of Physics, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Kubo, T.; Kubono, S.; Lorusso, G. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Maeda, Y. [Department of Applied Physics, University of Miyazaki, Miyazaki 889-2192 (Japan); Makinaga, A. [Graduate School of Medicine, Hokkaido University, North-14, West-5, Kita-ku, Sapporo 060-8648 (Japan); Momiyama, S. [Department of Physics, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Nakano, K. [Department of Advanced Energy Engineering Science, Kyushu University, Kasuga, Fukuoka 816-8580 (Japan); Niikura, M. [Department of Physics, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Shiga, Y. [Department of Physics, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima, Tokyo 171-8501 (Japan); RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Söderström, P.-A. [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); and others

    2016-03-10

    We have studied spallation reactions for the fission products {sup 137}Cs and {sup 90}Sr for the purpose of nuclear waste transmutation. The spallation cross sections on the proton and deuteron were obtained in inverse kinematics for the first time using secondary beams of {sup 137}Cs and {sup 90}Sr at 185 MeV/nucleon at the RIKEN Radioactive Isotope Beam Factory. The target dependence has been investigated systematically, and the cross-section differences between the proton and deuteron are found to be larger for lighter spallation products. The experimental data are compared with the PHITS calculation, which includes cascade and evaporation processes. Our results suggest that both proton- and deuteron-induced spallation reactions are promising mechanisms for the transmutation of radioactive fission products.

  12. Radiochemical separations of target-like reaction products from Au-, Pt-, and Th-targets after irradiation with GeV protons

    International Nuclear Information System (INIS)

    Szweryn, B.; Bruechle, W.; Schausten, B.; Schaedel, M.

    1988-08-01

    Chemical separation procedures for separations of reaction products after spallation reactions with 2.6 GeV protons and heavy element targets are presented. To determine independent cross sections of individual isotopes the elements Au, Pt, Ir, Os, Re, W, Ta, Hf, (Lu, Yb, Tm, Er), (Gd, Eu, Sm), were separated from gold targets, Pt, Ir, Os, W, Ta, Hf, (Lu, Yb, Tm, Er), (Gd, Eu, Sm) from a platinum target and Au, Tl from a thorium target. (orig.)

  13. Measurements of acetone yields from the OH-initiated oxidation of terpenes by proton-transfer-reaction mass spectrometry

    International Nuclear Information System (INIS)

    Wisthaler, A.; Lindinger, W.; Jensen, N.R.; Winterhalter, R.; Hjorth, J.

    2002-01-01

    Biogenic VOCs (Volatile Organic Compounds) are known to be emitted in large quantities from vegetation exceeding largely global emissions of anthropogenic VOCs. Monoterpenes (C 10 H 16 ) are important constituents of biogenic VOC emissions. The atmospheric oxidation of Monoterpenes appears to be a potentially relevant source of acetone in the atmosphere. Acetone is present as a significant trace gas in the whole troposphere and influences in particular the atmospheric chemistry in the upper troposphere by substantially contributing to the formation of HO x radicals and peroxyacetyl nitrate (PAN). Acetone is formed promptly, following attack by the OH-radical on the terpene, via a series of highly unstable radical intermediates, but it is also formed slowly via the degradation of stable non-radical intermediates such as pinonaldehyde and nopinone. In order to investigate the relative importance of these processes, the OH-initiated oxidation of α-pinene and β-pinene was investigated in a chamber study, where the concentrations of monoterpenes, acetone, pinonaldehyde and nopinone were monitored by proton-transfer-reaction mass spectrometry (PTR-MS). It was found that significant amounts of acetone are formed directly, whenα-pinene and β-pinene are oxidized by the OH radical, but also secondary chemistry (degradation of primary reaction products) gives a significant contribution to the formation of acetone from monoterpenes. It can be concluded that atmospheric oxidation of monoterpenes contributes a significant fraction to the global acetone source strength. (nevyjel)

  14. Characterisation of the volatile profiles of infant formulas by proton transfer reaction-mass spectrometry and gas chromatography-mass spectrometry

    NARCIS (Netherlands)

    Ruth, van S.M.; Floris, V.; Fayoux, S.

    2006-01-01

    The volatile profiles of 13 infant formulas were evaluated by proton transfer reaction-mass spectrometry (PTR-MS) and gas chromatography¿mass spectrometry (GC¿MS). The infant formulas varied in brand (Aptamil, Cow & Gate, SMA), type (for different infant target groups) and physical form

  15. Reaction cross sections for protons on {sup 12}C, {sup 40}Ca, {sup 90}Zr and {sup 208}Pb at energies between 80 and 180 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Auce, A.; Ingemarsson, A.; Johansson, R. [and others

    2005-04-01

    Results of reaction cross section measurements on {sup 12}C, {sup 40}Ca, {sup 90}Zr and {sup 208}Pb at incident proton energies between 80 and 180 MeV and for {sup 58}Ni at 81 MeV are presented. The experimental procedure is described and the results are compared with earlier measurements and predictions using macroscopic and microscopic models.

  16. Reaction cross sections for protons on 12C, 40Ca, 90Zr and 208Pb at energies between 80 and 180 MeV

    International Nuclear Information System (INIS)

    Auce, A.; Ingemarsson, A.; Johansson, R.

    2005-04-01

    Results of reaction cross section measurements on 12 C, 40 Ca, 90 Zr and 208 Pb at incident proton energies between 80 and 180 MeV and for 58 Ni at 81 MeV are presented. The experimental procedure is described and the results are compared with earlier measurements and predictions using macroscopic and microscopic models

  17. 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.

  18. Eddy covariance emission and deposition flux measurements using proton transfer reaction – time of flight – mass spectrometry (PTR-TOF-MS): comparison with PTR-MS measured vertical gradients and fluxes

    NARCIS (Netherlands)

    Park, J.H.; Goldstein, A.H.; Timkovsky, J|info:eu-repo/dai/nl/330541676; Fares, S.; Weber, R.; Karlik, J.; Holzinger, R.|info:eu-repo/dai/nl/337989338

    2013-01-01

    During summer 2010, a proton transfer reaction – time of flight – mass spectrometer (PTR-TOF-MS) and a quadrupole proton transfer reaction mass spectrometer (PTR-MS) were deployed simultaneously for one month in an orange orchard in the Central Valley of California to collect continuous data

  19. 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.

  20. 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

  1. Gamow-Teller transitions and neutron-proton-pair transfer reactions

    Science.gov (United States)

    Van Isacker, P.; Macchiavelli, A. O.

    2018-05-01

    We propose a schematic model of nucleons moving in spin-orbit partner levels, j = l ± 1/2, to explain Gamow-Teller and two-nucleon transfer data in N = Z nuclei above 40Ca. Use of the LS coupling scheme provides a more transparent approach to interpret the structure and reaction data. We apply the model to the analysis of charge-exchange, 42Ca(3He,t)42Sc, and np-transfer, 40Ca(3He,p)42Sc, reactions data to define the elementary modes of excitation in terms of both isovector and isoscalar pairs, whose properties can be determined by adjusting the parameters of the model (spin-orbit splitting, isovector pairing strength and quadrupole matrix element) to the available data. The overall agreement with experiment suggests that the approach captures the main physics ingredients and provides the basis for a boson approximation that can be extended to heavier nuclei. Our analysis also reveals that the SU(4)-symmetry limit is not realized in 42Sc.

  2. Optimization of the Pd-Fe-Mo Catalysts for Oxygen Reduction Reaction in Proton-Exchange Membrane Fuel Cells

    International Nuclear Information System (INIS)

    Lee, Yeayeon; Jang, Jeongseok; Lee, Jin Goo; Jeon, Ok Sung; Kim, Hyeong Su; Hwang, Ho Jung; Shul, Yong Gun

    2016-01-01

    Highlights: • Pd-Mo-Fe catalysts show high catalytic activity and stability for oxygen-reduction reactions in acid media. • The optimum compositions were 7.5:1.5:1.0 for Pd-Fe-Mo, and the optimum temperatures were 500 °C. • The Pd-Fe-Mo catalysts were successfully applied to the PEMFC cathode, showing ∼500 mA cm −1 at 0.6 V. • The lattice constant was strongly related to the activity and stability of the catalysts for oxygen-reduction reactions. - Abstract: Highly active and durable non-platinum catalysts for oxygen-reduction reaction (ORR) have been developed for energy conversion devices such as proton-exchange membrane fuel cells (PEMFCs). In this study, Pd-Fe-Mo catalyst is reported as a non-platinum catalyst for ORR. The atomic ratio and annealing temperatures are controlled on the catalysts to understand interplay between their physical and chemical properties and electrochemical activities. The Pd-Fe-Mo catalyst optimized with 7.5:1.5:1.0 of the atomic ratio and 500 °C of the annealing temperature shows 32.18 mA mg −1 PGM (PGM: platinum group metal) of the kinetic current density at 0.9 V for ORR, which is comparable to that of commercial Pt/C catalyst. The current density is degraded to 6.20 mA mg −1 PGM after 3000 cycling of cyclic voltammetry, but it is greatly enhanced value compared to other non-platinum catalysts. In actual application to PEMFCs, the 20% Pd-Fe-Mo catalyst supported on carbons exhibits a high performance of 506 mA cm −2 at 0.6 V. The results suggest that the Pd-Fe-Mo catalyst can be a good candidate for non-platinum ORR catalysts.

  3. Quantum mechanical study of the proton exchange in the ortho-para H2 conversion reaction at low temperature.

    Science.gov (United States)

    Honvault, P; Jorfi, M; González-Lezana, T; Faure, A; Pagani, L

    2011-11-14

    Ortho-para H(2) conversion reactions mediated by the exchange of a H(+) proton have been investigated at very low energy for the first time by means of a time independent quantum mechanical (TIQM) approach. State-to-state probabilities and cross sections for H(+) + H(2) (v = 0, j = 0,1) processes have been calculated for a collision energy, E(c), ranging between 10(-6) eV and 0.1 eV. Differential cross sections (DCSs) for H(+) + H(2) (v = 0, j = 1) → H(+) + H(2) (v' = 0, j' = 0) for very low energies only start to develop a proper global minimum around the sideways scattering direction (θ≈ 90°) at E(c) = 10(-3) eV. Rate coefficients, a crucial information required for astrophysical models, are provided between 10 K and 100 K. The relaxation ortho-para process j = 1 → j' = 0 is found to be more efficient than the j = 0 → j' = 1 conversion at low temperatures, in line with the extremely small ratio between the ortho and para species of molecular hydrogen predicted at the temperature of interstellar cold molecular clouds. The results obtained by means of a statistical quantum mechanical (SQM) model, which has previously proved to provide an adequate description of the dynamics of the title reactions at a higher collision energy regime, have been compared with the TIQM results. A reasonable good agreement has been found with the only exception of the DCSs for the H(+) + H(2) (v = 0, j = 1) → H(+) + H(2) (v' = 0, j' = 0) process at very low energy. SQM cross sections are also slightly below the quantum results. Estimates for the rate coefficients, in good accord with the TIQM values, are a clear improvement with respect to pioneering statistical studies on the reaction.

  4. Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: synergetic effect of ligands and barium enolates.

    Science.gov (United States)

    Chen, Wenyong; Chen, Ming; Hartwig, John F

    2014-11-12

    We report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from (R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

  5. 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.

  6. 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.

  7. 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.

  8. Charge-exchange breakup of the deuteron with the production of two protons and spin structure of the amplitude of the nucleon charge transfer reaction

    International Nuclear Information System (INIS)

    Glagolev, V.V.; Lyuboshits, V.L.; Lyuboshits, V.V.; Piskunov, N.M.

    1999-01-01

    In the framework of the impulse approximation, the relation between the effective cross section of the charge-exchange breakup of a fast deuteron d + a → (pp) + b and the effective cross section of the charge transfer process n + a → p + b is discussed. In doing so, the effects of the proton identity (Fermi-statistics) and of the Coulomb and strong interactions of protons in the final state are taken into account. The distribution over relative momenta of the protons, produced in the charge-exchange process d + p → (pp) + n in the forward direction, is investigated. At the transfer momenta being close to zero the effective cross section of the charge-exchange breakup of a fast deuteron, colliding with the proton target, is determined only by the spin-flip part of the amplitude of the charge transfer reaction n + p → p + n at the zero angle. It is shown that the study of the process d + p → (pp) + n in a beam of the polarized (aligned) deuterons allows one, in principle, to separate two spin-dependent terms in the amplitude of the charge transfer reaction n + p → p + n, one of which does not conserve and the other one conserves the projection of the nucleon spin onto the direction of momentum at the transition of the neutron into the proton

  9. Depth profiles of production yields of natPb(p, xn206,205,204,203,202 Bi reactions using 100-MeV proton beam

    Directory of Open Access Journals (Sweden)

    Oranj Leila Mokhtari

    2017-01-01

    Full Text Available In this study, results of the experimental study on the depth profiles of production yields of 206,205,204,203,202Bi radio-nuclei in the natural Pb target irradiated by a 100-MeV proton beam are presented. Irradiation was performed at proton linac facility (KOMAC in Korea. The target, irradiated by 100-MeV protons, was arranged in a stack consisting of natural Pb, Al, Au foils and Pb plates. The proton beam intensity was determined by activation analysis method using 27Al(p, 3p1n24Na, 197Au(p, p1n196Au, and 197Au(p, p3n194Au monitor reactions and also using dosimetry method by a Gafchromic film. The production yields of produced Bi radio-nuclei in the natural Pb foils and monitor reactions were measured by gamma-ray spectroscopy. Monte Carlo simulations were performed by FLUKA, PHITS, and MCNPX codes and compared with the measurements in order to verify validity of physical models and nuclear data libraries in the Monte Carlo codes. A fairly good agreement was observed between the present experimental data and the simulations by FLUKA, PHITS, and MCNPX. However, physical models and the nuclear data relevant to the end of range of protons in the codes need to be improved.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. Investigation of the Three-Nucleon System Dynamics in the Deuteron-Proton Breakup Reaction

    Science.gov (United States)

    Ciepał, I.; Kłos, B.; Kistryn, St.; Stephan, E.; Biegun, A.; Bodek, K.; Deltuva, A.; Epelbaum, E.; Eslami-Kalantari, M.; Fonseca, A. C.; Golak, J.; Jha, V.; Kalantar-Nayestanaki, N.; Kamada, H.; Khatri, G.; Kirillov, Da.; Kirillov, Di.; Kliczewski, St.; Kozela, A.; Kravcikova, M.; Machner, H.; Magiera, A.; Martinska, G.; Messchendorp, J.; Nogga, A.; Parol, W.; Ramazani-Moghaddam-Arani, A.; Roy, B. J.; Sakai, H.; Sekiguchi, K.; Sitnik, I.; Siudak, R.; Skibiński, R.; Sworst, R.; Urban, J.; Witała, H.; Zejma, J.

    2014-08-01

    Precise and large sets of cross section, vector A x , A y and tensor A xx , A xy , A yy analyzing power data for the 1 H( d, pp) n breakup reactions were measured at 100 and 130 MeV deuteron beam energies with the SALAD and BINA detectors at KVI and the Germanium Wall setup at FZ-Jülich. Results are compared with various theoretical approaches which model the three-nucleon system dynamics. The cross section data reveal a sizable three-nucleon force (3NF) and Coulomb force influence. In case of the analyzing powers very low sensitivity to these effects was found and the data are well describe by 2N models only. For A xy at 130 MeV, serious disagreements were observed when 3NF models are included in the calculations.

  15. Nuclear structure of weakly bound radioactive nuclei through elastic and and inelastic scattering on proton. Impacts of the couplings induced by these exotic nuclei on direct reactions

    International Nuclear Information System (INIS)

    Lapoux, V.

    2005-09-01

    Information on the structure, spectroscopy and target interaction potentials of exotic nuclei can be inferred by interpreting measured data from direct reactions on proton such as elastic or inelastic scattering of proton (p,p') or one-nucleon transfer reaction (p,d). A series of experimental results has been obtained at the GANIL facilities on the setting composed of the MUST telescope array used for the detection of light charged-particles and of CATS beam detectors. This setting aims at measuring reactions on light proton or deuteron targets through reverse kinematics. Particularly, results on C 10 , C 11 and on direct reactions with the He 8 beam of Spiral are presented. The first chapter is dedicated to the description of the most important theories concerning the nucleus. The experimental tools used to probe the nucleus are reported in the second chapter. The third and fourth chapters present the framework that has allowed us to analyse results from (p,p') and (p,d) reactions on weakly bound exotic nuclei. The last chapter is dedicated to the description of future experimental programs. (A.C.)

  16. Energy loss, range and fluence distributions, total reaction and projectile fragment production cross sections for proton-nucleus and nucleus-nucleus interactions

    International Nuclear Information System (INIS)

    Sihver, L.; Kanai, T.

    1992-07-01

    We have developed a computer code for calculations of energy loss (dE/dx) and range distributions for heavy ions in any media. The results from our calculations are in very good agreement with previous calculations. We have developed semiempirical total reaction cross section formulae for proton-nucleus (with Z p ≤26) and nucleus-nucleus (with Z p and Z t ≤26) reactions. These formulae apply for incident energies above 15 MeV and 100 MeV/nucleon respectively. From the total reaction cross sections, we can calculate the mean free paths and the fluence distributions of protons and heavy ions in any media. We have compared all the calculated reaction cross sections and the mean free paths with experimental data, and the agreement is good. We have also constructed a procedure for calculating projectile fragment production cross sections, by scaling semiempirical proton-nucleus partial cross section systematics. The scaling is performed using a scaling parameter deduced from our reaction cross sections formulae, and additional enhancements factors. All products with atomic number ranging from that of the projectile (Z p ) down to Z=2 can be calculated. The agreement between the calculated cross sections and the experimental data is better than earlier published results. (author)

  17. Cross sections for nuclide production in proton- and deuteron-induced reactions on 93Nb measured using the inverse kinematics method

    Directory of Open Access Journals (Sweden)

    Nakano Keita

    2017-01-01

    Full Text Available Isotopic production cross sections were measured for proton- and deuteron-induced reactions on 93Nb by means of the inverse kinematics method at RIKEN Radioactive Isotope Beam Factory. The measured production cross sections of residual nuclei in the reaction 93Nb + p at 113 MeV/u were compared with previous data measured by the conventional activation method in the proton energy range between 46 and 249 MeV. The present inverse kinematics data of four reaction products (90Mo, 90Nb, 88Y, and 86Y were in good agreement with the data of activation measurement. Also, the model calculations with PHITS describing the intra-nuclear cascade and evaporation processes generally well reproduced the measured isotopic production cross sections.

  18. 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.

  19. 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.

  20. Study of the properties of leading protons and antiprotons produced in p-barp exclusive reactions at 32 GeV/c

    International Nuclear Information System (INIS)

    Bogolyubskii, M.Y.; Boos, E.G.; Borovikov, A.A.

    1986-01-01

    We study the properties of leading protons and antiprotons from nondiffractive events in p-barp exclusive reactions at 32 GeV/c. It is found that the relative leading of protons and antiprotons does not depend on the final-state multiplicity and that the longitudinal momenta of leading hadrons are not correlated, but a significant part of the transverse momentum of a leading hadron is compensated by the transverse momentum of another hadron. It is shown that these experimental data are well described by the statistical model of independent particle emission but contradict the Lund string-fragmentation model

  1. Spallation reaction study for fission products in nuclear waste: Cross section measurements for 137Cs, 90Sr and 107Pd on proton and deuteron

    Directory of Open Access Journals (Sweden)

    Wang He

    2017-01-01

    Full Text Available Spallation reactions for the long-lived fission products 137Cs, 90Sr and 107Pd have been studied for the purpose of nuclear waste transmutation. The cross sections on the proton- and deuteron-induced spallation were obtained in inverse kinematics at the RIKEN Radioactive Isotope Beam Factory. Both the target and energy dependences of cross sections have been investigated systematically. and the cross-section differences between the proton and deuteron are found to be larger for lighter fragments. The experimental data are compared with the SPACS semi-empirical parameterization and the PHITS calculations including both the intra-nuclear cascade and evaporation processes.

  2. Studies of the Three-Nucleon System Dynamics in the Deuteron-Proton Breakup Reaction

    Science.gov (United States)

    Ciepał, I.; Kłos, B.; Stephan, E.; Kistryn, St.; Biegun, A.; Bodek, K.; Deltuva, A.; Epelbaum, E.; Eslami-Kalantari, M.; Fonseca, A. C.; Golak, J.; Jha, V.; Kalantar-Nayestanaki, N.; Kamada, H.; Khatri, G.; Kirillov, Da.; Kirillov, Di.; Kliczewski, St.; Kozela, A.; Kravcikova, M.; Machner, H.; Magiera, A.; Martinska, G.; Messchendorp, J.; Nogga, A.; Parol, W.; Ramazani-Moghaddam-Arani, A.; Roy, B. J.; Sakai, H.; Sekiguchi, K.; Sitnik, I.; Siudak, R.; Skibiński, R.; Sworst, R.; Urban, J.; Witała, H.; Zejma, J.

    2014-03-01

    One of the most important goals of modern nuclear physics is to contruct nuclear force model which properly describes the experimental data. To develop and test predictions of current models the breakup 1H(overrightarrow d, pp)n reaction was investigated experimentally at 100 and 130 MeV deuteron beam energies. Rich set of data for cross section, vector and tensor analyzing powers was obtained with the use of the SALAD and BINA detectors at KVI and Germanium Wall setup at FZ-Jülich. Results are compared with various theoretical approaches which describe the three-nucleon (3N) system dynamics. For correct description of the cross section data both, three-nucleon force (3NF) and Coulomb force, have to be included into calculations and influence of those ingredients is seizable at specific parts of the phase space. In case of the vector analyzing powers very low sensitivity to any effects beyond nucleon-nucleon interaction was found. At 130 MeV, the Axy data are not correctly described when 3NF models are included into calculations.

  3. 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.

  4. 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.

  5. Monoterpene separation by coupling proton transfer reaction time-of-flight mass spectrometry with fastGC.

    Science.gov (United States)

    Materić, Dušan; Lanza, Matteo; Sulzer, Philipp; Herbig, Jens; Bruhn, Dan; Turner, Claire; Mason, Nigel; Gauci, Vincent

    2015-10-01

    Proton transfer reaction mass spectrometry (PTR-MS) is a well-established technique for real-time analysis of volatile organic compounds (VOCs). Although it is extremely sensitive (with sensitivities of up to 4500 cps/ppbv, limits of detection monoterpenes, which belong to the most important plant VOCs, still cannot be distinguished so more traditional technologies, such as gas chromatography mass spectrometry (GC-MS), have to be utilised. GC-MS is very time consuming (up to 1 h) and cannot be used for real-time analysis. Here, we introduce a sensitive, near-to-real-time method for plant monoterpene research-PTR-MS coupled with fastGC. We successfully separated and identified six of the most abundant monoterpenes in plant studies (α- and β-pinenes, limonene, 3-carene, camphene and myrcene) in less than 80 s, using both standards and conifer branch enclosures (Norway spruce, Scots pine and black pine). Five monoterpenes usually present in Norway spruce samples with a high abundance were separated even when the compound concentrations were diluted to 20 ppbv. Thus, fastGC-PTR-ToF-MS was shown to be an adequate one-instrument solution for plant monoterpene research.

  6. Coplanarity of two-proton emissions in 400 MeV/nucleon Ne + NaF, Pb reactions

    International Nuclear Information System (INIS)

    Tanihata, Isao.

    1984-10-01

    Two-proton coincidence spectra have been measured in a wide kinematical range for 20 Ne + NaF and 20 Ne + Pb collisions at 400 MeV/nucleon. Coplanar-type correlations show different feature between Ne + NaF and Ne + Pb target reactions. A strong in-plane correlation, which correspond to quasi-elastic scatterings (QES) of nucleons, was observed in wide angular range (15 to 90 0 ) in NaF target collisions. Angular distributions of QES were reproduced reasonably well by a single nucleon-nucleon scattering model. Enhancement of the QES at momentum transfer around t = 2 - 3m/sub π/, which is predicted as an indication of pionic instability, was not observed. In Ne + Pb collisions, an azimuthally asymmetric emission of particles with respect to the beam axis were implied by the anti-coplanar correlation. A new type of coplanar correlation between the emission angle and the momentum suggests a back-to-back emission of projectile and target nucleons. 8 references, 8 figures

  7. Competitive roles of reagent vibration and translation in the exothermic proton transfer reaction H+2+Ar→HAr++H

    International Nuclear Information System (INIS)

    Bilotta, R.M.; Farrar, J.M.

    1981-01-01

    We present a crossed beam study of the title reaction at fixed collision energies of 1.2 and 2.3 eV with reagent H + 2 average vibrational energies of 0.44 and 0.89 eV; we also present data at fixed total energies with variable proportions of reagent vibrational and translational energy. At fixed collision energy, reagent vibrational excitation is found to have negligible effect on the total cross section for proton transfer. At fixed total energy, a decrease in reagent vibrational excitation with a corresponding increase in reagent translation leads to partial disposal of the incremental translation in product translation: At a total energy of 3.5 eV, 50% of this incremental reagent translation appears as product translation. At a total energy of 4.6 eV, 78% of the incremental translation appears in product translation. The experimental data are discussed in terms of induced attractive and repulsive energy release on an attractive potential surface. The role of noncollinear geometries and compressed reactant configurations is judged to be of substantial importance in assessing product rotational excitation and dissociation

  8. Continuous monitoring of the zinc-phosphate acid-base cement setting reaction by proton nuclear magnetic relaxation

    International Nuclear Information System (INIS)

    Apih, T.; Lebar, A.; Pawlig, O.; Trettin, R.

    2001-01-01

    Proton nuclear magnetic relaxation is a well-established technique for continuous and non destructive monitoring of hydration of conventional Portland building cements. Here, we demonstrate the feasibility of nuclear magnetic resonance (NMR) monitoring of the setting reaction of zinc-phosphate acid-base dental cements, which harden in minutes as compared to days, as in the case of Portland cements. We compare the setting of cement powder (mainly, zinc oxide) prepared with clinically used aluminum-modified orthophosphoric acid solution with the setting of a model system where cement powder is mixed with pure orthophosphoric acid solution. In contrast to previously published NMR studies of setting Portland cements, where a decrease of spin-lattice relaxation time is attributed to enhanced relaxation at the growing internal surface, spin-lattice relaxation time T 1 increases during the set of clinically used zinc-phosphate cement. Comparison of these results with a detailed study of diffusion, viscosity, and magnetic-field dispersion of T 1 in pure and aluminum-modified orthophosphoric acid demonstrates that the increase of T 1 in the setting cement is connected with the increase of molecular mobility in the residual phosphoric acid solution. Although not taken into account so far, such effects may also significantly influence the relaxation times in setting Portland cements, particularly when admixtures with an effect on water viscosity are used. [copyright] 2001 American Institute of Physics

  9. Helium production for 0.8-2.5 GeV proton induced spallation reactions, damage induced in metallic window materials

    International Nuclear Information System (INIS)

    Hilscher, D.; Herbach, C.-M.; Jahnke, U.; Tishchenko, V.; Enke, M.; Filges, D.; Goldenbaum, F.; Neef, R.-D.; Nuenighoff, K.; Paul, N.; Schaal, H.; Sterzenbach, G.; Letourneau, A.; Boehm, A.; Galin, J.; Lott, B.; Peghaire, A.; Pienkowski, L.

    2001-01-01

    Production cross-sections for neutrons and charged particles as well as excitation energy distributions in spallation reactions were measured recently by the NESSI-collaboration and have been employed to test different intra nuclear cascade models and the subsequent evaporation. The INCL/GEMINI code, which describes best the experimental data has been employed to calculate the damage cross-sections in Fe and Ta as well as the He/dpa ratio as a function of proton energy. For the same amount of neutron production in a typical target of a spallation neutron source the proton beam induced radiation damage in an Fe window is shown to decrease almost linearly with proton energy. For heavier materials such as Ta a similar decrease of the radiation damage is found only for energies above about 3 GeV

  10. Spectra of fast protons produced in the pA → pX reaction at the angle of 62 mrad

    International Nuclear Information System (INIS)

    Barabash, L.Z.; Buklej, A.E.; Gavrilov, V.B.

    1982-01-01

    Within the framework of a program of investigations into yields of secondary particles form internal targets of an accelerator obtained were experimetnal data on inclusive production of protons in pA interactions at 62 mradn angle at initial momenta of 4.0; 6.6; 9.5 GeV/c. The data obtained on differential cross sections of proton yields are tabulated. A- and t-dependences of quasi-elastic proton scattering with nuclei are discussed. A-dependence of cross sections of inelastic quasi-free reactions both in the region of isobar production and on the left of this region within the errors is the same as for quasi-elastic peak, α approximately 0.45. This α value is markedly less than a value characteristic of the A-dependence of total cross sections

  11. 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.

  12. 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.

  13. The proton spectral function of 40Ca and 48Ca studied with the (e,e'p) reaction

    International Nuclear Information System (INIS)

    Kramer, G.J.

    1990-01-01

    This thesis presents the results of an experimental study into the occupation of the orbitals around the Fermi level for 40 Ca and 48 Ca with quasi-elastic proton knock-out (e,e'p). Experiments have been carried out with the 500 MeV electron beam of the linear accelerator MEA at NIKHEF, Amsterdam. For 40 Ca the mechanism of the (e,e'p) reaction has been studied by comparing the measured momentum distributions of some strong transitions to discrete states in 39K , with various theoretical calculations. From this it has been concluded that uncertainties caused by deviations of the impulse approximation can be minimized if the measurements are carried out under parallel kinematical conditions. The spectroscopic strengths of the shell-model orbitals in states just below the Fermi level, for 40 Ca the 1d 3/2 , 1d 5/2 and 2s 1/2 orbitals, turned out to amount 50 to 70% of the IPSM limit. A small part of the missing strength has been found in the 1f 7/2 and 2p 3/2 orbitals which are just above the Fermi level (resp. 11 and 2% of the 2j+1 limit), which is an indication for ground state correlations. The spectroscopic strengths for the 1d 3/2 , 2s 1/2 and 1d 3/2 orbitals of 48 Ca turned out to be the same as for 40C a within the actual measuring accuracy. Above the Fermi level only strength in the 1f 7/2 orbital has been found (1% of the 2j+1 limit). The spectroscopic strengths determined with (e,e'p) experiments are about a factor two smaller than those obtained from (d, 3 He) experiments. This discrepancy has been studied by reviewing the model dependency of the DWBA analysis for the (d, 3 He) reaction with special emphasis on the sensitivities of the spectroscopic factors to the various approximations made in this theory. It is also investigated which part of the bound state wave function is probed by the (e,e'p) and the (d, 3 He) reactions in order to understand the model sensitivities arising from the exact shape of the bound state wave function. (H.W.).97 refs.; 48

  14. GAS-PHASE SYNTHESIS OF PRECURSORS OF INTERSTELLAR GLYCINE: A COMPUTATIONAL STUDY OF THE REACTIONS OF ACETIC ACID WITH HYDROXYLAMINE AND ITS IONIZED AND PROTONATED DERIVATIVES

    Energy Technology Data Exchange (ETDEWEB)

    Barrientos, Carmen; Redondo, Pilar; Largo, Laura; Rayon, Victor M.; Largo, Antonio, E-mail: alargo@qf.uva.es [Departamento de Quimica Fisica y Quimica Inorganica, Facultad de Ciencias, Universidad de Valladolid, 47005 Valladolid (Spain)

    2012-04-01

    A computational study of the reactions of hydroxylamine and its ionized and protonated derivatives with acetic acid is provided. The reaction of neutral hydroxylamine with acetic acid, despite being clearly exothermic, involves a very large energy barrier. The reaction of ionized hydroxylamine with acetic acid is also clearly exothermic, but again a significant energy barrier is found (around 24 kcal mol{sup -1} at the CCSD(T) level). The reaction of the most stable protonated isomer of hydroxylamine, NH{sub 3}OH{sup +}, with acetic acid also involves a high barrier (more than 27 kcal mol{sup -1} at the CCSD(T) level). Only the higher energy isomer, NH{sub 2}OH{sup +}{sub 2}, leads to a sensibly lower energy barrier (about 2.3 kcal mol{sup -1} at the CCSD(T) level). Nevertheless, an estimate of the reaction coefficient at low temperatures such as those reigning in the interstellar medium gives very low values. Therefore, it seems that precursors of interstellar glycine could not be efficiently produced from the reactions of hydroxylamine-derived ions with acetic acid.

  15. GAS-PHASE SYNTHESIS OF PRECURSORS OF INTERSTELLAR GLYCINE: A COMPUTATIONAL STUDY OF THE REACTIONS OF ACETIC ACID WITH HYDROXYLAMINE AND ITS IONIZED AND PROTONATED DERIVATIVES

    International Nuclear Information System (INIS)

    Barrientos, Carmen; Redondo, Pilar; Largo, Laura; Rayón, Víctor M.; Largo, Antonio

    2012-01-01

    A computational study of the reactions of hydroxylamine and its ionized and protonated derivatives with acetic acid is provided. The reaction of neutral hydroxylamine with acetic acid, despite being clearly exothermic, involves a very large energy barrier. The reaction of ionized hydroxylamine with acetic acid is also clearly exothermic, but again a significant energy barrier is found (around 24 kcal mol –1 at the CCSD(T) level). The reaction of the most stable protonated isomer of hydroxylamine, NH 3 OH + , with acetic acid also involves a high barrier (more than 27 kcal mol –1 at the CCSD(T) level). Only the higher energy isomer, NH 2 OH + 2 , leads to a sensibly lower energy barrier (about 2.3 kcal mol –1 at the CCSD(T) level). Nevertheless, an estimate of the reaction coefficient at low temperatures such as those reigning in the interstellar medium gives very low values. Therefore, it seems that precursors of interstellar glycine could not be efficiently produced from the reactions of hydroxylamine-derived ions with acetic acid.

  16. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

    Science.gov (United States)

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

    2016-10-24

    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Hyperthyroidism stimulates mitochondrial proton leak and ATP turnover in rat hepatocytes but does not change the overall kinetics of substrate oxidation reactions.

    Science.gov (United States)

    Harper, M E; Brand, M D

    1994-08-01

    Thyroid hormones have well-known effects on oxidative phosphorylation, but there is little quantitative information on their important sites of action. We have used top-down elasticity analysis, an extension of metabolic control analysis, to identify the sites of action of thyroid hormones on oxidative phosphorylation in rat hepatocytes. We divided the oxidative phosphorylation system into three blocks of reactions: the substrate oxidation subsystem, the phosphorylating subsystem, and the mitochondrial proton leak subsystem and have identified those blocks of reactions whose kinetics are significantly changed by hyperthyroidism. Our results show significant effects on the kinetics of the proton leak and the phosphorylating subsystems. Quantitative analyses revealed that 43% of the increase in resting respiration rate in hyperthyroid hepatocytes compared with euthyroid hepatocytes was due to differences in the proton leak and 59% was due to differences in the activity of the phosphorylating subsystem. There were no significant effects on the substrate oxidation subsystem. Changes in nonmitochondrial oxygen consumption accounted for -2% of the change in respiration rate. Top-down control analysis revealed that the distribution of control over the rates of mitochondrial oxygen consumption, ATP synthesis and consumption, and proton leak and over mitochondrial membrane potential (delta psi m) was similar in hepatocytes from hyperthyroid and littermate-paired euthyroid controls. The results of this study include the first complete top-down elasticity and control analyses of oxidative phosphorylation in hepatocytes from hyperthyroid rats.

  18. 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.

  19. Effects of an energy broadened proton beam on the neutron distribution for the "7Li(p,n)"7Be reaction near threshold

    International Nuclear Information System (INIS)

    Shor, A.; Eisen, Y.; Berkovits, D.; Hirsh, T.; Feinberg, G.; Friedman, M.; Paul, M.; Krasa, A.; Giorginis, G.; Plompen, A.

    2011-01-01

    A common method for simulating the thermal neutron conditions in the stellar interior is based on the "7Li(p,n)"7Be reaction near threshold energy. Maxwellian-averaged neutron capture cross-sections of mean energy 25 keV, relevant to the s-process nucleosynthesis, are measured at existing Van-de-Graaff (VdG) proton accelerators. Soreq NRC Applied Research superconducting linear Accelerator Facility (SARAF) phase 1 is in its final stage of commissioning. Maxwellian averaged neutron capture cross-section measurements are planned to be conducted using a forced-flow closed-loop liquid-lithium target (LiLiT). The proton beam energy spread of RF linear accelerators, such as SARAF, is typically larger than the spread of proton beams of VdG accelerators. The energy spread of SARAF proton beam at 1912 keV is calculated to be of the order of 20-40 keV FWHM as compared to about 3 keV FWHM for VdG accelerators. For simulating the SARAF proton beam we performed an experiment at the IRMM-Geel VdG using a gold foil degrader positioned before the LiF target. This degrader shifts the mean proton energy to 1912 keV and it broadens the proton beam energy to values simulating the spread of the proton beam at SARAF. For calibrating the cross-sections we also performed a "7Li(p,n)"7Be experiment without the gold foil degrader at a proton energy of 1912 keV. The VdG was operated in a pulse mode and the neutron energies were determined by time-of-flight measurements using "6Li glass detectors. Detector efficiencies were obtained by Monte Carlo calculations. We present our study and compare the results for both narrow and broad energy proton beams. It is shown that the energy distribution for the broad-energy beam with a spread of 15 keV is similar to that of the distribution of the narrow energy beam and they peak nearly at the same energy. The broad-energy distribution has a tail extending to higher energies than that of the narrow-energy beam. It appears also that the neutron

  20. An idea for the future proton detection of (p,2p) reactions with the R3B set-up at FAIR

    International Nuclear Information System (INIS)

    Ribeiro, G; Perea, A; Mårtensson, M

    2015-01-01

    The R 3 B Collaboration has a long experience in probing exotic nuclei via quasi-free scattering reactions. To continue these studies a new array capable of detecting protons and gamma rays of high energy is currently being developed, the CALIFA (R 3 B CALorimeterfor In Flight γ arrays and high energy charged pArticles). This contribution reports on the current solution for the forward Endcap of the CALIFA detector and on the latest test results. (paper)

  1. Investigation of the tensor analyzing power Ayy in the reaction A(d polarized, p)X at large transverse momenta of proton

    International Nuclear Information System (INIS)

    Afanas'ev, S.V.; Arkhipov, V.V.; Azhgirej, L.S.

    1997-01-01

    An experiment on the studying of the tensor analyzing power A yy in the reaction A(d polarized, p)X at large transverse momenta of proton using a polarized deuteron beam of LHE accelerator complex has been proposed. These measurements could provide the valuable information on the spin structure of the deuteron at short distances. The estimation of the beam request for SPHERE set-up is performed

  2. 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...

  3. Excitation functions of proton induced reactions on {sup nat}Fe in the energy region up to 45 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kwangsoo [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Khandaker, Mayeen Uddin [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Department of Physics, University of Malaya, 50603 Kuala Lumpur (Malaysia); Naik, Haladhara [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Radiochemistry Division, Bhabha Atomic Research Center, Trombay, Mumbai 400085 (India); Kim, Guinyun, E-mail: gnkim@knu.ac.kr [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

    2014-03-01

    The excitation functions of various reaction products such as {sup 55,56,57}Co, {sup 52}Fe, {sup 52,54}Mn, and {sup 51}Cr in the {sup nat}Fe(p, x) reactions were measured by the stacked-foil activation technique in the energy range between their respective reaction threshold and 45 MeV at the MC-50 cyclotron of the Korean Institute of Radiological and Medical Sciences, Korea. The present experimental data were compared with the existing literature data. It was found that excitation function of {sup 56,57}Co and {sup 51}Cr from the {sup nat}Fe(p, x) reaction are in agreement with the literature data. However, the cross-sections for {sup nat}Fe(p, x){sup 52}Fe reactions are lower and those for {sup nat}Fe(p, x){sup 52}Mn and {sup nat}Fe(p, x){sup 54}Mn reactions are higher than the literature data. The reaction cross-sections of the above mentioned reaction products were also compared with those from the TENDL-2012 library based on the TALYS-1.4 program as a function of proton energy, which was reproduced the trend of the excitation functions of the experimental {sup nat}Fe(p, x) reaction cross-section. The integral yields for thick target of the investigated radionuclides were calculated from the excitation function.

  4. Iridium-decorated palladium-platinum core-shell catalysts for oxygen reduction reaction in proton exchange membrane fuel cell.

    Science.gov (United States)

    Wang, Chen-Hao; Hsu, Hsin-Cheng; Wang, Kai-Ching

    2014-08-01

    Carbon-supported Pt, Pd, Pd-Pt core-shell (Pt(shell)-Pd(core)/C) and Ir-decorated Pd-Pt core-shell (Ir-decorated Pt(shell)-Pd(core)/C) catalysts were synthesized, and their physical properties, electrochemical behaviors, oxygen reduction reaction (ORR) characteristics and proton exchange membrane fuel cell (PEMFC) performances were investigated herein. From the XRD patterns and TEM images, Ir-decorated Pt(shell)-Pd(core)/C has been confirmed that Pt was deposited on the Pd nanoparticle which had the core-shell structure. Ir-decorated Pt(shell)-Pd(core)/C has more positive OH reduction peak than Pt/C, which is beneficial to weaken the binding energy of Pt-OH during the ORR. Thus, Ir-decorated Pt(shell)-Pd(core)/C has higher ORR activity than Pt/C. The maximum power density of H2-O2 PEMFC using Ir-decorated Pt(shell)-Pd(core)/C is 792.2 mW cm(-2) at 70°C, which is 24% higher than that using Pt/C. The single-cell accelerated degradation test of PEMFC using Ir-decorated Pt(shell)-Pd(core)/C shows good durability by the potential cycling of 40,000 cycles. This study concludes that Ir-decorated Pt(shell)-Pd(core)/C has the low Pt content, but it can facilitate the low-cost and high-efficient PEMFC. Copyright © 2013 Elsevier Inc. All rights reserved.

  5. Measurements of Volatile Organic Compounds Using Proton Transfer Reaction – Mass Spectrometry during the MILAGRO 2006 Campaign

    Directory of Open Access Journals (Sweden)

    E. C. Fortner

    2009-01-01

    Full Text Available Volatile organic compounds (VOCs were measured by proton transfer reaction – mass spectrometry (PTR-MS on a rooftop in the urban mixed residential and industrial area North Northeast of downtown Mexico City as part of the Megacity Initiative – Local and Global Research Observations (MILAGRO 2006 field campaign. Thirty eight individual masses were monitored during the campaign and many species were quantified including methanol, acetaldehyde, toluene, the sum of C2 benzenes, the sum of C3 benzenes, acetone, isoprene, benzene, and ethyl acetate. The VOC measurements were analyzed to gain a better understanding of the type of VOCs present in the MCMA, their diurnal patterns, and their origins. Diurnal profiles of weekday and weekend/holiday aromatic VOC concentrations showed the influence of vehicular traffic during the morning rush hours and during the afternoon hours. Plumes including elevated toluene as high as 216 parts per billion (ppb and ethyl acetate as high as 183 ppb were frequently observed during the late night and early morning hours, indicating the possibility of significant industrial sources of the two compounds in the region. Wind fields during those peak episodes revealed no specific direction for the majority of the toluene plumes but the ethyl acetate plumes arrived at the site when winds were from the Southwest or West. The PTR-MS measurements combined with other VOC measuring techniques at the field site as well as VOC measurements conducted in other areas of the Mexico City Metropolitan Area (MCMA will help to develop a better understanding of the spatial pattern of VOCs and its variability in the MCMA.

  6. Stripping of two protons and one alpha particle transfer reactions for 16 O + A Sm and their influence on the fusion cross section

    International Nuclear Information System (INIS)

    Maciel, A.M.M.; Gomes, P.R.S.

    1995-01-01

    Transfer cross section angular distribution data for the stripping of two protons and one alpha particle are studied for the 16 O + A Sm systems (A=144, 148, 150, 152 and 154), at near barrier energies. A semiclassical formalism is used to derive the corresponding transfer form factors. For only one channel the analysis shows evidences that the transfer reaction mechanism at backward angles - corresponding to small distances, may behave as a multi-step process leading to fusion. Simplified coupled channel calculations including transfer channels are performed for the study of the sub-barrier of these systems. The influence of short distance transfer reactions on the fusion is discussed. (author)

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. Proton solvation and proton transfer in chemical and electrochemical processes

    International Nuclear Information System (INIS)

    Lengyel, S.; Conway, B.E.

    1983-01-01

    This chapter examines the proton solvation and characterization of the H 3 O + ion, proton transfer in chemical ionization processes in solution, continuous proton transfer in conductance processes, and proton transfer in electrode processes. Topics considered include the condition of the proton in solution, the molecular structure of the H 3 O + ion, thermodynamics of proton solvation, overall hydration energy of the proton, hydration of H 3 O + , deuteron solvation, partial molal entropy and volume and the entropy of proton hydration, proton solvation in alcoholic solutions, analogies to electrons in semiconductors, continuous proton transfer in conductance, definition and phenomenology of the unusual mobility of the proton in solution, solvent structure changes in relation to anomalous proton mobility, the kinetics of the proton-transfer event, theories of abnormal proton conductance, and the general theory of the contribution of transfer reactions to overall transport processes

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

    KAUST Repository

    Lattanzi, Alessandra; De Fusco, Claudia; Russo, Alessio; Poater, Albert; Cavallo, Luigi

    2012-01-01

    A dramatic enhancement of the diastereo- and enantioselectivity in the nitro-Michael addition reaction organocatalysed by a commercially available α,α-l-diaryl prolinol was disclosed when performing the reaction in unconventional hexafluorobenzene

  13. Tailoring medium energy proton beam to induce low energy nuclear reactions in ⁸⁶SrCl₂ for production of PET radioisotope ⁸⁶Y.

    Science.gov (United States)

    Medvedev, Dmitri G; Mausner, Leonard F; Pile, Philip

    2015-07-01

    This paper reports results of experiments at Brookhaven Linac Isotope Producer (BLIP) aiming to investigate effective production of positron emitting radioisotope (86)Y by the low energy (86)Sr(p,n) reaction. BLIP is a facility at Brookhaven National Laboratory designed for the proton irradiation of the targets for isotope production at high and intermediate proton energies. The proton beam is delivered by the Linear Accelerator (LINAC) whose incident energy is tunable from 200 to 66 MeV in approximately 21 MeV increments. The array was designed to ensure energy degradation from 66 MeV down to less than 20 MeV. Aluminum slabs were used to degrade the proton energy down to the required range. The production yield of (86)Y (1.2+/-0.1 mCi (44.4+/-3.7) MBq/μAh) and ratio of radioisotopic impurities was determined by assaying an aliquot of the irradiated (86)SrCl2 solution by gamma spectroscopy. The analysis of energy dependence of the (86)Y production yield and the ratios of radioisotopic impurities has been used to adjust degrader thickness. Experimental data showed substantial discrepancies in actual energy propagation compared to energy loss calculations. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Nuclear structure of weakly bound radioactive nuclei through elastic and and inelastic scattering on proton. Impacts of the couplings induced by these exotic nuclei on direct reactions; Structure de noyaux radioactifs faiblement lies par diffusions elastiques et inelastiques sur proton. Effets des couplages induits par ces noyaux exotiques sur les reactions directes

    Energy Technology Data Exchange (ETDEWEB)

    Lapoux, V

    2005-09-15

    Information on the structure, spectroscopy and target interaction potentials of exotic nuclei can be inferred by interpreting measured data from direct reactions on proton such as elastic or inelastic scattering of proton (p,p') or one-nucleon transfer reaction (p,d). A series of experimental results has been obtained at the GANIL facilities on the setting composed of the MUST telescope array used for the detection of light charged-particles and of CATS beam detectors. This setting aims at measuring reactions on light proton or deuteron targets through reverse kinematics. Particularly, results on C{sup 10}, C{sup 11} and on direct reactions with the He{sup 8} beam of Spiral are presented. The first chapter is dedicated to the description of the most important theories concerning the nucleus. The experimental tools used to probe the nucleus are reported in the second chapter. The third and fourth chapters present the framework that has allowed us to analyse results from (p,p') and (p,d) reactions on weakly bound exotic nuclei. The last chapter is dedicated to the description of future experimental programs. (A.C.)

  15. 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.

  16. Analysis of expiration gas in intensive care patients with SIRS/sepsis using proton-transfer-reaction-mass-spectrometry

    International Nuclear Information System (INIS)

    Bodrogi, F.B.M.

    2003-11-01

    In 1971, Pauling and co-workers were the first to detect volatile organic compounds (VOC) in human breath. Since then, a number of technical applications for breath gas analyses have been designed and processed, among them gas chromatography and proton transfer reaction-mass spectrometry (PTR-MS). Due to this technical progress it is meanwhile possible to correlate different kinds and stages of diseases with measurable changes in the patient's VOC profile. The aim of the present study was to investigate the composition of VOC in exhaled air of patients with sepsis via PTR-MS. To isolate distinct volatile organic compounds that may serve as clinical markers for the onset, the progress, as well as the outcome of the disease, the results obtained from septic patients were compared with two different control groups: 25 healthy, non-smoking volunteers enrolled in the day-case-surgery and 25 post-operative in-patients residing in post-anaesthetic care units (PACU). PTR-MS is capable to analyze VOC according to their molecular weight with a range between 21-230 Da. A total of 210 different masses has been detected in the present study. 54 masses were significantly different in exhaled air of septic patients as compared to healthy controls as well as post-operative patients. Among them, mass 69 representing isoprene might be of special interest for the diagnosis of sepsis. Although no exact biochemical properties of isoprene have been described to date, it is known that isoprene synthesis is increased in plants following exposure to oxidative stress. Chronic, systemic infectious diseases like sepsis are accompanied by the production of reactive oxygen species, indicating that isoprene might be increased in the course of sepsis, too. In the present study, isoprene values were markedly higher in septic patients as compared to PACU residents (3.3-fold increase in mean value) and to healthy volunteers (2.2-fold increase in mean value). In addition (and in contrast to other VOC

  17. Rapid "breath-print" of liver cirrhosis by proton transfer reaction time-of-flight mass spectrometry. A pilot study.

    Directory of Open Access Journals (Sweden)

    Filomena Morisco

    Full Text Available UNLABELLED: The aim of the present work was to test the potential of Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS in the diagnosis of liver cirrhosis and the assessment of disease severity by direct analysis of exhaled breath. Twenty-six volunteers have been enrolled in this study: 12 patients (M/F 8/4, mean age 70.5 years, min-max 42-80 years with liver cirrhosis of different etiologies and at different severity of disease and 14 healthy subjects (M/F 5/9, mean age 52.3 years, min-max 35-77 years. Real time breath analysis was performed on fasting subjects using a buffered end-tidal on-line sampler directly coupled to a PTR-ToF-MS. Twelve volatile organic compounds (VOCs resulted significantly differently in cirrhotic patients (CP compared to healthy controls (CTRL: four ketones (2-butanone, 2- or 3- pentanone, C8-ketone, C9-ketone, two terpenes (monoterpene, monoterpene related, four sulphur or nitrogen compounds (sulfoxide-compound, S-compound, NS-compound, N-compound and two alcohols (heptadienol, methanol. Seven VOCs (2-butanone, C8-ketone, a monoterpene, 2,4-heptadienol and three compounds containing N, S or NS resulted significantly differently in compensate cirrhotic patients (Child-Pugh A; CP-A and decompensated cirrhotic subjects (Child-Pugh B+C; CP-B+C. ROC (Receiver Operating Characteristic analysis was performed considering three contrast groups: CP vs CTRL, CP-A vs CTRL and CP-A vs CP-B+C. In these comparisons monoterpene and N-compound showed the best diagnostic performance. CONCLUSIONS: Breath analysis by PTR-ToF-MS was able to distinguish cirrhotic patients from healthy subjects and to discriminate those with well compensated liver disease from those at more advanced severity stage. A breath-print of liver cirrhosis was assessed for the first time.

  18. Model-Independent Analysis of the Neutron-Proton Final-State Interaction Region in the $\\pi\\pi \\to pn\\pi^+$ Reaction

    CERN Document Server

    Uzikov, Yu N

    2001-01-01

    Experimental data on the \\pi\\pi\\to pn\\pi^+ reaction measured in an exclusive two-arm experiment at 800 MeV show a narrow peak arising from the strong proton-neutron final-state interaction. It was claimed, within the framework of a certain model, that this peak contained up to a 25 % spin-singlet final-state contribution. By comparing the data with those of \\pi\\pi\\to d\\pi^+ in a largely model-independent way, it is here demonstrated that at all the angles measured the whole of the peak could be explained as being due to spin-triplet final states, with the spin-singlet being at most a few percent. Good qualitative agreement with the measured proton analysing power is also found within this approach.

  19. Study of the reaction 35Cl(p,γγ)36Ar at the proton energy Esub(p) = 533 keV

    International Nuclear Information System (INIS)

    Grosswendt, B.

    1972-01-01

    Triple correlation experiments were carried out on the 35 Cl(p,γγ) 36 Ar reaction at the proton energy of Esub(p) = 533 keV for studies of the 9.025 MeV state in the 36 Ar nucleus. The analysis of the gamma cascades between the 36 Ar states at 9.025 MeV, 1.97 MeV and the ground state resulted in the spin assignment of J 1 =2 + for the proton capture level. Comparison of the 36 Ar level scheme with states in the isobar 36 Cl nucleus indicated that the 2 + state in 36 Ar as measured in this study may be the isobar state analogous with 2 + level at 1.949 MeV in the 36 Cl spectrum. (orig./RF) [de

  20. /sup 9/Be(p,n)/sup 9/B reaction with polarized protons from 2. 4 to 2. 9 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Rohrer, U [Basel Univ. (Switzerland); Brown, L [Carnegie Institution of Washington, D.C. (USA). Dept. of Terrestrial Magnetism

    1976-04-19

    A polarized beam was used to measure angular distributions of the proton analyzing power of the /sup 9/Be(p,n)/sup 9/B reaction at six energies from 2.4 to 2.9 MeV. The data were measured typically to an accuracy of 0.02 with a target 23 keV thick at 2.5 MeV bombarding energy. The analyzing power can be fitted with three associated Legendre polynomials, the coefficients of which show considerable variation in the vicinity of the pair of degenerate states at 2.56 MeV. The coefficients of the odd polynomials are not zero over the energy range of these states, indicating that they are of opposite parity. Comparison of these analyzing power measurements with previous data for the neutron polarization induced with unpolarized protons shows near equality at all energies, as expected from Conzett's theorem.

  1. Measurement of activation reaction rate distribution on a mercury target with a lead-reflector and light-water-moderator for high energy proton bombardment using AGS accelerator

    International Nuclear Information System (INIS)

    Kasugai, Yoshimi; Takada, Hiroshi; Meigo, Shin-ichiro

    2001-02-01

    Characteristic of spallation neutrons driven by GeV protons from a mercury target with a lead-reflector and light-water-moderator was studied experimentally using the Alternating Gradient Synchrotron (AGS) facility of Brookhaven National Laboratory in a framework of the ASTE (AGS Spallation Target Experiment) collaboration. Several reaction rates along with the mercury target were measured with the activation method at incident proton energies of 1.94, 12 and 24 GeV. Indium, niobium, aluminum, cobalt, nickel and bismuth were used as activation detectors to cover the threshold energy of between 0.33 and 40.9 MeV. This report summarizes the experimental procedure with all the measured data. (author)

  2. Formation of short-lived positron emitters in reactions of protons of energies up to 200 MeV with the target elements carbon, nitrogen and oxygen

    CERN Document Server

    Kettern, K; Qaim, S M; Shubin, Yu N; Steyn, G F; Van der Walt, T N; 10.1016/j.apradiso.2004.02.007

    2004-01-01

    Excitation functions were measured by the stacked-foil technique for proton induced reactions on carbon, nitrogen and oxygen leading to the formation of the short-lived positron emitters /sup 11/C (T/sub 1 /2/=20.38 min) and /sup 13/N (T/sub 1/2/=9.96 min). The energy region covered extended up to 200 MeV. The product activity was measured non-destructively via gamma -ray spectrometry. A careful decay curve analysis of the positron annihilation radiation was invariably performed. The experimental results were compared with theoretical data obtained using the modified hybrid nuclear model code ALICE-IPPE for intermediate energies. The agreement was found to be generally satisfactory. The data are of importance in proton therapy.

  3. 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

  4. The rate of second electron transfer to QB(-) in bacterial reaction center of impaired proton delivery shows hydrogen-isotope effect.

    Science.gov (United States)

    Maróti, Ágnes; Wraight, Colin A; Maróti, Péter

    2015-02-01

    The 2nd electron transfer in reaction center of photosynthetic bacterium Rhodobacter sphaeroides is a two step process in which protonation of QB(-) precedes interquinone electron transfer. The thermal activation and pH dependence of the overall rate constants of different RC variants were measured and compared in solvents of water (H2O) and heavy water (D2O). The electron transfer variants where the electron transfer is rate limiting (wild type and M17DN, L210DN and H173EQ mutants) do not show solvent isotope effect and the significant decrease of the rate constant of the second electron transfer in these mutants is due to lowering the operational pKa of QB(-)/QBH: 4.5 (native), 3.9 (L210DN), 3.7 (M17DN) and 3.1 (H173EQ) at pH7. On the other hand, the proton transfer variants where the proton transfer is rate limiting demonstrate solvent isotope effect of pH-independent moderate magnitude (2.11±0.26 (WT+Ni(2+)), 2.16±0.35 (WT+Cd(2+)) and 2.34±0.44 (L210DN/M17DN)) or pH-dependent large magnitude (5.7 at pH4 (L213DN)). Upon deuteration, the free energy and the enthalpy of activation increase in all proton transfer variants by about 1 kcal/mol and the entropy of activation becomes negligible in L210DN/M17DN mutant. The results are interpreted as manifestation of equilibrium and kinetic solvent isotope effects and the structural, energetic and kinetic possibility of alternate proton delivery pathways are discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. 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.

  6. Chemiosmotic Energy Conservation in Dinoroseobacter shibae: Proton Translocation Driven by Aerobic Respiration, Denitrification, and Photosynthetic Light Reaction

    Directory of Open Access Journals (Sweden)

    Christian Kirchhoff

    2018-05-01

    Full Text Available Dinoroseobacter shibae is an aerobic anoxygenic phototroph and able to utilize light energy to support its aerobic energy metabolism. Since the cells can also grow anaerobically with nitrate and nitrite as terminal electron acceptor, we were interested in how the cells profit from photosynthesis during denitrification and what the steps of chemiosmotic energy conservation are. Therefore, we conducted proton translocation experiments and compared O2-, NO3-, and NO2- respiration during different light regimes and in the dark. We used wild type cells and transposon mutants with knocked-out nitrate- and nitrite- reductase genes (napA and nirS, as well as a mutant (ppsR impaired in bacteriochlorophyll a synthesis. Light had a positive impact on proton translocation, independent of the type of terminal electron acceptor present. In the absence of an electron acceptor, however, light did not stimulate proton translocation. The light-driven add-on to proton translocation was about 1.4 H+/e- for O2 respiration and about 1.1 H+/e- for NO3- and NO2-. We could see that the chemiosmotic energy conservation during aerobic respiration involved proton translocation, mediated by the NADH dehydrogenase, the cytochrome bc1 complex, and the cytochrome c oxidase. During denitrification the last proton translocation step of the electron transport was missing, resulting in a lower H+/e- ratio during anoxia. Furthermore, we studied the type of light-harvesting and found that the cells were able to channel light from the green–blue spectrum most efficiently, while red light has only minor impact. This fits well with the depth profiles for D. shibae abundance in the ocean and the penetration depth of light with different wavelengths into the water column.

  7. Optimization of the pion beam for the HADES detector and determination of the {eta} form factor in proton-proton reactions at 2.2 GeV; Optimierung des Pionenstrahls zum HADES-Detektor und Bestimmung des {eta}-Formfaktors in Proton-Proton-Reaktionen bei 2.2 GeV

    Energy Technology Data Exchange (ETDEWEB)

    Spruck, Bjoern

    2008-02-08

    This thesis contains two tasks. The first part focuses on the development and optimization of the pion beam facility for the HADES experiment. The second part describes the measurement of the electromagnetic transition form factor of the {eta} meson in proton-proton reactions. To investigate pion-nucleon reaction, a secondary pion beam is required. The pions are produced by a heavy ion beam impinging on a beryllium target. In order to determine the profile of the beam focus, two scintillating fiber detectors have been built as part of this thesis and are read out with recently developed electronics. The measured size of the beam focus appeared to be not acceptable, which can be attributed to the achromatic magnetic focusing in the beam line. Simulations have shown, that an additional quadrupole magnet directly in front of HADES would solve this problem and improve the beam quality. A test experiment including this new quadrupole has been performed and the analysis is still in progress. Preliminary results show a significant reduction of the momentum dependency of the focus. The size of the actual beam spot has been deduced to 14 mm by using an indirect tracking approach. For deducing the electromagnetic structure of hadrons, a first step has been done by analyzing the {eta} Dalitz decay in p+p reactions at 2.2 GeV kinetic energy to determine the electromagnetic transition form factor of the {eta} meson. A fit to the data leads to a form factor slope of b=2.2{sub -1.4}{sup +1.2} GeV{sup -2}. This corresponds to a pole mass of {lambda}=680{sub -130}{sup +460} MeV/c{sup 2}. It has been shown, that a semi-exclusive analysis of the {eta} Dalitz decay within the event hypothesis framework including a kinematical fit is feasible. (orig.)

  8. 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.

  9. 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.

  10. 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.

  11. Combined experimental and theoretical study of the mechanism and enantioselectivity of palladium-catalyzed intermolecular Heck coupling

    DEFF Research Database (Denmark)

    Henriksen, Signe Teuber; Norrby, Per-Ola; Kaukoranta, Päivi

    2008-01-01

    . The steric interactions in this transition state fully account for the enantioselectivity observed with the ligands studied. The calculations also predict relative reactivity and nonlinear mixing effects for the investigated ligands; these predictions are fully validated by experimental testing. Finally......The asymmetric Heck reaction using P,N-ligands has been studied by a combination of theoretical and experimental methods. The reaction follows Halpern-style selectivity; that is, the major isomer is produced from the least favored form of the pre-insertion intermediate. The initially formed Ph......, the low conversion observed with some catalysts was found to be caused by inactivation due to weak binding of the ligand to Pd(0). Adding monodentate PPh3 alleviated the precipitation problem without deteriorating the enantioselectivity and led to one of the most effective catalytic systems to date....

  12. Investigation of the p+N → [Σ0K+]+N reaction at the proton energy Ep = 70 GeV

    International Nuclear Information System (INIS)

    Anon.

    1994-01-01

    The p+N → [Σ 0 K + ]+N reaction was studied in experiments using the SPHINX detector placed in the 70-GeV proton beam of the IHEP accelerator. In the effective mass spectrum of the M(Σ 0 K + ) system produced in the coherent diffractive transition, a clear peak with mass M = 1999 ± 7 MeV and width Γ = 91 ± 17 MeV was observed in addition to the near-threshold structure with mass M ≅ 1800 MeV. 7 refs., 3 figs

  13. Invariant mass spectroscopy of {sup 19,17}C and {sup 14}B using proton inelastic and charge-exchange reactions

    Energy Technology Data Exchange (ETDEWEB)

    Satou, Y., E-mail: satou@phya.snu.ac.k [Department of Physics and Astronomy, Seoul National University, Seoul (Korea, Republic of); Nakamura, T. [Department of Physics, Tokyo Institute of Technology, Tokyo (Japan); Fukuda, N. [Institute of Physical and Chemical Research (RIKEN), Saitama (Japan); Sugimoto, T.; Kondo, Y.; Matsui, N.; Hashimoto, Y.; Nakabayashi, T.; Okumura, Y.; Shinohara, M. [Department of Physics, Tokyo Institute of Technology, Tokyo (Japan); Motobayashi, T.; Yanagisawa, Y.; Aoi, N.; Takeuchi, S.; Gomi, T.; Togano, Y. [Institute of Physical and Chemical Research (RIKEN), Saitama (Japan); Kawai, S. [Department of Physics, Rikkyo University, Tokyo (Japan); Sakurai, H. [Institute of Physical and Chemical Research (RIKEN), Saitama (Japan); Ong, H.J.; Onishi, T.K. [Department of Physics, University of Tokyo, Tokyo (Japan)

    2010-03-01

    The neutron-rich carbon isotopes {sup 19,17}C and the boron isotope {sup 14}B have been investigated, respectively, by the proton inelastic and charge-exchange reactions on a liquid hydrogen target at around 70 MeV/nucleon. The invariant mass method in inverse kinematics was employed to map the energy spectrum above the neutron decay threshold of the residual nuclei. New states on carbon isotopes are reported. An experimental capability of extracting beta-decay strengths via forward angle (p,n) cross sections on unstable nuclei is shown.

  14. A statistical analysis of volatile organic compounds observed during the TEXAQS2000 air quality study at LaPorte, Tx, using proton-transfer-reaction mass spectrometry

    International Nuclear Information System (INIS)

    Kuster, B.; Williams, E.; Fehsenfeld, F.; Jobson, T.; Fall, R.; Lindinger, W.; Karl, T.

    2002-01-01

    Statistical analysis of online VOC measurements obtained by proton-transfer-reaction mass spectrometry (PTR-MS) during the TEXAQS2000 intensive period is presented. The experiment was based at the La Porte site, near the Houston ship channel (HSC), and deployed for continuous long-term monitoring. Multivariate techniques helped to identify various VOC sources in the vicinity of HSC and distinguish between different anthropogenic emissions. An assessment is given of the selectivity and interpretation of mass scans from this online technique in complex urban and industrial VOC matrix. (author)

  15. Proton and deuteron production in neutron-induced reactions on carbon at En=42.5, 62.7, and 72.8 MeV

    International Nuclear Information System (INIS)

    Slypen, I.; Corcalciuc, V.; Meulders, J.P.

    1995-01-01

    Double-differential cross sections for proton and deuteron production in fast neutron induced reactions on carbon are reported for three incident neutron energies: 42.5, 62.7, and 72.8 MeV. Angular distributions were measured at laboratory angles between 20 degree and 160 degree. Procedures for data taking and data reduction are presented. Energy-differential cross sections and total cross sections are also reported. Experimental cross sections are compared with existing data and with theoretical calculations in the frame of the intranuclear cascade model

  16. Light particle production in spallation reactions induced by protons of 0.8-2.5 GeV incident kinetic energy

    International Nuclear Information System (INIS)

    Herbach, Claus-Michael; Enke, Michael; Boehm, Andreas

    2002-01-01

    Absolute production cross sections have been measured simultaneously for neutrons and light charged particles in 0.8-2.5 GeV proton induced spallation reactions for a series of target nuclei from aluminum up to uranium. The high detection efficiency both for neutral and charged evaporative particles provides an event-wise access to the amount of projectile energy dissipated into nuclear excitation. Various intra nuclear cascade plus evaporation models have been confronted with the experimental data showing large discrepancies for hydrogen and helium production. (author)

  17. Dynamics of Chemical and Charge Transfer Reactions of Molecular Dications: IV. Proton Transfer and Reactions of Dication Isomers in the CHCl2+ +D2 System

    Czech Academy of Sciences Publication Activity Database

    Roithová, Jana; Žabka, Ján; Hrušák, Jan; Thissen, R.; Herman, Zdeněk

    2003-01-01

    Roč. 107, - (2003), s. 7347-7354 ISSN 1089-5639 R&D Projects: GA ČR GA203/00/0632; GA AV ČR KJB4040302 Grant - others:Barrande(FR) 2002-013-1 Institutional research plan: CEZ:AV0Z4040901 Keywords : dynamics of chemical * molecular dications * proton transfer Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.792, year: 2003

  18. Proton-transfer reaction mass spectrometry (PTR-MS) for the authentication of regionally unique South African lamb

    NARCIS (Netherlands)

    Erasmus, Sara W.; Muller, Magdalena; Alewijn, Martin; Koot, Alex H.; Ruth, van Saskia M.; Hoffman, Louwrens C.

    2017-01-01

    The volatile fingerprints of South African lamb meat and fat were measured by proton-transfer mass spectrometry (PTR-MS) to evaluate it as an authentication tool. Meat and fat of the Longissimus lumborum (LL) of lambs from six different regions were assessed. Analysis showed that the volatile

  19. 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.

  20. Electrostatics of the photosynthetic bacterial reaction center. Protonation of Glu L 212 and Asp L 213 - A new method of calculation.

    Science.gov (United States)

    Ptushenko, Vasily V; Cherepanov, Dmitry A; Krishtalik, Lev I

    2015-12-01

    Continuum electrostatic calculation of the transfer energies of anions from water into aprotic solvents gives the figures erroneous by order of magnitude. This is due to the hydrogen bond disruption that suggests the necessity to reconsider the traditional approach of the purely electrostatic calculation of the transfer energy from water into protein. In this paper, the method combining the experimental estimates of the transfer energies from water into aprotic solvent and the electrostatic calculation of the transfer energies from aprotic solvent into protein is proposed. Hydrogen bonds between aprotic solvent and solute are taken into account by introducing an imaginary aprotic medium incapable to form hydrogen bonds with the solute. Besides, a new treatment of the heterogeneous intraprotein dielectric permittivity based on the microscopic protein structure and electrometric measurements is elaborated. The method accounts semi-quantitatively for the electrostatic effect of diverse charged amino acid substitutions in the donor and acceptor parts of the photosynthetic bacterial reaction center from Rhodobacter sphaeroides. Analysis of the volatile secondary acceptor site QB revealed that in the conformation with a minimal distance between quinone QB and Glu L 212 the proton uptake upon the reduction of QB is prompted by Glu L 212 in alkaline and by Asp L 213 in slightly acidic regions. This agrees with the pH dependences of protonation degrees and the proton uptake. The method of pK calculation was applied successfully also for dissociation of Asp 26 in bacterial thioredoxin. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. THE HYDROVINYLATION AND RELATED REACTIONS: NEW PROTOCOLS AND CONTROL ELEMENTS IN SEARCH OF GREATER SYNTHETIC EFFICIENCY AND SELECTIVITY. (R826120)

    Science.gov (United States)

    New reaction conditions and stereochemical control elements for heterodimerization between ethylene (or propylene) and functionalized vinyl arenes are highlighted (see equation). For example, an enantioselective version of the hydrovinylation reaction uses [{(allyl)NiBr}...

  2. 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.

  3. A Study of the Angular Distributions of Neutrons from the {sup 9}Be (p,n) {sup 9}B Reaction at Low Proton Energies

    Energy Technology Data Exchange (ETDEWEB)

    Antolkovic, B; Holmqvist, B; Wiedling, T

    1964-10-15

    The angular distributions of neutrons from the reaction {sup 9}Be (p, n) {sup 9}B have been studied at the proton energies 2.300, 2.335, 2.389, and 2.560 MeV. Time-of-flight techniques have been used. The angular distribution measurements show remarkable differences compared to earlier published results using long-counters as detectors. The new results are ascribed to the different experimental methods. By using time-of-flight techniques it has been possible to eliminate disturbing influences from neutrons obtained from the {sup 9}Be (p,p'n) {sup 8}Be reaction which has a lower reaction threshold than the {sup 9}Be (p, n) {sup 9}B reaction as well as other Be-p-reactions emitting neutrons. The experimental distribution at 2.30 MeV has been compared with the simplified theories for direct interaction processes developed by Satchler and Rodberg. It is shown that Rodberg's proposal of using optical model wave functions describes the experiment better than Satchler's original theory. However, a good fitting leads to a nuclear radius as well as an optical potential which is appreciably smaller than ordinarily obtained in scattering experiments.

  4. 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

  5. Measurement of 58Fe (p , n)58Co reaction cross-section within the proton energy range of 3.38 to 19.63 MeV

    Science.gov (United States)

    Ghosh, Reetuparna; Badwar, Sylvia; Lawriniang, Bioletty; Jyrwa, Betylda; Naik, Haldhara; Naik, Yeshwant; Suryanarayana, Saraswatula Venkata; Ganesan, Srinivasan

    2017-08-01

    The 58Fe (p , n)58Co reaction cross-section within Giant Dipole Resonance (GDR) region i.e. from 3.38 to 19.63 MeV was measured by stacked-foil activation and off-line γ-ray spectrometric technique using the BARC-TIFR Pelletron facility at Mumbai. The present data were compared with the existing literature data and found to be in good agreement. The 58Fe (p , n)58Co reaction cross-section as a function of proton energy was also theoretically calculated by using the computer code TALYS-1.8 and found to be in good agreement, which shows the validity of the TALYS-1.8 program.

  6. Excitation functions of proton induced nuclear reactions on {sup nat}Fe up to 16 MeV, with emphasis on radiochemical determination of low cross sections

    Energy Technology Data Exchange (ETDEWEB)

    Uddin, Md. Shuza [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Neurowissenschaften und Medizin (INM), Nuklearchemie (INM-5); Atomic Energy Research Establishment, Dhaka (Bangladesh). Tandem Accelerator Facilities; Chakraborty, Animesh Kumer [Chittagong Univ. of Engineering and Technology (Bangladesh). Dept. of Physics; Atomic Energy Research Establishment, Dhaka (Bangladesh). Tandem Accelerator Facilities; Spellerberg, Stefan; Spahn, Ingo; Qaim, Syed M. [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Neurowissenschaften und Medizin (INM), Nuklearchemie (INM-5); Shariff, Md. Asad [Atomic Energy Research Establishment, Dhaka (Bangladesh). Tandem Accelerator Facilities; Rashid, Md. Abdur [Chittagong Univ. of Engineering and Technology (Bangladesh). Dept. of Physics

    2017-07-01

    Excitation functions for the formation of the radionuclides {sup 56}Co, {sup 57}Co, {sup 58m+g}Co and {sup 54}Mn via proton induced reactions on natural iron target were measured from their respective thresholds up to 16 MeV using the stacked-foil activation technique and HPGe detector γ-ray spectroscopy. In the threshold energy range, the low cross sections for {sup 54}Mn were measured radiochemically. All the measured values were compared with available experimental data and with theoretical calculations reproduced in TENDL-2015 nuclear data library. New data for the formation of {sup 57}Co, {sup 58}Co and {sup 54}Mn were obtained near their reaction thresholds. Other data obtained strengthen the database. Polynomial fittings of the data measured in this work as well as of all data sets (including the present data) were performed. The present data appear to be closer to theoretical calculations than the literature data.

  7. Stripping of two protons and one alpha particle transfer reactions for {sup 16} O + {sup A} Sm and their influence on the fusion cross section

    Energy Technology Data Exchange (ETDEWEB)

    Maciel, A.M.M.; Gomes, P.R.S

    1995-12-31

    Transfer cross section angular distribution data for the stripping of two protons and one alpha particle are studied for the {sup 16} O + {sup A} Sm systems (A=144, 148, 150, 152 and 154), at near barrier energies. A semiclassical formalism is used to derive the corresponding transfer form factors. For only one channel the analysis shows evidences that the transfer reaction mechanism at backward angles - corresponding to small distances, may behave as a multi-step process leading to fusion. Simplified coupled channel calculations including transfer channels are performed for the study of the sub-barrier of these systems. The influence of short distance transfer reactions on the fusion is discussed. (author) 16 refs., 5 figs., 5 tabs.

  8. Proton scattering on unstable nuclei: study of 40S(p,p') and 43Ar(p,p') reactions, development of detection system MUST

    International Nuclear Information System (INIS)

    Marechal, F.

    1998-01-01

    We measured for the first time the elastic and inelastic proton scattering on the 40 S unstable nucleus. The experiment was performed in inverse kinematics at the NSCL AT Michigan State University with a 40 S secondary beam bombarding a CH 2 target at 30 MeV/A. We obtained the elastic scattering angular distribution and two points of the inelastic distribution to the first 2 + excited state found to be located at 860±90 KeV. With a coupled channel analysis, the β 2 quadrupolar deformation parameter is found to be equal to 0.35±0.05. This value can be compared to 0.28±0.02 obtained by coulomb excitation. A macroscopic analysis allowed us to extract the neutron and proton transition matrix element ratio M n /M p which is equal to 1.88±0.38. This value, greater than N/Z, could indicate an isovector effect in the first 2 + state excitation which could be due to a difference between the neutron and proton vibrations. The microscopic analysis gives the possibility to test the densities and the transition densities to the first 2 + state. The calculated densities for the 40 S nucleus show a neutron skin. However the microscopic analysis yields a M n /M p ratio of 1.40±0.20. A similar elastic and inelastic proton scattering experiment allowed us to get a deformation parameter of 0.25±0.03 for the 43 Ar nucleus. To develop the study of direct reactions induced by radioactive beams at GANIL, we have developed and built, in collaboration with the CEA-Saclay and the CEA-Bruyeres, the new detector MUST.It is based on the silicon strip technology, and is dedicated to the measurement of recoiling light particles emitted in these reactions. The results obtained with a 40 Ar beam at 77 Me V/A, have shown the good performances of the detector for the particle identification as well as for the resolutions, and allow us to consider now a large experimental programme concerning these direct reactions induced by radioactive beams. These tests allowed us to establish a reference

  9. 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

  10. Determination of the parton distributions and structure functions of the proton from neutrino and antineutrino reactions on hydrogen and deuterium

    Science.gov (United States)

    Jones, G. T.; Jones, R. W. L.; Kennedy, B. W.; Klein, H.; Morrison, D. R. O.; Wachsmuth, H.; Miller, D. B.; Mobayyen, M. M.; Wainstein, S.; Aderholz, M.; Hantke, D.; Katz, U. F.; Kern, J.; Schmitz, N.; Wittek, W.; Borner, H. P.; Myatt, G.; Cooper-Sarkar, A. M.; Guy, J.; Venus, W.; Bullock, F. W.; Burke, S.

    1994-12-01

    This analysis is based on data from neutrino and antineutrino scattering on hydrogen and deuterium, obtained with BEBC in the (anti) neutrino wideband beam of the CERN SPS. The parton momentum distributions in the proton and the proton structure functions are determined in the range 0.01

  11. An intranuclear cascade-percolation approach for protons and light fragments production in neon-niobium reactions at 400 and 800 MeV per nucleon

    International Nuclear Information System (INIS)

    Montarou, G.; Marroncle, J.; Alard, J.P.; Augerat, J.; Bastid, N.; Charmensat, P.; Dupieux, P.; Fraysse, L.; Parizet, M.J.; Rahmani, A.; Brochard, F.; Gorodetzky, P.; Racca, C.; Cugnon, J.

    1992-01-01

    The results of intranuclear cascade calculations (ideal gas with two body collisions and no mean-field), complemented by a simple percolation procedure, are compared with experimental data on protons and light nuclear fragments (d, t, 3 He and 4 He) measured in 400 and 800 MeV/nucleon Ne+Nb collisions using the large solid angle detector DIOGENE. The model reproduces quite well global experimental observables like nuclear fragment multiplicity distributions or production cross-sections, and nuclear fragment to proton ratios. For rapidity distributions the best agreement occurs for peripheral reactions. Transverse momentum analysis confirms once again that the cascade, although being a microscopic approach, gives too small a collective flow. For heavier nuclear fragments conclusions are not so clear. Since the cross-sections are the main ingredients of the detailed treatment of the first stage of the reaction by the intranuclear cascade, such an approach can be very fruitful in order to infer informations on effective nucleon-nucleon cross-sections. (authors). 31 refs., 23 figs., 6 tabs

  12. Comparison of calculated and experimental values of the yields of xenon isotopes in reactions with high-energy protons

    International Nuclear Information System (INIS)

    Shukolyukov, A.Yu.; Katargin, N.V.; Baishev, I.S.

    1989-01-01

    Calculations of the cumulative yields of isotopes of Xe have been carried out on the basis of the semi-empirical formula of Silverberg and Tsao for Ba- and Dy-targets and bombarding proton energies in the range 100-1050 MeV. Results are compared with experimental data for the yields of Xe isotopes, and domains of applicability of the semi-empirical formula are determined

  13. On-line and precise measurement of iron wear using thin layer activation reactions by proton beam

    International Nuclear Information System (INIS)

    Kosako, Toshiso; Nishimura, Kazuo.

    1990-01-01

    For the purpose of the on-line measurement of iron wear, thin layer activation (TLA) method or surface layer activation (SLA) method has been carried out since early 1970s. This method uses the irradiation of charged particle beam like protons from an accelerator onto a metal surface to produce a thin activated layer of several tens μm. The wear of this activated layer is measured by nondestructive on-line method with a radiation detector. There are two methods of the measurement. One is the activity loss measurement on the surface, and the other is the activity measurement of the metal debris collected in a filter. The former method is considered here. The purpose it to measure the wear of engine cam noses to help the development of good engine oil. Proton beam irradiation with a tandem van de Graaff accelerator, wear calibration using a gamma ray spectrometer, on-line wear measurement of cam noses of car engines by TLA method and so on are reported. The 7.00 MeV proton beam from a van de Graaff accelerator was used for activation, and Co-56, Co-57 and Co-58 were obtained in thin layers. (K.I.)

  14. Angular distribution measurements of {sup 6}Li(p,{alpha}){sup 3}He reaction at 140 keV proton energy using nuclear track detectors

    Energy Technology Data Exchange (ETDEWEB)

    Al-Jarallah, M.I. E-mail: mibrahim@kfupm.edu.sa; Naqvi, A.A.; Abu-Jarad, F.A.; Fazal-ur-Rehman; Durrani, S.M.A.; Kidwai, S

    2001-06-01

    Angular distributions of a {sup 6}Li(p,{alpha}) {sup 3}He reaction were measured at six angles for 140 keV proton energy using nuclear track detectors (NTDs). The measurements were carried out over 60 deg. -160 deg. lab. angles in 20 deg. increments using a scattering chamber of 80 deg. beam line of the 350 kV accelerator. A semiconductor silicon surface barrier (SSB) detector was placed at +160 deg. and was used as a monitor. The results have shown that the CR-39 detector has excellent capabilities to distinguish 1.4-2.7 MeV {alpha}+ {sup 3}He particles from the {sup 6}Li(p,{alpha}) {sup 3}He reaction and 8-9.4 MeV {alpha}-particles from the {sup 7}Li(p,{alpha}) {sup 4}He reaction through their track diameters. However, it was not possible to distinguish between the 2.3 MeV {sup 3}He ions and the 1.7 MeV {sup 4}He ions from the {sup 6}Li(p,{alpha}) {sup 3}He reaction from their track diameter measurements, but it was possible to differentiate between the two, from the darker contrast of the {sup 3}He particles caused by its deeper tracks as compared to those of {sup 4}He.

  15. Proton-proton bremsstrahlung

    International Nuclear Information System (INIS)

    Fearing, H.W.

    1990-01-01

    We summarize some of the information about the nucleon-nucleon force which has been obtained by comparing recent calculations of proton-proton bremsstrahlung with cross section and analyzing power data from the new TRIUMF bremsstrahlung experiment. Some comments are made as to how these results can be extended to neutron-proton bremsstrahlung. (Author) 17 refs., 6 figs

  16. In honour of N. Yngve Öhrn: surveying proton cancer therapy reactions with Öhrn's electron nuclear dynamics method. Aqueous clusters radiolysis and DNA-base damage by proton collisions

    Science.gov (United States)

    Mclaurin, Patrick M.; Privett, Austin J.; Stopera, Christopher; Grimes, Thomas V.; Perera, Ajith; Morales, Jorge A.

    2015-02-01

    Proton cancer therapy (PCT) utilises high-energy H+ projectiles to cure cancer. PCT healing arises from its DNA damage in cancerous cells, which is mostly inflicted by the products from PCT water radiolysis reactions. While clinically established, a complete microscopic understanding of PCT remains elusive. To help in the microscopic elucidation of PCT, Professor Öhrn's simplest-level electron nuclear dynamics (SLEND) method is herein applied to H+ + (H2O)3-4 and H+ + DNA-bases at ELab = 1.0 keV. These are two types of computationally feasible prototypes to study water radiolysis reactions and H+-induced DNA damage, respectively. SLEND is a time-dependent, variational, non-adiabatic and direct-dynamics method that adopts a nuclear classical-mechanics description and an electronic single-determinantal wavefunction. Additionally, our SLEND + effective-core-potential method is herein employed to simulate some computationally demanding PCT reactions. Due to these attributes, SLEND proves appropriate for the simulation of various types of PCT reactions accurately and feasibly. H+ + (H2O)3-4 simulations reveal two main processes: H+ projectile scattering and the simultaneous formation of H and OH fragments; the latter process is quantified through total integrals cross sections. H+ + DNA-base simulations reveal atoms and groups displacements, ring openings and base-to-proton electron transfers as predominant damage processes. The authors warmly dedicate this SLEND investigation in honour of Professor N. Yngve Öhrn on the occasion of his 80th birthday celebration during the 54th Sanibel Symposium in St. Simons' Island, Georgia, on February 16-21, 2014. Associate Professor Jorge A. Morales was a former chemistry PhD student under the mentorship of Professor Öhrn and Dr Ajith Perera took various quantum chemistry courses taught by Professor Öhrn during his chemistry PhD studies. Both Jorge and Ajith look back to those great times of their scientific formation under

  17. Theoretical study of intermediate-mass fragments in proton-nucleus reactions at 200 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Sabra, Mohammad S. [NASA Marshall Space Flight Center, USRA Space Science Department, Huntsville, AL (United States)

    2017-03-15

    We have analyzed energy spectra, angular distributions, and mass and charge distributions of intermediate-mass fragments (IMFs) from the interaction of {sup 27}Al, {sup 59}Co, and {sup 197}Au with 200 MeV protons. Calculations within the modified statistical model with final-state interaction were performed using SAPTON code. Within the experimental uncertainty and constraint, SAPTON shows good agreement with the data, and suggests that the IMFs are produced after the intra-nuclear cascade stage, and during the surface coalescence, as well as the evaporation/fission stages. (orig.)

  18. 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.

  19. 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.

  20. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  1. 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.

  2. 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.

  3. 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.

  4. Arenethiolatecopper(I) complexes as homogeneous catalysts for Michael addition reactions

    NARCIS (Netherlands)

    Koten, G. van; Klaveren, M. van; Lambert, F.; Eijkelkamp, D.J.F.M.; Grove, D.M.

    1994-01-01

    Arenethiolatocopper(I) complexes are shown to be efficient homogeneous catalysts in Michael addition reactions of several Grignard reagents to acyclic enones; the addition products are formed with excellent chemoselectivity (>99%) and good enantioselectivity (76% e.e.).

  5. Recoil properties of antimony isotopes produced by the reaction of 570 MeV and 18.2 GeV protons with uranium

    CERN Document Server

    Hagebø, E

    1969-01-01

    Using the method of thick target and thick catchers, the ranges and other recoil properties of 13 (12) antimony isotopes between A = 115 and A = 131 (130) have been measured for the reaction of 570 MeV (18·2 GeV) protons with uranium. The kinetic energies T are almost independent of product mass number at 570 MeV but show a strong dependence at 18·2 GeV, the lightest isotopes having only about half the kinetic energy of the heavy ones. \\\\ \\\\The cascade deposition energies for production of antimony isotopes are almost equal at 570 MeV and 18·2 GeV and fit well to straight lines of the form E$^{∗}$ (A, Z) = E$^{∗}$ (A$_{0}$, Z) + b(A − A$_{0}$). Exceptions are the cascade deposition energies for $^{115}$Sb and $^{116}$Sb which seem to be somewhat too high at 18·2 GeV. By comparison with other work it seems that the slope $b$ of these lines is independent of product element, target and of proton irradiation energy above 450 MeV. \\\\ \\\\If we assume at 570 MeV, that the fissioning nucleus is a uranium ...

  6. Polarized proton capture reaction /sup 7/Li(p,. gamma. )/sup 8/Be in the energy range from 380 to 960 keV

    Energy Technology Data Exchange (ETDEWEB)

    Ulbricht, J; Arnold, W; Berg, H; Huttel, E; Krause, H H; Clausnitzer, G [Giessen Univ. (Germany, F.R.). Abt. Grossgeraete (Angewandte Kernphysik)

    1977-09-05

    The polarized proton capture in /sup 7/Li was used to study the reaction mechanism and to obtain spectroscopic information on the /sup 8/Be nucleus. Gamma-ray angular distributions of the analyzing power were measured as a function of proton energy from Esub(p) = 380-960 keV with three Ge(Li) detectors simultaneously. The excitation functions of the cross section and the analyzing power are strongly energy dependent. The data were analyzed unambiguously and represented by three R-matrix elements, two M1 and one E1. The energy dependence of the two M1 matrix elements agrees with the well-known two 1/sup +/ resonances at Esub(x) = 17.642 and 18.157 MeV. The energy dependence of the E1 matrix element shows a smooth background presumably caused by a direct-capture mechanism, and furthermore, a resonant contribution, which is a significant suggestion of a new 1/sup -/ state in the /sup 8/Be system at Esub(x) = 17.70 MeV with a width of GAMMAsub(p) = 180 keV.

  7. Photophysical properties of 1-acetoxy-8-hydroxy-1,4,4a,9a-tetrahydroanthraquinone: Evidence for excited state proton transfer reaction

    International Nuclear Information System (INIS)

    Singh, Rupashree Balia; Mahanta, Subrata; Guchhait, Nikhil

    2007-01-01

    The photophysical properties of 1-acetoxy-8-hydroxy-1,4,4a,9a-tetrahydroanthraquinone (HTHQ) have been investigated by steady state and time resolved spectroscopy in combination with quantum chemical calculations. The effects of various parameters such as the nature of solvent and pH of the medium on the spectral properties confirm the existence of different neutral and ionic species in the ground and excited states. In the ground state, HTHQ exists as intramolecularly hydrogen bonded closed conformer in non-polar and polar aprotic solvents. Apart from the closed conformer, the intermolecular hydrogen bonded solvated species and the anion of HTHQ are present in hydroxylic solvents. The closed conformer shows excited state intramolecular proton transfer in all solvents and the solvent polarity independent red shifted emission indicates only keto-enol tautomerism. Evaluation of the potential energy surfaces by quantum chemical calculation using density functional theory point towards the possibility of proton transfer reaction in the first excited state but not in the ground state

  8. Analytical detection of explosives and illicit, prescribed and designer drugs using proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, Bishu; Petersson, Fredrik; Juerschik, Simone [Institut fuer Ionenphysik und Angewandte Physik, Universitaet Innsbruck, Technikerstr. 25, 6020 Innsbruck (Austria); Sulzer, Philipp; Jordan, Alfons [IONICON Analytik GmbH, Eduard-Bodem-Gasse 3, 6020 Innsbruck (Austria); Maerk, Tilmann D. [Institut fuer Ionenphysik und Angewandte Physik, Universitaet Innsbruck, Technikerstr. 25, 6020 Innsbruck (Austria); IONICON Analytik GmbH, Eduard-Bodem-Gasse 3, 6020 Innsbruck (Austria); Watts, Peter; Mayhew, Chris A. [School of Physics and Astronomy, University of Birmingham, Edgbaston, Birmingham B15 4TT (United Kingdom)

    2011-07-01

    This work demonstrates the extremely favorable features of Proton Transfer Reaction Time-of-flight Mass Spectrometry (PTR-TOF-MS) for the detection and identification of solid explosives, chemical warfare agent simulants and illicit, prescribed and designer drugs in real time. Here, we report the use of PTR-TOF, for the detection of explosives (e.g., trinitrotoluene, trinitrobenzene) and illicit, prescribed and designer drugs (e.g., ecstasy, morphine, heroin, ethcathinone, 2C-D). For all substances, the protonated parent ion (as we used H{sub 3}O{sup +} as a reagent ion) could be detected, providing a high level of confidence in their identification since the high mass resolution allows compounds having the same nominal mass to be separated. We varied the E/N from 90 to 220 T{sub d} (1 T{sub d}=10{sup -17} Vcm{sup -1}). This allowed us to study fragmentation pathways as a function of E/N (reduced electric field). For a few compounds rather unusual E/N dependencies were also discovered.

  9. From bismuth oxide/hydroxide precursor clusters towards stable oxides: Proton transfer reactions and structural reorganization govern the stability of [Bi18O13(OH)10]-nitrate clusters

    Science.gov (United States)

    Walther, M.; Zahn, D.

    2018-01-01

    Structural relaxation and stability of a Bi18-cluster as obtained from association of [Bi6O4(OH)4](NO3)6 precursor clusters in DMSO solution is investigated from a combination of quantum chemical calculations and μs-scale molecular dynamics simulations using empirical interaction potentials. The Bi18-cluster undergoes a OH⋯OH proton transfer reaction, followed by considerable structural relaxation. While the aggregation of the Bi18-cluster is induced by the dissociation of a single nitrate ion leading to [Bi6O4(OH)4](NO3)5+ as an activated precursor species that can bind two more Bi6-clusters, we find the [Bi18O13(OH)10](NO3)18-x+x species (explored for x = 1-6) rather inert against either nitrate dissociation, collision with Bi6-precursors or combinations thereof.

  10. Consistency of neutron and proton capture intensity standards new relative intensities for 56Co, 66Ga decay and 35Cl(n,γ) reaction gamma rays

    International Nuclear Information System (INIS)

    Molnar, G.L.; Revay, Z.; Belgya, T.

    2000-01-01

    The equivalence of efficiency determination procedures based on neutron and proton capture lines has been verified and the deviation of high-energy efficiency from linearity confirmed. The new, accurate relative intensities for 56 Co and 66 Ga extend the range of secondary radioactive standards up to 4.8 MeV. Extreme care has to be taken with any high-energy intensity value obtained in the past with the help of 56 Co and 66 Ga calibration sources, and corrections have to be made using the present data of high accuracy. Relative intensities have also been improved for the 35 Cl(n,γ) reaction, a useful secondary standard in a wide energy range, between 0.3-8.5 MeV. The new data are supported by other most recent measurements of a slightly lower precision

  11. Calculations of nuclear data for the reactions of neutrons and protons with heavy nuclei at energy from 1 MeV up to 2 GeV

    International Nuclear Information System (INIS)

    Konshin, V.A.

    1995-01-01

    Several nuclear model codes were applied to calculations of nuclear data in the energy region from 1 MeV to 2 GeV. At energies from 1 to 20 MeV the statistical model code STAPRE was used for calculations of the neutron cross-sections for fission, (n,2n) and (n,3n) reaction cross-sections for 71 actinide isotopes. In the energy region from 10 to 100 MeV the nuclear theory code GNASH was used to calculate the neutron fission and (n,xn) cross-sections for 238 U, 235 U, 239 Pu, 232 Th, 237 Np, 238 Pu, 241 Am, 243 Am, 245 Cm and 246 Cm. At energies from 100 MeV to 2 GeV the intranuclear cascade-exciton model including the fission process was applied to calculations of the interactions of protons and neutrons with actinides and the calculated results are compared with experimental data. (author)

  12. Measurements and Monte Carlo calculations of neutron production cross-sections at 180o for the 140 MeV proton incident reactions on carbon, iron, and gold

    International Nuclear Information System (INIS)

    Iwamoto, Yosuke; Satoh, Daiki; Hagiwara, Masayuki; Yashima, Hiroshi; Nakane, Yoshihiro; Tamii, Atsushi; Iwase, Hiroshi; Endo, Akira; Nakashima, Hiroshi; Sakamoto, Yukio; Hatanaka, Kichiji; Niita, Koji

    2010-01-01

    The neutron production cross-sections of carbon, iron, and gold targets with 140 MeV protons at 180 o were measured at the RCNP cyclotron facility. The time-of-flight technique was used to obtain the neutron energy spectra in the energy range above 1 MeV. The carbon and iron target results were compared with the experimental data from 113 MeV (p,xn) reactions at 150 o reported by Meier et al. Our data agreed well with them in spite of different incident energies and angles. Calculations were then performed using different intra-nuclear cascade models (Bertini, ISOBAR, and JQMD) implemented with PHITS code. The results calculated using the ISOBAR and JQMD models roughly agreed with the experimental iron and gold target data, but the Bertini could not reproduce the high-energy neutrons above 10 MeV.

  13. Effect of NN correlations on predictions of nuclear transparencies for protons, knocked out in high Q2 (e,e'p) reactions

    International Nuclear Information System (INIS)

    Rinat, A.S.; Taragin, M.F.

    1996-01-01

    We study the transparency T of nuclei for nucleons knocked out in high-energy semi-inclusive (e,e'p) reactions, using an improved theoretical input, discussed by Nikolaev et al. We establish that neglect of NN correlations between the knocked-out and core nucleons reduces nuclear transparencies by ∼15 % for light, to ∼10% for heavy nuclei. About the same is predicted for transparencies, integrated over the transverse or longitudinal momentum of the outgoing proton. Hadron dynamics predicts a roughly constant T beyond Q 2 ∼2 GeV 2 , whereas for all targets the largest measured data point Q 2 =6.7 GeV 2 appears to lie above that plateau. Large error bars on those data points preclude a conclusion regarding the onset of colour transparency. (orig.)

  14. 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.

  15. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  16. Emission of light particles associated with a high transverse momentum proton in the reaction sup 16 O + sup 27 Al at 94 MeV/u. Emission de particules legeres associees a un proton de grand moment transverse dans la reaction sup 16 O + sup 27 Al a 94 MeV/u (E75)

    Energy Technology Data Exchange (ETDEWEB)

    Badala, A.; Barbera, R.; Palmeri, A.; Pappalardo, G.S.; Schillaci, A. (Istituto Nazionale di Fisica Nucleare, Catania (IT)); Bizard, G.; Bougault, R.; Durand, D.; Genoux-Lubain, A.; Lefebvres, F.; Patry, J.P. (Institut des Sciences de la Matiere du Rayonnement, 14 - Caen (FR)); Jin, G.; Laville, J.L.; Rosato, E. (Grand Accelerateur National d' Ions Lourds (GANIL), 14 - Caen (FR))

    1989-06-01

    The emission of light particles associated with a high transverse momentum proton in the reaction {sup 16}O + {sup 27}Al at 94 MeV/u has been studied with the help of the GANIL multidetectors (MUR and TONNEAU). Data are confronted with a model based on the standard high-energy participant-spectator picture coupled with the Weisskopf theory of evaporation. Reasonable agreement is achieved indicating that the mean-field effects for this light system at such a rather high incident energy are negligible.

  17. Proton pickup from /sup 27/Al via the (n,d) reaction at 56. 3 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Brady, F P; Shepard, J R; King, N S.P.; McNaughton, M W; Wang, J C [California Univ., Davis (USA)

    1977-09-26

    Energy spectra of deuterons from the /sup 27/Al(n,d)/sup 26/Mg reaction due to 56.3 MeV neutrons incident have been measured for 10/sup 0/ <= thetasub(c.m.) <= 55 /sup 0/. The angular distributions for the excitations observed at 0.0, 1.81, and 4.33 MeV are quite well described by DWBA calculations and yield spectroscopic factors in agreement with shell model calculations; but with calculations based on the rotational model, the agreement is less satisfactory particularly for the 4.33 MeV level. For the states at 7.86 and 9.16 MeV the fits, assuming p-shell pick-up, are only fair. Comparison with /sup 27/Al(d,/sup 3/He)/sup 26/Mg measurements shows that the deduced spectroscopic factors for the two reactions agree quite well.

  18. Angular distributions of the quasifree deuteron-proton and deuteron-neutron scattering in the reaction dd → dpn

    International Nuclear Information System (INIS)

    Schneider, H.

    1978-06-01

    The mechanism of the quasifree scattering (QFS) in the reaction dd → dpn has been investigated systematically by means of kinematically complete coincidence experiments using 52 MeV deuterons. In order to measure the angular distributions of the quasifree dp scattering and the quasifree dn scattering, the kinematical conditions were chosen to favour quasifree scattering of deuterons on bound nucleons of the target deuteron. (orig.) [de

  19. Feasibility studies for the open-charm production in proton-antiproton reactions for the PANDA experiment

    Energy Technology Data Exchange (ETDEWEB)

    Vejdani, Solmaz [KVI-CART, University of Groningen (Netherlands); Forschungszentrum Juelich, Juelich (Germany); Collaboration: PANDA-Collaboration

    2016-07-01

    The PANDA experiment is one of the pillars of the future Facility for Antiproton and Ion Research (FAIR) in Darmstadt, Germany. The PANDA physics program is focused on answering fundamental questions related to Quantum Chromodynamics (QCD), mostly in the non-perturbative energy regime. Spectroscopy exploiting Λc-baryons that are composed of a heavy charm valence quark and two light valence quarks is an integral part of the PANDA physics program. Such systems can systematically provide information on various key features of QCD, such as heavy-quark symmetry, chiral symmetry breaking, and the nature of exotic states. In this work, the experimental feasibility of studying the production mechanisms of associative open-charm baryons in antiproton-proton annihilations is investigated by using Monte Carlo simulations. I present results obtained for the channel p anti p → Λ{sup -}{sub c}Λ{sub c}, highlighting the detector performances (efficiencies and resolutions) and the statistical significance that can be achieved with the foreseen luminosities.

  20. Proton-transfer reaction mass spectrometry (PTR-MS) for the authentication of regionally unique South African lamb.

    Science.gov (United States)

    Erasmus, Sara W; Muller, Magdalena; Alewijn, Martin; Koot, Alex H; van Ruth, Saskia M; Hoffman, Louwrens C

    2017-10-15

    The volatile fingerprints of South African lamb meat and fat were measured by proton-transfer mass spectrometry (PTR-MS) to evaluate it as an authentication tool. Meat and fat of the Longissimus lumborum (LL) of lambs from six different regions were assessed. Analysis showed that the volatile fingerprints were affected by the origin of the meat. The classification of the origin of the lamb was achieved by examining the calculated and recorded fingerprints in combination with chemometrics. Four different partial least squares discriminant analysis (PLS-DA) models were fitted to the data to classify lamb meat and fat samples into "region of origin" (six different regions) and "origin" (Karoo vs. Non-Karoo). The estimation models classified samples 100% correctly. Validation of the first two models gave 42% (fat) and 58% (meat) correct classification of region, while the second two models performed better with 92% (fat) and 83% (meat) correct classification of origin. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Preliminary study on 2-dimensional distributions of 10B reaction rate in a water phantom with boron-doped CR-39 for 7Li(p, n)7Be neutrons by 1.95 MeV protons

    International Nuclear Information System (INIS)

    Hasegawa, Y.; Tanaka, K.; Tsuruta, T.

    2000-01-01

    In an Accelerator-based neutron irradiation field using 7 Li(p, n) 7 Be neutrons by 1.95 MeV protons, the distributions of 10 B reaction rates and thermal neutron fluence in a water phantom were measured using Boron-doped CR-39 and Au activation analysis, respectively. Comparing the results of the measurements, we discussed the validity of the evaluation method of 10 B reaction rate using thermal neutron fluence. (author)

  2. 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.

  3. Calculations of neutron and proton induced reaction cross sections for actinides in the energy region from 10 MeV to 1 GeV

    International Nuclear Information System (INIS)

    Konshin, V.A.

    1995-01-01

    Several nuclear model codes were applied to calculations of nuclear data in the energy region from 10 MeV to 1 GeV. At energies up to 100 MeV the nuclear theory code GNASH was used for nuclear data calculation for incident neutrons for 238 U, 233-236 U, 238-242 Pu, 237 Np, 232 Th, 241-243 Am and 242-247 Cm. At energies from 100 MeV to 1 GeV the intranuclear cascade exciton model including the fission process was applied to calculations of protons and neutrons with 233 U, 235 U, 238 U, 232 Th, 232 Pa, 237 Np, 238 Np, 239 Pu, 241 Am, 242 Am and 242-248 Cm. Determination of parameter systematics was a major effort in the present work that was aimed at improving the predictive capability of the models used. An emphasis was made on a simultaneous analysis of data for a variety of reaction channels for the nucleus considered, as well as of data that are available for nearby nuclei or other incident particles. Comparison with experimental data available on multiple reaction cross sections, isotope yields, fission cross sections, particle multiplicities, secondary particle spectra, and double differential cross sections indicates that the calculations reproduce the trends, and often the details, of the experimental data. (author)

  4. Excitation functions of proton-induced reactions on {sup nat}Fe and enriched {sup 57}Fe with particular reference to the production of {sup 57}Co

    Energy Technology Data Exchange (ETDEWEB)

    Al-Abyad, M. [Institut fuer Nuklearchemie, Forschungszentrum Juelich GmbH, D-52425 Juelich (Germany); Cyclotron Facility, Nuclear Research Centre, Atomic Energy Authority, Cairo 13759 (Egypt); Comsan, M.N.H. [Cyclotron Facility, Nuclear Research Centre, Atomic Energy Authority, Cairo 13759 (Egypt); Qaim, S.M. [Institut fuer Nuklearchemie, Forschungszentrum Juelich GmbH, D-52425 Juelich (Germany)], E-mail: s.m.qaim@fz-juelich.de

    2009-01-15

    Excitation functions of the reactions {sup nat}Fe(p,xn){sup 55,56,57,58}Co, {sup nat}Fe(p,x){sup 51}Cr, {sup nat}Fe(p,x){sup 54}Mn, {sup 57}Fe(p,n){sup 57}Co and {sup 57}Fe(p,{alpha}){sup 54}Mn were measured from their respective thresholds up to 18.5 MeV, with particular emphasis on data for the production of the radionuclide {sup 57}Co (T{sub 1/2}=271.8 d). The conventional stacked-foil technique was used, and the samples for irradiation were prepared by an electroplating or sedimentation process. The measured excitation curves were compared with the data available in the literature as well as with results of nuclear model calculations. From the experimental data, the theoretical yields of the investigated radionuclides were calculated as a function of the proton energy. Over the energy range E{sub p}=15{yields}5 MeV the calculated yield of {sup 57}Co from the {sup 57}Fe(p,n){sup 57}Co process amounts to 1.2 MBq/{mu}A h and from the {sup nat}Fe(p,xn){sup 57}Co reaction to 0.025 MBq/{mu}A h. The radionuclidic impurity levels are discussed. Use of highly enriched {sup 57}Fe as target material would lead to formation of high-purity {sup 57}Co.

  5. Calculations of neutron and proton induced reaction cross sections for actinides in the energy region from 10MeV to 1GeV

    International Nuclear Information System (INIS)

    Konshin, V.A.

    1995-06-01

    Several nuclear model codes were applied to calculations of nuclear data in the energy region from 10MeV to 1GeV. At energies up to 100MeV the nuclear theory code GNASH was used for nuclear data calculation for neutrons incident for on 238 U, 233-236 U, 238-242 Pu, 237 Np, 232 Th, 241-243 Am and 242-247 Cm. At energies from 100MeV to 1GeV the intranuclear cascade exciton model including the fission process was applied to calculations of protons and neutrons with 233 U, 235 U, 238 U, 232 Th, 232 Pa, 237 Np, 238 Np, 239 Pu, 241 Am, 242 Am and 242-248 Cm. Determination of parameter systematics was a major effort in the present work that was aimed at improving the predictive capability of the models used. An emphasis was placed upon a simultaneous analysis of data for a variety of reaction channels for the nuclei considered, as well as of data that are available for nearby nuclei or for other incident particles. Comparisons with experimental data available on multiple reaction cross sections, isotope yields, fission cross sections, particle multiplicities, secondary particle spectra, and double differential cross sections indicate that the calculations reproduce the trends, and often the details, of the measurements data. (author) 82 refs

  6. A selected ion flow tube study of the ion molecule association reactions of protonated (MH+), nitrosonated (MNO+) and dehydroxidated (M-OH)(+) carboxylic acids (M) with H2O

    Czech Academy of Sciences Publication Activity Database

    Brůhová Michalčíková, R.; Španěl, Patrik

    2014-01-01

    Roč. 368, JUL 2014 (2014), s. 15-22 ISSN 1387-3806 R&D Projects: GA ČR GA13-28882S Institutional support: RVO:61388955 Keywords : ion molecule reactions * proton transfer * selected ion flow tube mass spectrometry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.972, year: 2014

  7. Excitation functions of proton-induced reactions on natural Nd in the 10-30 MeV energy range, and production of radionuclides relevant for double-beta decay

    Czech Academy of Sciences Publication Activity Database

    Lebeda, Ondřej; Lozza, V.; Schrock, P.; Štursa, Jan; Zuber, K.

    2012-01-01

    Roč. 89, č. 4 (2012), 049905/1-049905/12 ISSN 0556-2813 R&D Projects: GA MŠk LA09013 Institutional research plan: CEZ:AV0Z10480505 Keywords : proton-induced reactions * radionuclides Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 3.715, year: 2012

  8. Proton transfer events in GFP

    NARCIS (Netherlands)

    Di Donato, M.; van Wilderen, L.J.G.W.; van Stokkum, I.H.M.; Cohen Stuart, T.A.; Kennis, J.T.M.; Hellingwerf, K.J.; van Grondelle, R.; Groot, M.L.

    2011-01-01

    Proton transfer is one of the most important elementary processes in biology. Green fluorescent protein (GFP) serves as an important model system to elucidate the mechanistic details of this reaction, because in GFP proton transfer can be induced by light absorption. Illumination initiates proton

  9. Proton scattering on unstable nuclei: study of {sup 40}S(p,p`) and {sup 43}Ar(p,p`) reactions, development of detection system MUST; Diffusion de protons par des noyaux instables: Etudes des reactions {sup 40}S(p,p`) et {sup 43}Ar(p,p`), developpement du systeme de detection MUST

    Energy Technology Data Exchange (ETDEWEB)

    Marechal, F

    1998-02-06

    We measured for the first time the elastic and inelastic proton scattering on the {sup 40}S unstable nucleus. The experiment was performed in inverse kinematics at the NSCL AT Michigan State University with a {sup 40}S secondary beam bombarding a CH{sub 2} target at 30 MeV/A. We obtained the elastic scattering angular distribution and two points of the inelastic distribution to the first 2{sup +} excited state found to be located at 860{+-}90 KeV. With a coupled channel analysis, the {beta}{sub 2} quadrupolar deformation parameter is found to be equal to 0.35{+-}0.05. This value can be compared to 0.28{+-}0.02 obtained by coulomb excitation. A macroscopic analysis allowed us to extract the neutron and proton transition matrix element ratio M{sub n}/M{sub p} which is equal to 1.88{+-}0.38. This value, greater than N/Z, could indicate an isovector effect in the first 2{sup +} state excitation which could be due to a difference between the neutron and proton vibrations. The microscopic analysis gives the possibility to test the densities and the transition densities to the first 2{sup +} state. The calculated densities for the {sup 40}S nucleus show a neutron skin. However the microscopic analysis yields a M{sub n}/M{sub p} ratio of 1.40{+-}0.20. A similar elastic and inelastic proton scattering experiment allowed us to get a deformation parameter of 0.25{+-}0.03 for the {sup 43}Ar nucleus. To develop the study of direct reactions induced by radioactive beams at GANIL, we have developed and built, in collaboration with the CEA-Saclay and the CEA-Bruyeres, the new detector MUST.It is based on the silicon strip technology, and is dedicated to the measurement of recoiling light particles emitted in these reactions. The results obtained with a {sup 40}Ar beam at 77 Me V/A, have shown the good performances of the detector for the particle identification as well as for the resolutions, and allow us to consider now a large experimental programme concerning these direct

  10. Special features of the inverse-beta-decay reaction proceeding on a proton in a reactor-antineutrino flux

    Energy Technology Data Exchange (ETDEWEB)

    Kopeikin, V. I., E-mail: kopeikin46@yandex.ru; Skorokhvatov, M. D., E-mail: skorokhvatov-md@nrcki.ru [National Research Center Kurchatov Institute (Russian Federation)

    2017-03-15

    The evolution of the reactor-antineutrino spectrum and the evolution of the spectrum of positrons from the inverse-beta-decay reaction in the course of reactor operation and after reactor shutdown are considered. The present-day status in determining the initial reactor-antineutrino spectrum on the basis of spectra of beta particles from mixtures of products originating from uranium and plutonium fission is described. A local rise of the experimental spectrum of reactor antineutrinos with respect to the expected spectrum is studied.

  11. 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.

  12. Predicting CYP2C19 Catalytic Parameters for Enantioselective Oxidations Using Artificial Neural Networks and a Chirality Code

    Science.gov (United States)

    Hartman, Jessica H.; Cothren, Steven D.; Park, Sun-Ha; Yun, Chul-Ho; Darsey, Jerry A.; Miller, Grover P.

    2013-01-01

    Cytochromes P450 (CYP for isoforms) play a central role in biological processes especially metabolism of chiral molecules; thus, development of computational methods to predict parameters for chiral reactions is important for advancing this field. In this study, we identified the most optimal artificial neural networks using conformation-independent chirality codes to predict CYP2C19 catalytic parameters for enantioselective reactions. Optimization of the neural networks required identifying the most suitable representation of structure among a diverse array of training substrates, normalizing distribution of the corresponding catalytic parameters (kcat, Km, and kcat/Km), and determining the best topology for networks to make predictions. Among different structural descriptors, the use of partial atomic charges according to the CHelpG scheme and inclusion of hydrogens yielded the most optimal artificial neural networks. Their training also required resolution of poorly distributed output catalytic parameters using a Box-Cox transformation. End point leave-one-out cross correlations of the best neural networks revealed that predictions for individual catalytic parameters (kcat and Km) were more consistent with experimental values than those for catalytic efficiency (kcat/Km). Lastly, neural networks predicted correctly enantioselectivity and comparable catalytic parameters measured in this study for previously uncharacterized CYP2C19 substrates, R- and S-propranolol. Taken together, these seminal computational studies for CYP2C19 are the first to predict all catalytic parameters for enantioselective reactions using artificial neural networks and thus provide a foundation for expanding the prediction of cytochrome P450 reactions to chiral drugs, pollutants, and other biologically active compounds. PMID:23673224

  13. Use of Proton-Transfer-Reaction Mass Spectrometry to Characterize Volatile Organic Compound Sources at the La Porte Super Site During the Texas Air Quality Study 2000

    Energy Technology Data Exchange (ETDEWEB)

    Karl, Thomas G.; Jobson, B Tom T.; Kuster, W. C.; Williams, Eric; Stutz, Jochen P.; Shetter, Rick; Hall, Samual R.; Goldan, P. D.; Fehsenfeld, Fred C.; Lindinger, Werner

    2003-08-19

    Proton-transfer-reaction mass spectrometry (PTR-MS) was deployed for continuous real-time monitoring of volatile organic compounds (VOCs) at a site near the Houston Ship Channel during the Texas Air Quality Study 2000. Overall, 28 ions dominated the PTR-MS mass spectra and were assigned as anthropogenic aromatics (e.g., benzene, toluene, xylenes) and hydrocarbons (propene, isoprene), oxygenated compounds (e.g., formaldehyde, acetaldehyde, acetone, methanol, C7 carbonyls), and three nitrogencontaining compounds (e.g., HCN, acetonitrile and acrylonitrile). Biogenic VOCs were minor components at this site. Propene was the most abundant lightweight hydrocarbon detected by this technique with concentrations up to 100+ nmol mol-1, and was highly correlated with its oxidation products, formaldehyde (up to ~40 nmol mol-1) and acetaldehyde (up to ~80 nmol/mol), with typical ratios close to 1 in propene-dominated plumes. In the case of aromatic species the high time resolution of the obtained data set helped in identifying different anthropogenic sources (e.g., industrial from urban emissions) and testing current emission inventories. A comparison with results from complimentary techniques (gas chromatography, differential optical absorption spectroscopy) was used to assess the selectivity of this on-line technique in a complex urban and industrial VOC matrix and give an interpretation of mass scans obtained by ‘‘soft’’ chemical ionization using proton-transfer via H3O+. The method was especially valuable in monitoring rapidly changing VOC plumes which passed over the site, and when coupled with meteorological data it was possible to identify likely sources.

  14. In situ formation of a 3D core-shell and triple-conducting oxygen reduction reaction electrode for proton-conducting SOFCs

    Science.gov (United States)

    Zhang, Zhenbao; Wang, Jian; Chen, Yubo; Tan, Shaozao; Shao, Zongping; Chen, Dengjie

    2018-05-01

    BaZrxCeyY1-x-yO3-δ are recognized proton-conducting electrolyte materials for proton-conducting solid oxide fuel cells (H+-SOFCs) below 650 °C. Here Co cations are incorporated into the BaZr0.4Ce0.4Y0.2O3-δ (BZCY) scaffold to generate a 3D core-shell and triple-conducting (H+/O2-/e-) electrode in situ via infiltrating and reactive sintering. The core is the bulk BZCY scaffold, while the shell is composed of the cubic Ba(Zr0.4Ce0.4Y0.2)1-xCoxO3-δ, cubic spinel Co3O4 and cubic fluorite (Ce, Zr, Y)O2. The obtained electrode exhibits an excellent compatibility with the BZCY electrolyte, and performs well in yielding a low and stable polarization resistance for oxygen reduction reaction for intermediate-temperature H+-SOFCs. In particular, it achieves polarization resistances as low as 0.094 and 0.198 Ω cm2 at 650 and 600 °C in wet air (3% H2O) when the sintering temperature for the electrode is 900 °C. In addition, a symmetrical cell also exhibits operation stability of 70 h at 650 °C. Furthermore, a fuel cell assembled with the 3D core-shell and triple-conducting electrode delivers a peak power density of ∼330 mW cm-2 at 650 °C. The substantially improved electrochemical performance and high stability are ascribed to the unique core-shell structure and the formation of Ba(Zr0.4Ce0.4Y0.2)1-xCoxO3-δ in the shell.

  15. 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

  16. Chiral gold(I vs chiral silver complexes as catalysts for the enantioselective synthesis of the second generation GSK-hepatitis C virus inhibitor

    Directory of Open Access Journals (Sweden)

    María Martín-Rodríguez

    2011-07-01

    Full Text Available The synthesis of a GSK 2nd generation inhibitor of the hepatitis C virus, by enantioselective 1,3-dipolar cycloaddition between a leucine derived iminoester and tert-butyl acrylate, was studied. The comparison between silver(I and gold(I catalysts in this reaction was established by working with chiral phosphoramidites or with chiral BINAP. The best reaction conditions were used for the total synthesis of the hepatitis C virus inhibitor by a four step procedure affording this product in 99% ee and in 63% overall yield. The origin of the enantioselectivity of the chiral gold(I catalyst was justified according to DFT calculations, the stabilizing coulombic interaction between the nitrogen atom of the thiazole moiety and one of the gold atoms being crucial.

  17. Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to Five-, Six-, and Seven-Membered β-Substituted Cyclic Enones: Enantioselective Construction of All-Carbon Quaternary Stereocenters

    KAUST Repository

    Kikushima, Kotaro; Holder, Jeffrey C.; Gatti, Michele; Stoltz, Brian M.

    2011-01-01

    The first enantioselective Pd-catalyzed construction of all-carbon quaternary stereocenters via 1,4-addition of arylboronic acids to β-substituted cyclic enones is reported. Reaction of a wide range of arylboronic acids and cyclic enones using a

  18. Virtual disjunct eddy covariance measurements of organic compound fluxes from a subalpine forest using proton transfer reaction mass spectrometry

    Directory of Open Access Journals (Sweden)

    T. G. Karl

    2002-01-01

    Full Text Available A `virtual' disjunct eddy covariance (vDEC device was tested with field measurements of biogenic VOC fluxes at a subalpine forest site in the Rocky Mountains of the USA. A PTR-MS instrument was used as the VOC sensor. Daily peak emission fluxes of 2-methyl-3-buten-2-ol (MBO, methanol, acetone and acetaldehyde were around 1.5, 1, 0.8 and 0.4 mg m-2 h-1, respectively. High pass filtering due to long sampling lines was investigated in laboratory experiments, and suggested that VOC losses in PTFA lines are generally governed by diffusion laws. Memory effects and surface reactions did not seem to play a dominant role. Model estimates of MBO fluxes compared well with measured fluxes. The results also suggest that latent heat and sensible heat fluxes are reasonably well correlated with VOC fluxes and could be used to predict variations in VOC emissions. The release of MBO, methanol, acetone and acetaldehyde resulted in significant change of tropospheric oxidant levels and a 10--40% increase in ozone levels, as inferred from a photochemical box model. We conclude that vDEC with a PTR-MS instrument is a versatile tool for simultaneous field analysis of multiple VOC fluxes.

  19. 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.

  20. 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.

  1. 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.

  2. Valence and inner proton hole states in 207Tl via the (d,3He) reaction at 108 MeV

    International Nuclear Information System (INIS)

    Langevin-Joliot, H.; Gerlic, E.; Guillot, J.; Van de Wiele, J.

    1983-01-01

    The excitation energy spectra of the residual nucleus 207 Tl have been investigated up to 14 MeV using the (d, 3 He) reaction at 108 MeV. New groups and high lying structures are first observed up to 8.3 MeV, in addition to the five known low lying levels. Beyond a minimum at 7.13 MeV, weaker structures are observed riding over an asymetric bump located around 9 MeV. DWBA analysis of angular distributions have allowed l attributions and the determination of valence and inner hole spectroscopic factors. It is found that the valence levels at 1.33 MeV, 1.67 MeV and 3.47 MeV exhaust respectively about 65%, 60% and 45% of the 1hsub(11/2), 2dsub(5/2) and 1gsub(7/2) sum rules. The missing strengths are found below 8.3 MeV. The 2dsub(5/2) and 1gsub(7/2) holes contribute mainly to some well concentrated groups, whereas the 1hsub(11/2) strength is distributed more smoothly. Small contributions of 1gsub(9/2) and 2p strengths are tentatively identified below 7.13 MeV. The highest lying energy region up to 14 MeV may approximately account for the 1gsub(9/2) and (1fsub(5/2)) total sum-rule and about 70% of the 2p strength. The 1gsub(9/2) strength gives the largest contribution to the asymetric bump around 9 MeV. The deduced experimental strength functions are compared with theoretical calculations

  3. Study of the production of residual evaporation nuclei issued from the spallation reaction of uranium-238 by 1 GeV protons; Etude de la production de noyaux residuels d'evaporation issus de la reaction de spallation de l'uranium-238 par des protons a 1 GeV

    Energy Technology Data Exchange (ETDEWEB)

    Taieb, J

    2000-10-01

    The spallation reaction by high energy protons is one of the envisaged nuclear reactions for production of exotic nuclei. We have measured the production of more than 300 different evaporation residues issued by the spallation reaction of Uranium-238 by 1 GeV protons. We used the reverse kinematics technique in order to produce the relativistic nuclei and therefore to be able to detect those nuclides within a very short time, shorter in most cases than the radioactive disintegration period. The achieved nuclear charge and mass resolution are excellent. They allow a good accuracy on the values of the measured cross-sections (10 to 15%). We have observed for the first time the nuclide Actinium-235 obtained consequently to the loss of 3 protons by the projectile. The measured isotopic distribution are strongly influenced by the mechanism of fission which leads to a strong reduction of the production of the heavy neutron deficient isotopes. We have compared our results to some other measurements achieved with radio-chemical methods at a similar energy. We observed a systematic disagreement of about 40%. Some comparison with the available systematics show that those are presently not able to reproduce the data with a reasonable precision. We could also measure the recoil momentum distribution for each studied isotopes. We show that Goldhaber's model agrees very well with the experiment in case. of 'cold' channels where the evaporation of particles never occurs. On the other hand, when the produced pre-fragment is excited the data show that Goldhaber's model does not reproduce.the data showing the limitation of such an approach. We finally tried to reproduce the measurement of evaporation residue cross-section thanks to the coupling of intra-nuclear cascade and statistical evaporation codes. The influence of the fission process is rather important is the system p+U; we therefore had to account for the dynamical aspect of the fission. We also showed

  4. Fission coincident neutrons from the reactions p + sup(235,236,238)U with protons between 12,7 and 25.5 MeV

    International Nuclear Information System (INIS)

    Plischke, P.

    1981-01-01

    With the proton beam of the Hamburg isochronous cyclotron (HAIZY) thin uranium targets with the mass numbers 235, 236, and 238 were bombarded. Both fragments from the fission of the Np reaction systems and the neutrons coincident with the fragments were detected in the plane perpendicular to the beam direction. Measured and stored event by event were for all particles the times of flight. The detection of the neutron succeeded in conventional time-of-flight technique with NE213 liquid scintillators. A fission detector system with plastic scintillator foils was developed. It permits high event rates over long measuring times and allows the choice of so long neutron flight paths that a neutron energy resolution between 2% and 4% could be reached. The determination of the fragment masses is in spite of the short flight paths of 15 respectively 21 cm possible to +-2 amu. The isotropic component das discussed under the assumption that it is composed of prefission and scission neutrons which were emitted befor fission respectively during the fragmentation. From the post fission results the distribution of the excitation energy to both fragments was determined in dependence of Esup(*) and the fragment mass. (orig./HSI) [de

  5. Measurement of excitation functions and analysis of isomeric population in some reactions induced by proton on natural indium at low energy

    Science.gov (United States)

    Muhammed Shan, P. T.; Musthafa, M. M.; Najmunnisa, T.; Mohamed Aslam, P.; Rajesh, K. K.; Hajara, K.; Surendran, P.; Nair, J. P.; Shanbagh, Anil; Ghugre, S.

    2018-06-01

    The excitation functions for reaction residues populated via 115In(p , p) 115 mIn, 115In(p , pn) 114 mIn, 115In(p , p 2 n) 113 mIn, 113In(p , p) 113 mIn, 115In(p , nα) 111 mCd, 115In(p , 3 n) 113Sn and 113In(p , n) 113Sn channels were measured over the proton energy range of 8-22 MeV using stacked foil activation technique. Theoretical analysis of the data were performed within the framework of two statistical model codes EMPIRE-3.2 and TALYS-1.8. Isomeric cross section ratio for isomeric pairs m,g 115In, m,g 114In, m,g 113In, 113Sn m,g and m,g 111Cd were determined for the first time. The dependence of isomeric cross section ratio on various factors are analysed.

  6. Hydride, hydrogen, proton, and electron affinities of imines and their reaction intermediates in acetonitrile and construction of thermodynamic characteristic graphs (TCGs) of imines as a "molecule ID card".

    Science.gov (United States)

    Zhu, Xiao-Qing; Liu, Qiao-Yun; Chen, Qiang; Mei, Lian-Rui

    2010-02-05

    A series of 61 imines with various typical structures were synthesized, and the thermodynamic affinities (defined as enthalpy changes or redox potentials in this work) of the imines to abstract hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the imines to abstract hydrogen atoms and protons, and the thermodynamic affinities of the hydrogen adducts of the imines to abstract electrons in acetonitrile were determined by using titration calorimetry and electrochemical methods. The pure heterolytic and homolytic dissociation energies of the C=N pi-bond in the imines were estimated. The polarity of the C=N double bond in the imines was examined using a linear free-energy relationship. The idea of a thermodynamic characteristic graph (TCG) of imines as an efficient "Molecule ID Card" was introduced. The TCG can be used to quantitatively diagnose and predict the characteristic chemical properties of imines and their various reaction intermediates as well as the reduction mechanism of the imines. The information disclosed in this work could not only supply a gap of thermodynamics for the chemistry of imines but also strongly promote the fast development of the applications of imines.

  7. Effects of airflow on odorants' emissions in a model pig house — A laboratory study using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS)

    International Nuclear Information System (INIS)

    Saha, Chayan Kumer; Feilberg, Anders; Zhang, Guoqiang; Adamsen, Anders Peter S.

    2011-01-01

    Identification of different factors that affect emissions of gasses, including volatile organic compounds (VOCs) is necessary to develop emission abatement technology. The objectives of this research were to quantify and study temporal variation of gas emissions from a model pig house under varying ventilation rates. The used model was a 1:12.5 scale of a section of a commercial finishing pig house. The VOC concentrations at inlet, outlet, and slurry pit of the model space were measured using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS). PTR-MS can measure the temporal variations of odor compounds' emission from the slurry pit in real time. The emissions of H 2 S and 14 VOCs were lower compared to real pig buildings except for ammonia, which indicated possible other sources of those compounds than the slurry in the slurry pit. The ventilation rate affected significantly on ammonia and trimethylamine emission (p 2 S) emission was independent of the ventilation rate. VFAs' emission dependency on ventilation rate increased with the increase of carbon chain. Phenols, indoles and ketones showed the positive correlation with ventilation rate to some extent. Generally, compounds with high solubility (low Henry's constant) showed stronger correlation with ventilation rates than the compounds with high Henry's constant.

  8. Direct sampling of sub-µm atmospheric particulate organic matter in sub-ng m-3 mass concentrations by proton-transfer-reaction mass spectrometry

    Science.gov (United States)

    Armin, W.; Mueller, M.; Klinger, A.; Striednig, M.

    2017-12-01

    A quantitative characterization of the organic fraction of atmospheric particulate matter is still challenging. Herein we present the novel modular "Chemical Analysis of Aerosol Online" (CHARON) particle inlet system coupled to a new-generation proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF 6000 X2, Ionicon Analytik, Austria) that quantitatively detects organic analytes in real-time and sub-pptV levels by chemical ionization with hydronium reagent ions. CHARON consists of a gas-phase denuder for stripping off gas-phase analytes (efficiency > 99.999%), an aerodynamic lens for particle collimation combined with an inertial sampler for the particle-enriched flow and a thermodesorption unit for particle volatilization prior to chemical analysis. With typical particle enrichment factors of around 30 for particle diameters (DP) between 120 nm and 1000 nm (somewhat reduced enrichment for 60 nm 6000) and excellent mass accuracies (< 10 ppm) chemical compositions can be assigned and included in further analyses. In addition to a detailed characterization of the CHARON PTR-TOF 6000 X2 we will present first results on the chemical composition of sub-µm particulate organic matter in the urban atmosphere in Innsbruck (Austria).

  9. Study of nuclear reactions involving heavy nuclei and intermediate- and high-energy protons and an application in nuclear reactor physics (ADS)

    International Nuclear Information System (INIS)

    Matuoka, Paula Fernanda Toledo

    2016-01-01

    In the present work, intermediate- and high-energy nuclear reactions involving heavy nuclei and protons were studied with the Monte Carlo CRISP (Rio - Ilheus - Sao Paulo Collaboration) model. The most relevant nuclear processes studied were intranuclear cascade and fission-evaporation competition. Preliminary studies showed fair agreement between CRISP model calculation and experimental data of multiplicity of evaporated neutrons (E 20 MeV) were emitted mostly in the intranuclear cascade stage, while evaporation presented larger neutron multiplicity. Fission cross section of 209 mb and spallation cross section of 1788 mb were calculated { both in agreement with experimental data. The fission process resulted in a symmetric mass distribution. Another Monte Carlo code, MCNP, was used for radiation transport in order to understand the role of a spallation neutron source in a ADS (Accelerator Driven System) nuclear reactor. Initially, a PWR reactor was simulated to study the isotopic compositions in spent nuclear fuel. As a rst attempt, a spallation neutron source was adapted to an industrial size nuclear reactor. The results showed no evidence of incineration of transuranic elements and modifications were suggested. (author)

  10. Investigation of the aroma of commercial peach (Prunus persica L. Batsch) types by Proton Transfer Reaction-Mass Spectrometry (PTR-MS) and sensory analysis.

    Science.gov (United States)

    Bianchi, Tiago; Weesepoel, Yannick; Koot, Alex; Iglesias, Ignasi; Eduardo, Iban; Gratacós-Cubarsí, Marta; Guerrero, Luis; Hortós, Maria; van Ruth, Saskia

    2017-09-01

    The aim of this study was to investigate the aroma and sensory profiles of various types of peaches (Prunus persica L. Batsch.). Forty-three commercial cultivars comprising peaches, flat peaches, nectarines, and canning peaches (pavías) were grown over two consecutive harvest years. Fruits were assessed for chemical aroma and sensory profiles. Chemical aroma profile was obtained by proton transfer reaction-mass spectrometry (PTR-MS) and spectral masses were tentatively identified with PTR-Time of Flight-MS (PTR-Tof-MS). Sensory analysis was performed at commercial maturity considering seven aroma/flavor attributes. The four types of peaches showed both distinct chemical aroma and sensory profiles. Flat peaches and canning peaches showed most distinct patterns according to discriminant analysis. The sensory data were related to the volatile compounds by partial least square regression. γ-Hexalactone, γ-octalactone, hotrienol, acetic acid and ethyl acetate correlated positively, and benzeneacetaldehyde, trimethylbenzene and acetaldehyde negatively to the intensities of aroma and ripe fruit sensory scores. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Real-time monitoring of respiratory absorption factors of volatile organic compounds in ambient air by proton transfer reaction time-of-flight mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhonghui [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Zhang, Yanli [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Center for Excellence in Urban Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021 (China); Yan, Qiong [Department of Respiratory Diseases, Guangzhou No. 12 People' s Hospital, Guangzhou 510620 (China); Zhang, Zhou [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Wang, Xinming, E-mail: wangxm@gig.ac.cn [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Center for Excellence in Urban Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021 (China)

    2016-12-15

    Respiratory absorption factors (AFs) are essential parameters in the evaluation of human health risks from toxic volatile organic compounds (VOCs) in ambient air. A method for the real time monitoring of VOCs in inhaled and exhaled air by proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) has been developed to permit the calculation of respiratory AFs of VOCs. Isoprene was found to be a better breath tracer than O{sub 2}, CO{sub 2}, humidity, or acetone for distinguishing between the expiratory and inspiratory phases, and a homemade online breath sampling device with a buffer tube was used to optimize signal peak shapes. Preliminary tests with seven subjects exposed to aromatic hydrocarbons in an indoor environment revealed mean respiratory AFs of 55.0%, 55.9%, and 66.9% for benzene, toluene, and C8-aromatics (ethylbenzene and xylenes), respectively. These AFs were lower than the values of 90% or 100% used in previous studies when assessing the health risks of inhalation exposure to hazardous VOCs. The mean respiratory AFs of benzene, toluene and C8-aromatics were 66.5%, 70.2% and 82.3% for the three female subjects; they were noticeably much higher than that of 46.4%, 45.2% and 55.3%, respectively, for the four male subjects.

  12. Study of the kinematically complete breakup reaction 2H(p vector, pp)n at Ep=13.0 MeV with polarized protons

    International Nuclear Information System (INIS)

    Rauprich, G.; Lemaitre, S.; Niessen, P.; Nyga, K.R.; Reckenfelderbaeumer, R.; Sydow, L.; Paetz genannt Schieck, H.; Witala, H.; Gloeckle, W.

    1991-01-01

    The breakup reaction 2 H(p vector,pp)n at E p =13.0 MeV has been measured in a kinematically complete experiment with polarized protons in four special kinematical situations: np final-state interaction, pp quasi-free scattering, collinearity and symmetric space star. These configurations are identical to those of a corresponding 2 H(n,nn) 1 H experiment. The cross sections d 3 σ/dΩ 3 dΩ 4 dS and the vector analyzing powers A y are presented as a function of the arclength of the relevant kinematical loci. They are compared to the rigorous Faddeev calculations using realistic meson-exchange NN potentials, i.e. the Paris and Bonn potential. Comparison with the cross section data of the analog neutron experiment is made. In the quasi-free scattering and the space-star cross sections marked discrepancies with the theoretical predictions, in the latter case also with the neutron results are found. In the collinear and final-state interaction situations the agreement is rather good as well as for all analyzing powers and is even improved by taking the finite angular spread into account. (orig.)

  13. 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.

  14. 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.

  15. Proton microanalysis in plants

    International Nuclear Information System (INIS)

    Garrec, J.P.

    Micro-analyses by nuclear reactions and atomic excitation are used to determine the distribution of fluorine and calcium in the needles of Abies Alba. Fluorine is detected by the nuclear reaction 19 F(p,α) 16 O at the 1.35 MeV resonance. Calcium is measured by its characteristic X-rays due to proton excitation [fr

  16. Electronic device for measuring the polarization parameter in the {pi}{sup -}p {yields} {pi}{sup 0}n charge exchange reaction on a polarized proton target; Un appareillage electronique destine a la mesure du parametre de polarisation dans la reaction d'echange de charge {pi}{sup -}p {yields} {pi}{sup 0}n sur cible de protons polarises

    Energy Technology Data Exchange (ETDEWEB)

    Brehin, S [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-12-15

    An electronic apparatus has been constructed to measure the polarization parameter P{sub 0}(t) in {pi}{sup -}p {yields} {pi}{sup 0}n charge exchange scattering at 5.9 GeV/c and 11,2 GeV/c on polarized proton target. This device insures triggering of a heavy plate spark chamber, allowing visualisation of {gamma} rays from the {pi}{sup 0} decays when the associated neutron offers suitable characteristics in direction and energy. The neutron is detected by an array of 32 counters and his energy is measured by a time of flight method. Electronic circuits of this apparatus are described as test and calibration methods used. (author) [French] Un appareillage electronique a ete realise pour mesurer le parametre de polarisation P{sub 0}(t) dans la reaction d'echange de charge {pi}{sup -}p {yields} {pi}{sup 0}n a 5,9 GeV/c et 11,2 GeV/c sur une cible de protons polarises. Ce dispositif assure le declenchement d'une chambre a etincelles a plaques lourdes, permettant de visualiser les {gamma} de desitegration du {pi}{sup 0}, lorsque le neutron associe presente les caracteristiques convenables en direction et en energie. Le neutron est detecte par un ensemble de 32 compteurs et son energie est mesuree par une methode de temps de vol. Les circuits composant cet appareillage sont decrits ainsi que les methodes d'etalonnage et de verification utilisees. (auteur)

  17. 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.

  18. 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.

  19. 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.

  20. Excitation functions and yields of proton induced reactions at intermediate energies leading to important diagnostics radioisotopes of 52Fe, 77Br, 82Rb, 97Ru, 111In, 123I, 127Xe, 128Cs, 178Ta and 201Tl

    International Nuclear Information System (INIS)

    Rurarz, E.

    1994-01-01

    This report describes investigations of the excitation functions of the proton induced reactions on 14 targets (Mn, Co, Br, Rb, 99 Tc, 113 Cd, 114 Cd, Cd, I, Cs, Ta, 206,207,208 Pb) leading directly or indirectly to the formation of radionuclides 52 Fe, 77 Br, 82 Rb, 97 Ru, 111 In, 123 I, 127 Xe, 128 Cs, 178 Ta and 201 Tl frequently used in diagnostic procedures of nuclear medicine. The measurements of the excitation functions were made over a wide proton energy range from the reaction threshold up to 100 MeV using the stacked foil (or pellet) technique. Small energy steps were used to allow for accurate determination of the structure of excitation functions. For 97 Ru, 111 In and 127 Xe formation with protons, new reaction channels and targets were used and data concerning this method are published for the first time. The data for 52 Fe, 77 Br, 82 Rb, 123 I, 128 Cs and 201 Tl obtained in the present work for the E p =70-100 MeV region are also published for the first time. The measured excitation functions for the formation of desired (and undesired) radionuclides (altogether 28 excitation functions) are compared with the theoretical ones calculated on the basis of a hybrid model of nuclear reactions in the form of the Overlaid Alice computer code. In order to determine the contribution of the competitive reaction channels to the purity of the produced, desired radionuclide, the excitation functions of the accompanying reactions were also calculated. The 122 calculated excitation functions for the possible contaminant are given in the present work. The comparison of experimental excitation functions with the results of model calculations showed satisfactory agreement, especially if one considers, that no parameter adjustment for individual reaction products was undertaken. From the measured excitation functions the production yields for 28 radionuclides mentioned above have been determined (author). 262 refs, 65 figs, 34 tabs