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

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.

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.

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.

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

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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...

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.

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.

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...

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.)

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.

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.

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.

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.

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

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.

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

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.

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)

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.

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

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%)

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.

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

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.

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.

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)

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.

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.

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.)

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.

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.

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

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.

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

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.)

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.

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.

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

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.

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...

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.

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.

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...

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

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.

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.

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...

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.

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.

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.

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.

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

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.

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

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.

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.

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

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.

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

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

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.

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.

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.

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

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.

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.

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.

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

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.

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...

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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....

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.

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....

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.

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

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

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

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.

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-.

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

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)

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)

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.

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.

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

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.

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

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.

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.

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...

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).

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

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

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.

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.

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.

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.

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

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.

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.

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)

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)

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

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.)

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.

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.

High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

KAUST Repository

Stoltz, Brian

2010-06-14

The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

KAUST Repository

Stoltz, Brian; McDougal, Nolan; Virgil, Scott

2010-01-01

The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

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.

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

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.

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

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)

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

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.

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

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.

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.

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

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.

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.

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)

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

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

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.

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

Science.gov (United States)

Qian, Yi; Zhou, Peixue; Zhang, Quan

2017-01-01

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

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.

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)

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)

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)

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

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.

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)

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

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

Science.gov (United States)

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

2012-09-19

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

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.

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.)

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

Science.gov (United States)

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

2008-07-17

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

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)

Reduction of α,β-Unsaturated Ketones by Old Yellow Enzymes: Mechanistic Insights from Quantum Mechanics/Molecular Mechanics Calculations.

Science.gov (United States)

Lonsdale, Richard; Reetz, Manfred T

2015-11-25

Enoate reductases catalyze the reduction of activated C═C bonds with high enantioselectivity. The oxidative half-reaction, which involves the addition of a hydride and a proton to opposite faces of the C═C bond, has been studied for the first time by hybrid quantum mechanics/molecular mechanics (QM/MM). The reduction of 2-cyclohexen-1-one by YqjM from Bacillus subtilis was selected as the model system. Two-dimensional QM/MM (B3LYP-D/OPLS2005) reaction pathways suggest that the hydride and proton are added as distinct steps, with the former step preceding the latter. Furthermore, we present interesting insights into the reactivity of this enzyme, including the weak binding of the substrate in the active site, the role of the two active site histidine residues for polarization of the substrate C═O bond, structural details of the transition states to hydride and proton transfer, and the role of Tyr196 as proton donor. The information presented here will be useful for the future design of enantioselective YqjM mutants for other substrates.

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.

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...

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.

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

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

Science.gov (United States)

Wang, Chuan; Yamamoto, Hisashi

2015-04-08

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

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)

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)

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)

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

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)

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-05-15

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

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

International Nuclear Information System (INIS)

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

2010-01-01

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

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

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

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.

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

Science.gov (United States)

Zhang, Chunlong; Wen, Yuezhong; Liu, Weiping

2012-01-01

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

Enantioselective carbenoid insertion into C(sp3–H bonds

Directory of Open Access Journals (Sweden)

J. V. Santiago

2016-05-01

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

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.

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.

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.

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.

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)

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.

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

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

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.

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.

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.

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

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

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

Directory of Open Access Journals (Sweden)

Akihiko Shimada

2012-05-01

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

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.

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)

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.

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)

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.

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 .

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

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

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.

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.)

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

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.

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.

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.

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.

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.

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

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.

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.

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 ...

Asymmetric Diels-Alder Reaction of α-Substituted and β,β-Disubstituted α,β-Enals via Diarylprolinol Silyl Ether for the Construction of All-Carbon Quaternary Stereocenters.

Science.gov (United States)

Hayashi, Yujiro; Bondzic, Bojan P; Yamazaki, Tatsuya; Gupta, Yogesh; Ogasawara, Shin; Taniguchi, Tohru; Monde, Kenji

2016-10-24

The asymmetric Diels-Alder reaction of α-substituted acrolein proceeds in the presence of the trifluoroacetic acid salt of trifluoromethyl-substituted diarylprolinol silyl ether to afford the exo-isomer with both excellent diastereoselectivity and high enantioselectivity. In the Diels-Alder reaction of a β,β-disubstituted α,β-unsaturated aldehyde, good exo-selectivity and excellent enantioselectivity was obtained when the perchloric acid salt of the bulky triisopropyl silyl ether of trifluoromethyl substituted diarylprolinol was employed as an organocatalyst in the presence of water. In both cases, all-carbon quaternary stereocenters are constructed enantioselectively. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Bifunctional nanocrystalline MgO for chiral epoxy ketones via Claisen-Schmidt condensation-asymmetric epoxidation reactions.

Science.gov (United States)

Choudary, Boyapati M; Kantam, Mannepalli L; Ranganath, Kalluri V S; Mahendar, Koosam; Sreedhar, Bojja

2004-03-24

Design and development of a truly nanobifunctional heterogeneous catalyst for the Claisen-Schmidt condensation (CSC) of benzaldehydes with acetophenones to yield chalcones quantitatively followed by asymmetric epoxidation (AE) to afford chiral epoxy ketones with moderate to good yields and impressive ee's is described. The nanomagnesium oxide (aerogel prepared) NAP-MgO was found to be superior over the NA-MgO and CM-MgO in terms of activity and enantioselectivity as applicable in these reactions. An elegant strategy for heterogenization of homogeneous catalysts is presented here to evolve single-site chiral catalysts for AE by a successful transfer of molecular chemistry to surface metal-organic chemistry with the retention of activity, selectivity/enantioselectivity. Brønsted hydroxyls are established as sole contributors for the epoxidation reaction, while they add on to the CSC, which is largely driven by Lewis basic O2-sites. Strong hydrogen-bond interactions between the surface -OH on MgO and -OH groups of diethyl tartrate are found inducing enantioselectivity in the AE reaction. Thus, the nanocrystalline NAP-MgO with its defined shape, size, and accessible OH groups allows the chemisorption of TBHP, DET, and olefin on its surface to accomplish single-site chiral catalysts to provide optimum ee's in AE reactions.

Asymmetric Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene

Directory of Open Access Journals (Sweden)

Magnus Rueping

2012-10-01

Full Text Available A new chiral Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene has been developed. The reaction provides optically active aza-tetracycles in good yields with high diastereo- and enantioselectivities under mild reaction conditions.

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.

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

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-...

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.

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.

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.

Enantiomerization and enantioselective bioaccumulation of metalaxyl in Tenebrio molitor larvae.

Science.gov (United States)

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

2014-02-01

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

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

Directory of Open Access Journals (Sweden)

Patrícia de O. Carvalho

2005-08-01

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

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.).

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

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)

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)

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.

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)

Enantioselective Analysis in instruments onboard ROSETTA/PHILAE and ExoMars

Science.gov (United States)

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

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

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

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

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

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.

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

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

Science.gov (United States)

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

2016-03-24

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

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

Science.gov (United States)

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

2018-03-07

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

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

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.)

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

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.

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.

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.

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...

Using chiral ionic liquid additives to enhance asymmetric induction in a Diels-Alder reaction.

Science.gov (United States)

Goodrich, P; Nimal Gunaratne, H Q; Hall, L; Wang, Y; Jin, L; Muldoon, M J; Ribeiro, A P C; Pombeiro, A J L; Pârvulescu, V I; Davey, P; Hardacre, C

2017-01-31

A bis-oxazoline ligand has been complexed using Cu(ii) and Zn(ii) trifluoromethanesulfonate and a range of chiral ionic liquid (CIL) additives based on natural products were used as a co-catalyst for a Diels-Alder reaction. The catalytic performance of these systems was compared for the asymmetric Diels-Alder reaction between N-acryloyloxazolidinone and cyclopentadiene with and without the presence of a CIL additive. In the absence of the CIL, both catalysts resulted in low enantioselectivities in conventional solvents and ionic liquids. However, whilst only a minor effect of the CIL was observed for the Cu based catalyst, in the case of the Zn based catalyst, significant enhancements in endo enantioselectivity of up to 50% were found on the addition of a CIL.

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

NARCIS (Netherlands)

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

1997-01-01

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

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)

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}...

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.

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

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.

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.

Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

KAUST Repository

Thomas, Renee M.

2010-11-24

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

Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

KAUST Repository

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

2010-01-01

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

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

NARCIS (Netherlands)

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

1997-01-01

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

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

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

Science.gov (United States)

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

2015-04-01

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

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.

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

Science.gov (United States)

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

2015-07-24

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

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

KAUST Repository

Lattanzi, Alessandra

2012-01-01

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

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.

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

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.)

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

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

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

Directory of Open Access Journals (Sweden)

Francesco P. Ballistreri

2018-03-01

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

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

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

International Nuclear Information System (INIS)

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

2014-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-04-18

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

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.)

Intramolecular and Transannular Diels-Alder Reactions

DEFF Research Database (Denmark)

Tanner, David Ackland; Ascic, Erhad

2014-01-01

Few reactions can compete with the Diels-Alder (DA) [4+2] cycloaddition for the rapid and efficient generation of molecular complexity. The DA reaction is atom-economic and stereospecific, as well as diastereo- and regioselective. The intramolecular version (IMDA) of the DA cycloaddition and its...... and dienophile, methods for acceleration of IMDA reactions (such as use of high pressure) and catalysis (using oxophilic or carbophilic metal complexes, Brønsted acids, and enzymes). The use of furans as diene components (IMDAF), intramolecular hetero-DA (IMHDA) and IMDA reactions with inverse electron demand...... are also covered. Applications of IMDA to asymmetric synthesis (from substrate control through to enantioselective catalysis, including organocatalysis) are presented, along with tandem sequences involving IMDA cycloaddition. A theme pervading the whole chapter is the use of IMDA reactions for the total...

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

KAUST Repository

Ahmed, Syud M.

2013-12-18

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

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

KAUST Repository

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

2013-01-01

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

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

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

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

Directory of Open Access Journals (Sweden)

Ping Zhang

2017-01-01

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

Regio- and Enantioselective Sequential Dehalogenation of rac-1,3-Dibromobutane by Haloalkane Dehalogenase LinB.

Science.gov (United States)

Gross, Johannes; Prokop, Zbyněk; Janssen, Dick; Faber, Kurt; Hall, Mélanie

2016-08-03

The hydrolytic dehalogenation of rac-1,3-dibromobutane catalyzed by the haloalkane dehalogenase LinB from Sphingobium japonicum UT26 proceeds in a sequential fashion: initial formation of intermediate haloalcohols followed by a second hydrolytic step to produce the final diol. Detailed investigation of the course of the reaction revealed favored nucleophilic displacement of the sec-halogen in the first hydrolytic event with pronounced R enantioselectivity. The second hydrolysis step proceeded with a regioselectivity switch at the primary position, with preference for the S enantiomer. Because of complex competition between all eight possible reactions, intermediate haloalcohols formed with moderate to good ee ((S)-4-bromobutan-2-ol: up to 87 %). Similarly, (S)-butane-1,3-diol was formed at a maximum ee of 35 % before full hydrolysis furnished the racemic diol product. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

Sharma, Ankit; Hartwig, John F

2013-11-27

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

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).

N,N'-dioxide/nickel(II)-catalyzed asymmetric inverse-electron-demand hetero-diels-alder reaction of β,γ-unsaturated α-ketoesters with enecarbamates.

Science.gov (United States)

Zhou, Yuhang; Zhu, Yin; Lin, Lili; Zhang, Yulong; Zheng, Jianfeng; Liu, Xiaohua; Feng, Xiaoming

2014-12-08

N,N'-Dioxide/nickel(II) complexes have been developed to catalyze the inverse-electron-demand hetero-Diels-Alder reaction of β,γ-unsaturated α-ketoesters with acyclic enecarbamates. After detailed screening of the reaction parameters, mild optimized reaction conditions were established, affording 3,4-dihydro-2H-pyranamines in up to 99 % yield, 99 % ee and more than 95:5 d.r. The catalytic system was also efficient for β-substituted acyclic enecarbamates, affording more challenging 2,3,4-trisubstituted 3,4-dihydro-2H-pyranamine with three contiguous stereogenic centers in excellent yields, diastereoselectivities, and enantioselectivities. The reaction could be scaled up to a gram scale with no deterioration of either enantioselectivity or yield. Based on these experiments and on previous reports, a possible transition state was proposed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

Science.gov (United States)

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

2015-01-21

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

Inter- and intra-annular proton exchange in gaseous benzylbenzenium ions (protonated diphenylmethane)

OpenAIRE

Kuck, Dietmar; Bäther, Wolfgang

1986-01-01

Two distinct proton exchange reactions occur in metastable gaseous benzylbenzenium ions, generated by isobutane chemical ionization of diphenylmethane and four deuterium-labelled analogues. Whereas the proton ring-walk at the benzenium moiety is fast giving rise to a completely random intraannular proton exchange, the interannular proton exchange is surprisingly slow and competes with the elimination of benzene. A kinetic isotope effect of kH/kD= 5 has been determined for the interannular pro...

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

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.

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

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

Science.gov (United States)

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

2017-08-01

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

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

Science.gov (United States)

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

2016-07-18

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

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

Science.gov (United States)

2016-01-01

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

Homologation Reaction of Ketones with Diazo Compounds.

Science.gov (United States)

Candeias, Nuno R; Paterna, Roberta; Gois, Pedro M P

2016-03-09

This review covers the addition of diazo compounds to ketones to afford homologated ketones, either in the presence or in the absence of promoters or catalysts. Reactions with diazoalkanes, aryldiazomethanes, trimethylsilyldiazomethane, α-diazo esters, and disubstituted diazo compounds are covered, commenting on the complex regiochemistry of the reaction and the nature of the catalysts and promoters. The recent reports on the enantioselective version of ketone homologation reactions are gathered in one section, followed by reports on the use of cyclic ketones ring expansion in total synthesis. Although the first reports of this reaction appeared in the literature almost one century ago, the recent achievements, in particular, for the asymmetric version, forecast the development of new breakthroughs in the synthetically valuable field of diazo chemistry.

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

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).

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.

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.

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)

Proton-proton and deuteron-deuteron correlations in interactions of relativistic helium nuclei with protons

International Nuclear Information System (INIS)

Galazka-Friedman, J.; Sobczak, T.; Stepaniak, J.; Zielinski, I.P.; Bano, M.; Hlavacova, J.; Martinska, G.; Patocka, J.; Seman, M.; Sandor, L.; Urban, J.

1993-01-01

The reactions 4 Hep→pp+X, 3 Hep→pp+X and 4 Hep→ddp have been investigated and the correlation function has been measured for protons and deuterons with small relative momenta. Strong positive correlation has been observed for protons related mainly to the final state interactions in 1 S 0 state. The root mean square radius of the proton source calculated from the correlation function has been found to be equal to (1.7±0.3) fm and (2.1±0.3) fm for 4 He and 3 He respectively. It agrees with the known radii of these nuclei. (orig.)

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

Directory of Open Access Journals (Sweden)

Yiyang Liu

2014-10-01

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

An enantioselective synthesis of S-γ-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3-14C] hydrochloride, an important metabolite of fluoxetine hydrochloride

International Nuclear Information System (INIS)

Wheeler, W.J.

1992-01-01

The S-enantiomer of γ-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3- 14 C] hydrochloride has been prepared in eight steps from acetophenone-[carbonyl- 14 C]. The key step in the synthesis involved the enantioselective reduction of R-2-chloroacetophenone-[1- 14 C]with (-)-diisopinocampheyl-chloroborane in an 86.5% yield. The chlorohydrin was converted to R-phenyloxirane-[1- 14 C], which was subsequently converted to the corresponding R-cyanohydrin by reaction with TMS-CN/CaO. Borane reduction and arylation, followed by salt formation yielded S-γ-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3- 14 C] hydrochloride. (author)

Enantioselective degradation and enantiomerization of indoxacarb in soil.

Science.gov (United States)

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

2013-11-27

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

Enantioselective inhibition of carprofen towards UDP-glucuronosyltransferase (UGT) 2B7.

Science.gov (United States)

Fang, Zhong-Ze; Wang, Haina; Cao, Yun-Feng; Sun, Dong-Xue; Wang, Li-Xuan; Hong, Mo; Huang, Ting; Chen, Jian-Xing; Zeng, Jia

2015-03-01

UDP-glucuronosyltransferases (UGTs)-catalyzed glucuronidation conjugation reaction plays an important role in the elimination of many important clinical drugs and endogenous substances. The present study aims to investigate the enantioselective inhibition of carprofen towards UGT isoforms. In vitro a recombinant UGT isoforms-catalyzed 4-methylumbelliferone (4-MU) glucuronidation incubation mixture was used to screen the inhibition potential of (R)-carprofen and (S)-carprofen towards multiple UGT isoforms. The results showed that (S)-carprofen exhibited stronger inhibition potential than (R)-carprofen towards UGT2B7. However, no significant difference was observed for the inhibition of (R)-carprofen and (S)-carprofen towards other UGT isoforms. Furthermore, the inhibition kinetic behavior was compared for the inhibition of (S)-carprofen and (R)-carprofen towards UGT2B7. A Lineweaver-Burk plot showed that both (S)-carprofen and (R)-carprofen exhibited competitive inhibition towards UGT2B7-catalyzed 4-MU glucuronidation. The inhibition kinetic parameter (Ki ) was calculated to be 7.0 μM and 31.1 μM for (S)-carprofen and (R)-carprofen, respectively. Based on the standard for drug-drug interaction, the threshold for (S)-carprofen and (R)-carprofen to induce a drug-drug interaction is 0.7 μM and 3.1 μM, respectively. In conclusion, enantioselective inhibition of carprofen towards UDP-glucuronosyltransferase (UGT) 2B7 was demonstrated in the present study. Using the in vitro inhibition kinetic parameter, the concentration threshold of (S)-carprofen and (R)-carprofen to possibly induce the drug-drug interaction was obtained. Therefore, clinical monitoring of the plasma concentration of (S)-carprofen is more important than (R)-carprofen to avoid a possible drug-drug interaction between carprofen and the drugs mainly undergoing UGT2B7-catalyzed metabolism. © 2014 Wiley Periodicals, Inc.

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

Metal-Free Catalytic Enantioselective C–B Bond Formation: (Pinacolato)boron Conjugate Additions to α,β-Unsaturated Ketones, Esters, Weinreb Amides and Aldehydes Promoted by Chiral N-Heterocyclic Carbenes

Science.gov (United States)

Wu, Hao; Radomkit, Suttipol; O’Brien, Jeannette M.; Hoveyda, Amir H.

2012-01-01

The first broadly applicable metal-free enantioselective method for boron conjugate addition (BCA) to α,β-unsaturated carbonyls is presented. The C–B bond forming reactions are promoted in the presence of 2.5–7.5 mol % of a readily accessible C1-symmetric chiral imidazolinium salt, which is converted, in situ, to the catalytically active diastereo- and enantiomerically pure N-heterocyclic carbene (NHC) by the common organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu). In addition to the commercially available bis(pinacolato)diboron [B2(pin)2], and in contrast to reactions with the less sterically demanding achiral NHCs, the presence of MeOH is required for high efficiency. Acyclic and cyclic α,β-unsaturated ketones, as well as acyclic esters, Weinreb amides and aldehydes can serve as suitable substrates; the desired β-boryl carbonyls are isolated in up to 94% yield and >98:2 enantiomer ratio (er). Transformations are often carried out at ambient temperature. In certain cases, such as when the relatively less reactive unsaturated amides are used, elevated temperatures are required (50–66 °C); nonetheless, reactions remain highly enantioselective. The utility of the NHC-catalyzed method is demonstrated through comparison with the alternative Cu-catalyzed protocols; in cases involving a polyfunctional substrate, unique profiles in chemoselectivity are exhibited by the metal-free approach (e.g., conjugate addition vs reaction with an alkyne, allene or aldehyde). PMID:22559866

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

Evaluation of the Induced Activity in Air by the External Proton Beam in the Target Room of the Proton Accelerator Facility of Proton Engineering Frontier Project

International Nuclear Information System (INIS)

Lee, Cheol Woo; Lee, Young Ouk; Cho, Young Sik; Ahn, So Hyun

2007-01-01

One of the radiological concerns is the worker's exposure level and the concentration of the radionuclides in the air after shutdown, for the safety analysis on the proton accelerator facility. Although, the primary radiation source is the protons accelerated up to design value, all of the radio-nuclide is produced from the secondary neutron and photon induced reaction in air. Because, the protons don't penetrate the acceleration equipment like the DTL tank wall or BTL wall, secondary neutrons or photons are only in the air in the accelerator tunnel building because of the short range of the proton in the materials. But, for the case of the target rooms, external proton beams are occasionally used in the various experiments. When these external proton beams travel through air from the end of the beam transport line to the target, they interact directly with air and produce activation products from the proton induced reaction. The external proton beam will be used in the target rooms in the accelerator facility of the Proton Accelerator Frontier Project (PEFP). In this study, interaction characteristics of the external proton beam with air and induced activity in air from the direct interaction of the proton beam were evaluated

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

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.

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

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

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.)

Enantioselective conjugate radical addition to alpha'-hydroxy enones.

Science.gov (United States)

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

2006-09-14

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

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

KAUST Repository

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

2018-01-01

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

Enantioselective synthesis of almorexant via iridium-catalysed intramolecular allylic amidation

NARCIS (Netherlands)

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

2013-01-01

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

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

Science.gov (United States)

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

2016-07-01

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

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.

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.

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

Science.gov (United States)

Yu, Yue-Na; Xu, Ming-Hua

2013-03-15

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

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.

Conformation and Catalytic Properties Studies of Candida rugosa Lip7 via Enantioselective Esterification of Ibuprofen in Organic Solvents and Ionic Liquids

Directory of Open Access Journals (Sweden)

Xiang Li

2013-01-01

Full Text Available Enantioselective esterification of ibuprofen was conducted to evaluate the enzyme activity and ees of lipase from Candida rugosa (CRL7 in ten conventional organic solvents and three ionic liquids. Different alcohols were tested for selecting the most suitable acyl acceptor due to the fact that the structure of alcohols (branch and length of carbon chains; location of –OH functional group could affect the enzyme activity and ees. The results of alcohol and solvent selection revealed that 1-isooctanol and isooctane were the best substrate and reaction medium, respectively, because of the highest enzyme activity and ees. Compared with the control, conformational studies via FT-IR indicate that the variations of CRL7’s secondary structure elements are probably responsible for the differences of enzyme activity and ees in the organic solvents and ionic liquids. Moreover, the effects of reaction parameters, such as molar ratio, water content, temperature, and reaction time, in the selected reaction medium, were also examined.

Proton Transfer Time-of-Flight Mass Spectrometer

Energy Technology Data Exchange (ETDEWEB)

Watson, Thomas B. [Brookhaven National Lab. (BNL), Upton, NY (United States)

2016-03-01

The Proton Transfer Reaction Mass Spectrometer (PTRMS) measures gas-phase compounds in ambient air and headspace samples before using chemical ionization to produce positively charged molecules, which are detected with a time-of-flight (TOF) mass spectrometer. This ionization method uses a gentle proton transfer reaction method between the molecule of interest and protonated water, or hydronium ion (H₃O⁺), to produce limited fragmentation of the parent molecule. The ions produced are primarily positively charged with the mass of the parent ion, plus an additional proton. Ion concentration is determined by adding the number of ions counted at the molecular ion’s mass-to-charge ratio to the number of air molecules in the reaction chamber, which can be identified according to the pressure levels in the reaction chamber. The PTRMS allows many volatile organic compounds in ambient air to be detected at levels from 10–100 parts per trillion by volume (pptv). The response time is 1 to 10 seconds.

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

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

OpenAIRE

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

2016-01-01

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

Enantioselective developmental toxicity and immunotoxicity of pyraclofos toward zebrafish (Danio rerio)

Energy Technology Data Exchange (ETDEWEB)

Zhuang, Shulin, E-mail: shulin@zju.edu.cn [Institute of Environmental Science, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Hangzhou 310058 (China); Zhang, Zhisheng [Institute of Environmental Science, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhang, Wenjing; Bao, Lingling [Institute of Environmental Science, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Hangzhou 310058 (China); Xu, Chao, E-mail: chaoxu@zjut.edu.cn [Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Zhang, Hu [Institute of Quality and Standard for Agro-products, Zhejiang Academy of Agricultural Sciences, Hangzhou 210021 (China)

2015-02-15

Highlights: • Pyraclofos has significant enantioselective aquatic toxicities to zebrafish. • Pyraclofos induces time- and concentration-dependent developmental toxicity and immunotoxicity. • The mRNA level of IL-1β gene was significantly up-regulated by pyraclofos. • Pyraclofos binds potently to IL-1β, potentially affecting IL-1β-dependent proinflammatory signal transduction. • Our in vitro and in silico studies help to understand the molecular basis for aquatic toxicity of pyraclofos. - Abstract: Pyraclofos, a relatively new organophosphorus pesticide, has shown potential ecotoxicities, however, its aquatic toxicity, especially enantioselective aquatic toxicity, remains largely unknown. Using zebrafish (Danio rerio) as a preeminent vertebrate aquatic model, the enantioselective differences in the developmental toxicity and immunotoxicity of pyraclofos were evaluated. Following 96-h exposure, pyraclofos enantiomers exhibited acute toxicity and showed lethal concentration 50 of 2.23 and 3.99 mg/L for (R)-Pyraclofos and (S)-Pyraclofos, respectively. Exposure to pyraclofos caused time- and concentration-dependent malformations such as pericardial edema, yolk sac edema, crooked bodies and hatching during the embryonic development, with markedly higher percentages of malformation at higher concentrations. The concentration-dependent immunotoxicity to zebrafish embryo exposed to low level pyraclofos was induced with significant up-regulation of mRNA levels of immune-related interleukin-1β (IL-1β) gene. (R)-Pyraclofos was consistently more toxic than (S)-Pyraclofos for the acute toxicity, developmental toxicity and immunotoxicity to zebrafish. Molecular dynamics simulations revealed that at the atomic level, (R)-Pyraclofos binds more potently to IL-1β protein than (S)-Pyraclofos. This enantioselective binding is mainly contributed by the distinct binding mode of pyraclofos enantiomers and their electrostatic interactions with IL-1β, which potentially

Enantioselective developmental toxicity and immunotoxicity of pyraclofos toward zebrafish (Danio rerio)

International Nuclear Information System (INIS)

Zhuang, Shulin; Zhang, Zhisheng; Zhang, Wenjing; Bao, Lingling; Xu, Chao; Zhang, Hu

2015-01-01

Highlights: • Pyraclofos has significant enantioselective aquatic toxicities to zebrafish. • Pyraclofos induces time- and concentration-dependent developmental toxicity and immunotoxicity. • The mRNA level of IL-1β gene was significantly up-regulated by pyraclofos. • Pyraclofos binds potently to IL-1β, potentially affecting IL-1β-dependent proinflammatory signal transduction. • Our in vitro and in silico studies help to understand the molecular basis for aquatic toxicity of pyraclofos. - Abstract: Pyraclofos, a relatively new organophosphorus pesticide, has shown potential ecotoxicities, however, its aquatic toxicity, especially enantioselective aquatic toxicity, remains largely unknown. Using zebrafish (Danio rerio) as a preeminent vertebrate aquatic model, the enantioselective differences in the developmental toxicity and immunotoxicity of pyraclofos were evaluated. Following 96-h exposure, pyraclofos enantiomers exhibited acute toxicity and showed lethal concentration 50 of 2.23 and 3.99 mg/L for (R)-Pyraclofos and (S)-Pyraclofos, respectively. Exposure to pyraclofos caused time- and concentration-dependent malformations such as pericardial edema, yolk sac edema, crooked bodies and hatching during the embryonic development, with markedly higher percentages of malformation at higher concentrations. The concentration-dependent immunotoxicity to zebrafish embryo exposed to low level pyraclofos was induced with significant up-regulation of mRNA levels of immune-related interleukin-1β (IL-1β) gene. (R)-Pyraclofos was consistently more toxic than (S)-Pyraclofos for the acute toxicity, developmental toxicity and immunotoxicity to zebrafish. Molecular dynamics simulations revealed that at the atomic level, (R)-Pyraclofos binds more potently to IL-1β protein than (S)-Pyraclofos. This enantioselective binding is mainly contributed by the distinct binding mode of pyraclofos enantiomers and their electrostatic interactions with IL-1β, which potentially

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

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

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.

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

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

Exploiting the enantioselectivity of Baeyer-Villiger monooxygenases via boron oxidation

NARCIS (Netherlands)

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

2012-01-01

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

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.)

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

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

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.

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.

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)

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

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

2011-05-11

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 catalyst prepared from Pd(OCOCF(3))(2) and a chiral pyridinooxazoline ligand yields enantioenriched products bearing benzylic stereocenters. Notably, this transformation is tolerant to air and moisture, providing a practical and operationally simple method of synthesizing enantioenriched all-carbon quaternary stereocenters.

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

Science.gov (United States)

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

2009-01-01

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

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.

Enantioselective N-demethylation and hydroxylation of sibutramine in human liver microsomes and recombinant cytochrome p-450 isoforms.

Science.gov (United States)

Shinde, Dhananjay D; Kim, Min-Jung; Jeong, Eun-Sook; Kim, Yang-Weon; Lee, Ji-Woo; Shin, Jae-Gook; Kim, Dong-Hyun

2014-01-01

The enantioselective metabolism of sibutramine was examined using human liver microsomes (HLM) and recombinant cytochrome P-450 (CYP) isoforms. This drug is metabolized to N-mono-desmethyl- (M1) and N,N-di-desmethylsibutramine (M2), and subsequent hydroxylation results in hydroxyl M1 (HM1) and hydroxyl M2 (HM2). No significant difference was noted in formation of M1from sibutramine between R- and S-sibutramine in HLM. However, S-enantiomers of M1 and M2 were preferentially metabolized to M2, HM1, and HM2compared to R-enantiomers in HLM, and intrinsic clearance (Clint) ratios of S-enantiomers/R-enantiomers were 1.97, 4.83, and 9.94 for M2, HM1, and HM2, respectively. CYP3A4 and CYP3A5 were only involved in the formation of M1, whereas CYP2B6 and CYP2C19 were responsible for all metabolic reactions of sibutramine. CYP2C19 and CYP3A5 displayed catalytic preference for S-sibutramine to S-M1, whereas CYP2B6 and CYP3A4 showed little or no stereoselectivity in metabolism of sibutramine to M1. In the case of M2 formation, CYP2B6 metabolized S-M1 more rapidly than R-M1 with a Clint ratio of 2.14. However, CYP2C19 catalyzed less S-M1 than R-M1 and the Clint ratio of S-M1 to R-M1 was 0.65. The most significant enantioselectivity was observed in formation of HM1 from M1, and HM2 from M2. CYP2B6 and CYP2C19 exhibited preferential catalysis of formation of hydroxyl metabolites from S-enantiomers rather than R-enantiomers. These results indicate that S-sibutramine was more rapidly metabolized by CYP isoforms than R-sibutramine, and that enantioselective metabolism needs to be considered in drug interactions involving sibutramine and co-administered drugs.

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

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

International Nuclear Information System (INIS)

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

2008-01-01

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

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

Science.gov (United States)

Sayin, Serkan; Akoz, Enise; Yilmaz, Mustafa

2014-09-14

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

Reactions of carbon acids and 1,3-dipoles in the presence of ionic liquids

International Nuclear Information System (INIS)

Zlotin, Sergei G; Makhova, Nina N

2010-01-01

The review is devoted to the use of ionic liquids as solvents, immobilized organocatalysts and reagents in reactions involving carbon acids and 1,3-dipoles, which are widely used to prepare practically valuable organic compounds of various classes. The characteristic features of processes in the presence of ionic liquids, the effects of the structure of cations and anions on the regio-, stereo- and enantioselectivities of reactions and methods of recovery of ionic liquids are considered.

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-04-01

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

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

International Nuclear Information System (INIS)

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

2016-01-01

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

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

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.

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.

Two-proton knockout on neutron-rich nuclei

International Nuclear Information System (INIS)

Bazin, D.; Brown, B.A.; Campbell, C.M.; Church, J.A.; Dinca, D.C.; Enders, J.; Gade, A.; Glasmacher, T.; Hansen, P.G.; Mueller, W.F.; Olliver, H.; Perry, B.C.; Sherrill, B.M.; Terry, J.R.; Tostevin, J.A.

2004-01-01

Two-proton knockout reactions on neutron-rich nuclei [Phys. Rev. Lett. 91 (2003) 012501] have been studied in inverse kinematics at intermediate energy. Strong evidence that the two-proton removal from a neutron-rich system proceeds as a direct reaction is presented, together with a preliminary theoretical discussion of the partial cross sections based on eikonal reaction theory and the many-body shell model. They show that this reaction can be used to characterize the wave functions of the projectiles and holds great promise for the study of neutron-rich nuclei

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

Science.gov (United States)

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

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)

Influence of isovector pairing and particle-number projection effects on spectroscopic factors for one-pair like-particle transfer reactions in proton-rich even-even nuclei

Science.gov (United States)

Benbouzid, Y.; Allal, N. H.; Fellah, M.; Oudih, M. R.

2018-04-01

Isovector neutron-proton (np) pairing and particle-number fluctuation effects on the spectroscopic factors (SF) corresponding to one-pair like-particle transfer reactions in proton-rich even-even nuclei are studied. With this aim, expressions of the SF corresponding to two-neutron stripping and two-proton pick-up reactions, which take into account the isovector np pairing effect, are established within the generalized BCS approach, using a schematic definition proposed by Chasman. Expressions of the same SF which strictly conserve the particle number are also established within the Sharp-BCS (SBCS) discrete projection method. In both cases, it is shown that these expressions generalize those obtained when only the pairing between like particles is considered. First, the formalism is tested within the Richardson schematic model. Second, it is applied to study even-even proton-rich nuclei using the single-particle energies of a Woods-Saxon mean-field. In both cases, it is shown that the np pairing effect and the particle-number projection effect on the SF values are important, particularly in N = Z nuclei, and must then be taken into account.

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

Science.gov (United States)

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

2015-02-01

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

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

International Nuclear Information System (INIS)

Kang, Seock Yong; Park, Yong Sun

2016-01-01

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

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.

Restrained Proton Indicator in Combined Quantum-Mechanics/Molecular-Mechanics Dynamics Simulations of Proton Transfer through a Carbon Nanotube.

Science.gov (United States)

Duster, Adam W; Lin, Hai

2017-09-14

Recently, a collective variable "proton indicator" was purposed for tracking an excess proton solvated in bulk water in molecular dynamics simulations. In this work, we demonstrate the feasibility of utilizing the position of this proton indicator as a reaction coordinate to model an excess proton migrating through a hydrophobic carbon nanotube in combined quantum-mechanics/molecular-mechanics simulations. Our results indicate that applying a harmonic restraint to the proton indicator in the bulk solvent near the nanotube pore entrance leads to the recruitment of water molecules into the pore. This is consistent with an earlier study that employed a multistate empirical valence bond potential and a different representation (center of excess charge) of the proton. We attribute this water recruitment to the delocalized nature of the solvated proton, which prefers to be in high-dielectric bulk solvent. While water recruitment into the pore is considered an artifact in the present simulations (because of the artificially imposed restraint on the proton), if the proton were naturally restrained, it could assist in building water wires prior to proton transfer through the pore. The potential of mean force for a proton translocation through the water-filled pore was computed by umbrella sampling, where the bias potentials were applied to the proton indicator. The free energy curve and barrier heights agree reasonably with those in the literature. The results suggest that the proton indicator can be used as a reaction coordinate in simulations of proton transport in confined environments.

An experimental investigation of proton-induced phenomena in krypton

International Nuclear Information System (INIS)

Mulders, J.J.L.

1985-01-01

In this thesis proton-induced phenomena in krypton gas are described. The considered reactions of protons on krypton are both nuclear and atomic. The nuclear conversion processes mainly result in the production of several Rb radioisotopes, such as 81 Rb that is used in 81 Rb-sup(81m)Kr generator systems for medical diagnostics. The irradiation of krypton gas (natural composition) with protons of about 26 MeV can be used for the routine production of 81 Rb from the direct production reaction 82 Kr(p,2n) 81 Rb and from the indirect reaction 82 Kr(p,2n)sup(81m)Rb → 81 Rb. To determine the scattering of protons in krypton gas targets a quantitative autoradiographic technique was developed. Proton profiles have been determined from the proton-induced activity distribution on a copper foil. For the on-line detection of produced Rb radioisotopes several optical detection techniques were investigated. (Auth.)

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

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 ...

Hydrogen-bond dynamics and proton transfer in nanoconfinement

NARCIS (Netherlands)

van der Loop, T.H.

2015-01-01

Proton transfer is of fundamental importance to both biology and chemistry. Much is known about proton transfer in large water volumes but often proton transfer reactions take place in very small nanometer sized volumes for example between lipid layers and in proton channels in mitochondria and

An enantioselective synthesis of S-[gamma]-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3-[sup 14]C] hydrochloride, an important metabolite of fluoxetine hydrochloride

Energy Technology Data Exchange (ETDEWEB)

Wheeler, W.J. (Lilly (Eli) and Co., Indianapolis, IN (United States). Lilly Research Labs.)

1992-06-01

The S-enantiomer of [gamma]-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3-[sup 14]C] hydrochloride has been prepared in eight steps from acetophenone-[carbonyl-[sup 14]C]. The key step in the synthesis involved the enantioselective reduction of R-2-chloroacetophenone-[1-[sup 14]C]with (-)-diisopinocampheyl-chloroborane in an 86.5% yield. The chlorohydrin was converted to R-phenyloxirane-[1-[sup 14]C], which was subsequently converted to the corresponding R-cyanohydrin by reaction with TMS-CN/CaO. Borane reduction and arylation, followed by salt formation yielded S-[gamma]-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[3-[sup 14]C] hydrochloride. (author).

Thermodynamic analysis of Bacillus subtilis endospore protonation using isothermal titration calorimetry

Science.gov (United States)

Harrold, Zoë R.; Gorman-Lewis, Drew

2013-05-01

Bacterial proton and metal adsorption reactions have the capacity to affect metal speciation and transport in aqueous environments. We coupled potentiometric titration and isothermal titration calorimetry (ITC) analyses to study Bacillus subtilis spore-proton adsorption. We modeled the potentiometric data using a four and five-site non-electrostatic surface complexation model (NE-SCM). Heats of spore surface protonation from coupled ITC analyses were used to determine site specific enthalpies of protonation based on NE-SCMs. The five-site model resulted in a substantially better model fit for the heats of protonation but did not significantly improve the potentiometric titration model fit. The improvement observed in the five-site protonation heat model suggests the presence of a highly exothermic protonation reaction circa pH 7 that cannot be resolved in the less sensitive potentiometric data. From the log Ks and enthalpies we calculated corresponding site specific entropies. Log Ks and site concentrations describing spore surface protonation are statistically equivalent to B. subtilis cell surface protonation constants. Spore surface protonation enthalpies, however, are more exothermic relative to cell based adsorption suggesting a different bonding environment. The thermodynamic parameters defined in this study provide insight on molecular scale spore-surface protonation reactions. Coupled ITC and potentiometric titrations can reveal highly exothermic, and possibly endothermic, adsorption reactions that are overshadowed in potentiometric models alone. Spore-proton adsorption NE-SCMs derived in this study provide a framework for future metal adsorption studies.

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

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

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.

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

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

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.)

Stereo-controlled synthesis of polyheterocycles via the diene-transmissive hetero-Diels-Alder reaction of β,γ-unsaturated α-keto esters.

Science.gov (United States)

Otani, Takashi; Tamai, Yumiko; Seki, Kazunori; Kikuchi, Tomohiro; Miyazawa, Taiichiro; Saito, Takao

2015-06-07

We describe the stereoselective synthesis of polyring-fused heterocyclic compounds based on diene-transmissive hetero-Diels-Alder reactions utilizing β,γ-unsaturated α-keto esters. This protocol involves the initial endo- or exo-selective Diels-Alder (DA) reactions with electron-rich dienophiles, methylenation of the ester carbonyl groups with the Tebbe reagent, and a stereoselective second DA reaction with electron-deficient dienophiles. The use of enantioselective DA reactions in the initial reaction enables access to chiral polyring-fused heterocyclic compounds with multiple chiral centres.

An enantioselective approach toward 3,4-dihydroisocoumarin through the bromocyclization of styrene-type carboxylic acids.

Science.gov (United States)

Chen, Jie; Zhou, Ling; Tan, Chong Kiat; Yeung, Ying-Yeung

2012-01-20

A facile and enantioselective approach toward 3,4-dihydroisocoumarin was developed. The method involved an amino-thiocarbamate catalyzed enantioselective bromocyclization of styrene-type carboxylic acids, yielding 3-bromo-3,4-dihydroisocoumarins with good yields and ee's. 3-Bromo-3,4-dihydroisocoumarins are versatile building blocks for various dihydroisocoumarin derivatives in which the Br group can readily be modified to achieve biologically important 4-O-type and 4-N-type 3,4-dihydroisocoumarin systems. In addition, studies indicated that, by refining some parameters, the synthetically useful 5-exo phthalide products could be achieved with good yields and ee's.

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

Science.gov (United States)

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

2010-01-01

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

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

Science.gov (United States)

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

2009-01-01

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

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

Science.gov (United States)

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

2015-03-27

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

Proton position near QB and coupling of electron and proton transfer in photosynthesis

International Nuclear Information System (INIS)

Belousov, R V; Poltev, S V; Kukushkin, A K

2003-01-01

We have calculated the energy levels and wavefunctions of a proton in a histidine (His)-plastoquinone (PQ) system in the reaction centre (RC) of photosystem 2 of higher plants and the RC of purple bacteria for different redox states of PQ Q B . For oxidized Q B , the proton is located near His. For once-reduced PQ, it is positioned in the middle between the nitrogen of His and the oxygen of PQ. For twofold-reduced PQ, the proton is localized near the oxygen of PQ. Using the values of total energy of the system in these states, we have also estimated the frequency of proton oscillations. On the basis of these results we propose a hypothesis about the coupling of electron-proton transfer

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

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.)

Catalytic Asymmetric Total Synthesis of (+)- and (-)-Paeoveitol via a Hetero-Diels-Alder Reaction.

Science.gov (United States)

Li, Tian-Ze; Geng, Chang-An; Yin, Xiu-Juan; Yang, Tong-Hua; Chen, Xing-Long; Huang, Xiao-Yan; Ma, Yun-Bao; Zhang, Xue-Mei; Chen, Ji-Jun

2017-02-03

The first catalytic asymmetric total synthesis of (+)- and (-)-paeoveitol has been accomplished in 42% overall yield via a biomimetic hetero-Diels-Alder reaction. The chiral phosphoric acid catalyzed hetero-Diels-Alder reaction showed excellent diastereo- and enantioselectivity (>99:1 dr and 90% ee); two rings and three stereocenters were constructed in a single step to produce (-)-paeoveitol on a scale of 452 mg. This strategy enabled us to selectively synthesize both paeoveitol enantiomers from the same substrates by simply changing the enantiomer of the catalyst.

Enantioselective Copper-Catalyzed Carboetherification of Unactivated Alkenes**

Science.gov (United States)

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

2014-01-01

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

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

Science.gov (United States)

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

2016-06-07

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

Role of keto–enol tautomerization in a chiral phosphoric acid catalyzed asymmetric thiocarboxylysis of meso-epoxide: a DFT study

KAUST Repository

Ajitha, Manjaly John; Huang, Kuo-Wei

2015-01-01

The mechanism of a chiral phosphoric acid catalyzed thiocarboxylysis of meso-epoxide was investigated by density functional theory (DFT) calculations (M06-2X). The nucleophilic ring opening of epoxide by thiobenzoic acid was found to proceed via a concerted termolecular transition state with a simultaneous dual proton transfer to yield the β-hydroxy thioester product. Electrostatic interactions together with the steric environment inside the chiral catalyst play an important role in determining the enantioselectivity of the reaction.

Role of keto–enol tautomerization in a chiral phosphoric acid catalyzed asymmetric thiocarboxylysis of meso-epoxide: a DFT study

KAUST Repository

Ajitha, Manjaly John

2015-09-15

The mechanism of a chiral phosphoric acid catalyzed thiocarboxylysis of meso-epoxide was investigated by density functional theory (DFT) calculations (M06-2X). The nucleophilic ring opening of epoxide by thiobenzoic acid was found to proceed via a concerted termolecular transition state with a simultaneous dual proton transfer to yield the β-hydroxy thioester product. Electrostatic interactions together with the steric environment inside the chiral catalyst play an important role in determining the enantioselectivity of the reaction.

Insight into the stereospecificity of short-chain thermus thermophilus alcohol dehydrogenase showing pro-S hydride transfer and prelog enantioselectivity.

Science.gov (United States)

Pennacchio, Angela; Giordano, Assunta; Esposito, Luciana; Langella, Emma; Rossi, Mosè; Raia, Carlo A

2010-04-01

The stereochemistry of the hydride transfer in reactions catalyzed by NAD(H)-dependent alcohol dehydrogenase from Thermus thermophilus HB27 was determined by means of (1)H-NMR spectroscopy. The enzyme transfers the pro-S hydrogen of [4R-(2)H]NADH and exhibits Prelog specificity. Enzyme-substrate docking calculations provided structural details about the enantioselectivity of this thermophilic enzyme. These results give additional insights into the diverse active site architectures of the largely versatile short-chain dehydrogenase superfamily enzymes. A feasible protocol for the synthesis of [4R-(2)H]NADH with high yield was also set up by enzymatic oxidation of 2-propanol-d(8) catalyzed by Bacillus stearothermophilus alcohol dehydrogenase.

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.

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.)

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.)

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

NARCIS (Netherlands)

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

2001-01-01

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

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

Science.gov (United States)

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

2015-03-01

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

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

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

Science.gov (United States)

Kraft, Philip; Mannschreck, Albrecht

2010-01-01

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

Kinetic Effects Of Increased Proton Transfer Distance On Proton-Coupled Oxidations Of Phenol-Amines

Science.gov (United States)

Rhile, Ian J.

2011-01-01

To test the effect of varying the proton donor-acceptor distance in proton-coupled electron transfer (PCET) reactions, the oxidation of a bicyclic amino-indanol (2) is compared with that of a closely related phenol with an ortho CPh2NH2 substituent (1). Spectroscopic, structural, thermochemical and computational studies show that the two amino-phenols are very similar, except that the O⋯N distance (dON) is >0.1 Å longer in 2 than in 1. The difference in dON is 0.13 ± 0.03 Å from X-ray crystallography and 0.165 Å from DFT calculations. Oxidations of these phenols by outer-sphere oxidants yield distonic radical cations •OAr–NH3+ by concerted proton-electron transfer (CPET). Simple tunneling and classical kinetic models both predict that the longer donor-acceptor distance in 2 should lead to slower reactions, by ca. two orders of magnitude, as well as larger H/D kinetic isotope effects (KIEs). However, kinetic studies show that the compound with the longer proton-transfer distance, 2, exhibits smaller KIEs and has rate constants that are quite close to those of 1. For example, the oxidation of 2 by the triarylamminium radical cation N(C6H4OMe)3•+ (3a+) occurs at (1.4 ± 0.1) × 104 M-1 s-1, only a factor of two slower than the closely related reaction of 1 with N(C6H4OMe)2(C6H4Br)•+ (3b+). This difference in rate constants is well accounted for by the slightly different free energies of reaction: ΔG°(2 + 3a+) = +0.078 V vs. ΔG°(1 + 3b+) = +0.04 V. The two phenol-amines do display some subtle kinetic differences: for instance, compound 2 has a shallower dependence of CPET rate constants on driving force (Brønsted α, Δln(k)/Δln(Keq)). These results show that the simple tunneling model is not a good predictor of the effect of proton donor-acceptor distance on concerted-electron transfer reactions involving strongly hydrogen-bonded systems. Computational analysis of the observed similarity of the two phenols emphasizes the importance of the highly

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.

Approaches to proton single-event rate calculations

International Nuclear Information System (INIS)

Petersen, E.L.

1996-01-01

This article discusses the fundamentals of proton-induced single-event upsets and of the various methods that have been developed to calculate upset rates. Two types of approaches are used based on nuclear-reaction analysis. Several aspects can be analyzed using analytic methods, but a complete description is not available. The paper presents an analytic description for the component due to elastic-scattering recoils. There have been a number of studies made using Monte Carlo methods. These can completely describe the reaction processes, including the effect of nuclear reactions occurring outside the device-sensitive volume. They have not included the elastic-scattering processes. The article describes the semiempirical approaches that are most widely used. The quality of previous upset predictions relative to space observations is discussed and leads to comments about the desired quality of future predictions. Brief sections treat the possible testing limitation due to total ionizing dose effects, the relationship of proton and heavy-ion upsets, upsets due to direct proton ionization, and relative proton and cosmic-ray upset rates

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

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)

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.)

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

Czech Academy of Sciences Publication Activity Database

Kotík, Michael; Kyslík, Pavel

2006-01-01

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

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.

Proton transfer and complex formation of angiotensin I ions with gaseous molecules at various temperature

International Nuclear Information System (INIS)

Nonose, Shinji; Yamashita, Kazuki; Sudo, Ayako; Kawashima, Minami

2013-01-01

Highlights: • Proton transfer from angiotensin I ions (z = 2, 3) to gaseous molecules was studied. • Temperature dependence of absolute reaction rate constants was measured. • Remarkable changes were obtained for distribution of product ions and reaction rate constants. • Proton transfer reaction was enhanced and reduced by complex formation. • Conformation changes are induced by complex formation and or by thermal collision with He. - Abstract: Proton transfer reactions of angiotensin I ions for +2 charge state, [M + 2H] 2+ , to primary, secondary and aromatic amines were examined in the gas phase. Absolute reaction rate constants for proton transfer were determined from intensities of parent and product ions in the mass spectra. Temperature dependence of the reaction rate constants was measured. Remarkable change was observed for distribution of product ions and reaction rate constants. Proton transfer reaction was enhanced or reduced by complex formation of [M + 2H] 2+ with gaseous molecules. The results relate to conformation changes of [M + 2H] 2+ with change of temperature, which are induced by complex formation and or by thermal collision with He. Proton transfer reactions of angiotensin I ions for +3 charge state, [M + 3H] 3+ , were also studied. The reaction rates did not depend on temperature so definitely

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.

Recent advances in the chemistry of Rh carbenoids: multicomponent reactions of diazocarbonyl compounds

International Nuclear Information System (INIS)

Medvedev, J J; Nikolaev, V A

2015-01-01

Multicomponent reactions of diazo compounds catalyzed by Rh II complexes become a powerful tool for organic synthesis. They enable three- or four-step processes to be carried out as one-pot procedures (actually as one step) with high stereoselectivity to give complex organic molecules, including biologically active compounds. This review addresses recent results in the chemistry of Rh-catalyzed multicomponent reactions of diazocarbonyl compounds with the intermediate formation of N-, O- and C=O–ylides. The diastereo- and enantioselectivity of these reactions and the possibility of using various co-catalysts to increase the efficiency of the processes under consideration are discussed. The bibliography includes 120 references

Ion-molecule reactions in the binary mixture of ethylene oxide and trioxane, 1

International Nuclear Information System (INIS)

Kumakura, Minoru; Sugiura, Toshio.

1977-01-01

The formation mechanism of protonated molecular ions by cross-reactions in ethylene oxide-trioxane mixtures has been studied with use of a modified time-of-flight mass spectrometer. The precursors of the product ions were determined by analysis of the fine structure of their ionization efficiency curves using deuterated ethylene oxide. Protonated ethylene oxide is formed by the hydrogen atom transfer reaction of ethylene oxide molecular ion with trioxane, and protonated trioxane by the proton transfer reaction of CHO + (from ethylene oxide) with trioxane. In the ion-molecule reactions of ethylene-d 4 oxide-trioxane mixtures, appreciable isotope effect was observed. The CHO + from ethylene oxide is an important reactant ion as compared with that from trioxane in the proton transfer reaction, and CHO + from ethylene oxide was suggested as a thermal reactive ion. The order of proton affinity could be estimated from the proton transfer reactions involving CHO + . It was found that the proton affinity of trioxane is smaller than that of ethylene oxide. (auth.)

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

DEFF Research Database (Denmark)

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

2003-01-01

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

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).

Protonation sites of aromatic compounds in (+) atmospheric pressure photoionization

Energy Technology Data Exchange (ETDEWEB)

Kim, Sung Hwan; Ahmed, Arif [Dept. of Chemistry, Kyungpoo k National University, Daegu (Korea, Republic of)

2017-02-15

Reaction enthalpy of hydrogen transfer reactions of aromatic compounds has been observed to be greatly affected by the exact location of the protonation site. Therefore, to clearly identify the protonation location, each candidate protonation site for 43 aromatic compounds were theoretically determined and their location was compared with that determined based on experimental MS data. Only the basic nitrogen atom is favorable as a protonation site for pyridine-type aromatic compounds, whereas carbon atoms are preferable for the protonation of pyrrole-type compounds. The most favorable protonation sites for aniline or methylated aniline-type aromatic compounds are either the nitrogen atom in the amine group or the carbon atom at the para-position to the amine group. Like pyrrole-type compounds, aromatic compounds with amine groups also favor protonation at the carbon atom instead of at the nitrogen atom. In addition, hydrocarbons having an anthracene structural motif without heteroatoms produced higher or equal percentages of protonated ions compared to that achieved with molecular ions. The results of this study can be used to improve the analyses of aromatic compounds.

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.)

Note: A monoenergetic proton backlighter for the National Ignition Facility

Energy Technology Data Exchange (ETDEWEB)

Rygg, J. R.; LePape, S.; Bachmann, B.; Khan, S. F.; Sayre, D. B. [Lawrence Livermore National Laboratory, Livermore, California 94551 (United States); Zylstra, A. B.; Séguin, F. H.; Gatu-Johnson, M.; Lahmann, B. J.; Petrasso, R. D.; Sio, H. W. [Plasma Science and Fusion Center, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Craxton, R. S.; Garcia, E. M.; Kong, Y. Z.; McKenty, P. W. [Laboratory for Laser Energetics, University of Rochester, Rochester, New York 14623 (United States); Rinderknecht, H. G. [Lawrence Livermore National Laboratory, Livermore, California 94551 (United States); Plasma Science and Fusion Center, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Rosenberg, M. J. [Plasma Science and Fusion Center, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Laboratory for Laser Energetics, University of Rochester, Rochester, New York 14623 (United States)

2015-11-15

A monoenergetic, isotropic proton source suitable for proton radiography applications has been demonstrated at the National Ignition Facility (NIF). A deuterium and helium-3 gas-filled glass capsule was imploded with 39 kJ of laser energy from 24 of NIF’s 192 beams. Spectral, spatial, and temporal measurements of the 15-MeV proton product of the {sup 3}He(d,p){sup 4}He nuclear reaction reveal a bright (10{sup 10} protons/sphere), monoenergetic (ΔE/E = 4%) spectrum with a compact size (80 μm) and isotropic emission (∼13% proton fluence variation and <0.4% mean energy variation). Simultaneous measurements of products produced by the D(d,p)T and D(d,n){sup 3}He reactions also show 2 × 10{sup 10} isotropically distributed 3-MeV protons.

Experimental determination of the complete spin structure for anti-proton + proton -> anti-\\Lambda + \\Lambda at anti-proton beam momentum of 1.637 GeV/c

CERN Document Server

Paschke, K.D.; Berdoz, A.; Franklin, G.B.; Khaustov, P.; Meyer, C.A.; Bradtke, C.; Gehring, R.; Goertz, S.; Harmsen, J.; Meier, A.; Meyer, W.; Radtke, E.; Reicherz, G.; Dutz, H.; Pluckthun, M.; Schoch, B.; Dennert, H.; Eyrich, W.; Hauffe, J.; Metzger, A.; Moosburger, M.; Stinzing, F.; Wirth, St.; Fischer, H.; Franz, J.; Heinsius, F.H.; Kriegler, E.; Schmitt, H.; Bunker, B.; Hertzog, D.; Jones, T.; Tayloe, R.; Broders, R.; Geyer, R.; Kilian, K.; Oelert, W.; Rohrich, K.; Sachs, K.; Sefzick, T.; Bassalleck, B.; Eilerts, S.; Fields, D.E.; Kingsberry, P.; Lowe, J.; Stotzer, R.; Johansson, T.; Pomp, S.; Wirth, St.

2006-01-01

The reaction anti-proton + proton -> anti-\\Lambda + \\Lambda -> anti-proton + \\pi^+ + proton + \\pi^- has been measured with high statistics at anti-proton beam momentum of 1.637 GeV/c. The use of a transversely-polarized frozen-spin target combined with the self-analyzing property of \\Lambda/anti-\\Lambda decay allows access to unprecedented information on the spin structure of the interaction. The most general spin-scattering matrix can be written in terms of eleven real parameters for each bin of scattering angle, each of these parameters is determined with reasonable precision. From these results all conceivable spin-correlations are determined with inherent self-consistency. Good agreement is found with the few previously existing measurements of spin observables in anti-proton + proton -> anti-\\Lambda + \\Lambda near this energy. Existing theoretical models do not give good predictions for those spin-observables that had not been previously measured.

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

Science.gov (United States)

Liu, Huigang; Li, Juan

2015-03-01

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

Proton knock-out in Hall A

International Nuclear Information System (INIS)

Jager, K. de

2003-01-01

Proton knock-out is studied in a broad program in Hall A at Jefferson Lab. The first experiment performed in Hall A studied the 16 O(e,e'p) reaction. Since then proton knock-out experiments have studied a variety of aspects of that reaction, from single-nucleon properties to its mechanism, such as final-state interactions and two-body currents, in nuclei from 2 H to 16 O. In this review the accomplishments of this program will be summarized and an outlook given of expected future results. (orig.)

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

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.

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

Science.gov (United States)

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

2017-11-08

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

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

Science.gov (United States)

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

2014-12-01

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

Lewis Acid Catalyzed Asymmetric Three-Component Coupling Reaction: Facile Synthesis of α-Fluoromethylated Tertiary Alcohols.

Science.gov (United States)

Aikawa, Kohsuke; Kondo, Daisuke; Honda, Kazuya; Mikami, Koichi

2015-12-01

A chiral dicationic palladium complex is found to be an efficient Lewis acid catalyst for the synthesis of α-fluoromethyl-substituted tertiary alcohols using a three-component coupling reaction. The reaction transforms three simple and readily available components (terminal alkyne, arene, and fluoromethylpyruvate) to valuable chiral organofluorine compounds. This strategy is completely atom-economical and results in perfect regioselectivities and high enantioselectivities of the corresponding tertiary allylic alcohols in good to excellent yields. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Enantioselective effect of bifenthrin on antioxidant enzyme gene expression and stress protein response in PC12 cells.

Science.gov (United States)

Lu, Xianting

2013-07-01

Enantioselectivity in toxicology and the health risk of chiral xenobiotics have become frontier topics interfacing chemistry and toxicology. Our previous results showed that cis-bifenthrin (cis-BF) induced cytotoxicity and apoptosis in vitro in an enantioselective manner. However, the exact molecular mechanisms of synthetic pyrethroid-induced enantioselective apoptosis and cytotoxicity have so far received limited research attention. In the present study, the expression patterns of different genes encoding heat shock protein and antioxidant enzymes were investigated by real-time quantitative PCR in rat adrenal pheochromocytoma (PC12) cells after exposure to cis-BF and its enantiomers. The results showed that exposure to 1S-cis-BF resulted in increased transcription of HSP90, HSP70, HSP60, Cu-Zn-superoxide dismutase, Mn-superoxide dismutase, catalase and glutathione-s-transferase at a concentration of 5 µm and above, while exposure to 1R-cis-BF and rac-cis-BF exhibited these effects to lesser degrees. In addition, induction of antioxidant enzyme gene expression produced by 1S-cis-BF might occur, at least in part, through activation of p38 mitogen-activated protein kinases (MAPK) and extracellular regulated kinases, while increase in stress protein response produced by 1S-cis-BF might occur through the p38 MAPK signaling pathway. The results not only suggest that enantioselectivity should be considered in evaluating the ecotoxicological effects and health risk of chiral contaminants, but also will improve the understanding of molecular mechanism for chiral chemical-induced cytotoxicity. Copyright © 2012 John Wiley & Sons, Ltd.

Kinetics of water-mediated proton transfer in our atmosphere

International Nuclear Information System (INIS)

Loerting, T.

2000-07-01

Variational transition state theory and multidimensional tunneling methods on hybrid density functional theory generated hypersurfaces have been used to investigate the temperature dependence of the reaction rate constants of water-mediated proton transfer reactions relevant to the chemistry of our atmosphere, namely the hydration of sulfur dioxide and sulfur trioxide and the decomposition of chlorine nitrate. Highly accurate reaction barriers were calculated using ab initio methods taking into account most of the electron correlation, namely CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ and G2(MP2). On comparing the determined rate constants with laboratory and atmospheric data, the following points could be established: All of the investigated reactions are highly sensitive to changes in humidity, as water acts as efficient catalyst, i.e., the barrier to the reaction is reduced drastically. Present-day atmospheric chemistry can only be explained when a limited number of water molecules is available for the formation of molecular clusters. Both in the troposphere and in the stratosphere SO 3 is hydrated rather than SO 2 . SO 2 emissions have to be oxidized, therefore, before being subject to hydration. A mechanism involving two or three water molecules is relevant for the production of sulfate aerosols, which play a decisive role in the context of global climate change and acid rain. A third water molecule has the function of assisting double-proton transfer rather than acting as active participant in triple-proton transfer in the case of the hydration of sulfur oxides. The observed ozone depletion above Arctica and Antarctica can be explained either by decomposition of chlorine nitrate in the presence of three water molecules (triple proton transfer) or by decomposition of chlorine nitrate in the presence of one molecule of HCl and one molecule of water (double proton transfer). The preassociation reaction required for homogeneous gas-phase conversion of chlorine

(SalenMn(III Catalyzed Asymmetric Epoxidation Reactions by Hydrogen Peroxide in Water: A Green Protocol

Directory of Open Access Journals (Sweden)

Francesco Paolo Ballistreri

2016-07-01

Full Text Available Enantioselective epoxidation reactions of some chosen reactive alkenes by a chiral Mn(III salen catalyst were performed in H2O employing H2O2 as oxidant and diethyltetradecylamine N-oxide (AOE-14 as surfactant. This procedure represents an environmentally benign protocol which leads to e.e. values ranging from good to excellent (up to 95%.

Experimental and theoretical study of two-proton and proton-deuteron correlations at very small relative momenta

International Nuclear Information System (INIS)

Martin, Lilian

1993-01-01

In this research thesis, the author first reports the analysis of light particle correlations by two theoretical approaches. The first one is the classical approximation of correlations: formulation, characteristics of the emitter nucleus and initial conditions, construction of the correlation function with notably the comparison with experimental proton-proton and proton-deuteron correlation functions measured in the 40 Ar + 108 Ag at 44 MeV/nucleon. The second one is the quantum approach of correlations: formulations, predictions of the quantum model with the same comparison as above. The second part addresses the measurement and analysis of the proton-proton correlation function at very small relative momenta: presentation of the studied reaction, description of the experiment (sensors, magnetic spectrometer, event recording), analysis of protons detected within the spectrometer) [fr

Enantioselective Effects of o,p'-DDT on Cell Invasion and Adhesion of Breast Cancer Cells: Chirality in Cancer Development.

Science.gov (United States)

He, Xiangming; Dong, Xiaowu; Zou, Dehong; Yu, Yang; Fang, Qunying; Zhang, Quan; Zhao, Meirong

2015-08-18

The o,p'-dichlorodiphenyltrichloroethane (DDT) with a chiral center possesses enantioselective estrogenic activity, in which R-(-)-o,p'-DDT exerts a more potent estrogenic effect than S-(+)-o,p'-DDT. Although concern regarding DDT exposure and breast cancer has increased in recent decades, the mode of enantioselective action of o,p'-DDT in breast cancer development is still unknown. Herein, we conducted a systematic study of the effect of o,p'-DDT on stereoselective breast tumor cell progression in a widely used in vitro breast tumor cell model, MCF-7 cells. We demonstrated that R-(-)-o,p'-DDT promoted more cancer cell invasion mediated by the human estrogen receptor (ER) by inducing invasion-promoted genes (matrix metalloproteinase-2 and -9 and human telomerase reverse transcriptase) and inhibiting invasion-inhibited genes (tissue inhibitor of metalloproteinase-1 and -4). Molecular docking verified that the binding affinity between R-(-)-o,p'-DDT and human ER was stronger than that of S-(+)-o,p'-DDT. The enantioselective-induced decrease in cell-to-cell adhesion may involve the downregulation of adhesion-promoted genes (E-cadherin and β-catenin). For the first time, these results reveal that estrogenic-like chiral compounds are of significant concern in the progression of human cancers and that human health risk assessment of chiral chemicals should consider enantioselectivity.

Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

KAUST Repository

Widger, Peter C. B.; Ahmed, Syud M.; Coates, Geoffrey W.

2011-01-01

Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

KAUST Repository

Widger, Peter C. B.

2011-07-26

Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

Scaling in inelastic proton-proton interactions at storage ring energies of 23-63 GeV

International Nuclear Information System (INIS)

Thome, W.

1980-02-01

In this paper inelastic proton-proton interactions are studied with low transversal momenta ( approx. equal to 350 MeV/c) of the final state hadrons. The reaction products from p-p collisions have been detected for the first time visually, using two large streamer chambers which enclose one interaction region of the CERN storage rings almost completely. (orig./HSI) [de

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.

Design, Synthesis and Biological Activity of Novel Reversible Peptidyl FVIIa Inhibitors Rh-Catalyzed Enantioselective Synthesis of Diaryl Amines

DEFF Research Database (Denmark)

Storgaard, Morten

functional group tolerance. Unfortunately, these -aryl tetramic acids were too unreactive and ring opening toward the synthesis of the building block did not succeed. However, -aryl tetramic acids are still interesting compounds due to their potential biological activity. The building block 3.15 (P1......-catalyzed enantioselective synthesis of diaryl amines, which is an important class of compounds (Chapter 4). For example it is found in the third generation anti-histaminic agent levocetirizine. Development of efficient synthetic routes is therefore of considerably interest. The rhodium-catalyzed enantioselective synthesis...

Proton drip-line studies at HRIBF

International Nuclear Information System (INIS)

Rykaczewski, K.P.; Batchelder, J.C.; Bingham, C.R.; Bryan, R.E.; Davinson, T.; Woods, P.J.; Ginter, T.N.; Hamilton, J. H.; Gross, C.J.; Grzywacz, R.; Janas, Z.; Karny, M.; MacDonald, B.D.; McConnell, J.W.; Toth, K.S.; Piechaczek, A.; Zganjar, E.F.; Szerypo, J.; Walters, W. B.

2000-01-01

Proton radioactivity studies performed at the Holifield Radioactive Ion Beam Facility (HFBR) within the last few years are reviewed. The discovery of five new proton radioactivities 140 Ho, 141m Ho, 145 Tm, 150m Lu and 151m Lu is presented together with a recent observation of fine structure in proton emission from 146gs,m Tm. These proton emitters were produced by means of fusion-evaporation reactions and studied with the HFBR Recoil Mass Separator and detection system based on a Double-sided Silicon Strip Detector. For 113 Cs and 151 Lu, the studies of level structure were extended beyond the proton-emitting states via the measurements with a clover array Clarion using Recoil Decay Tagging

Study of the proton-proton interaction involving a πO production

International Nuclear Information System (INIS)

Reposeur, T.

1989-01-01

The proton-proton inelastic interaction, giving a neutral single pion, is studied. The reaction with two protons and one pi-zero in the final state for incident kinetic energies ranging from 480-560 MeV in 20 MeV steps is studied. It is necessary to develop a neutral pion spectrometer to detect in coincidence the two gammas of the decaying pi-zero. The detector has a good selectivity for neutral pion detection, and quantitative measurements require an accurate simulation of its response. The experiment shows that it is possible to measure the non resonant partial cross section. The relative accuracy on the total cross sections allows to search for a few percent effect. An isovector narrow dibaryonic resonance in that energy range, is suggested [fr

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.)

Proton transfer events in GFP.

Science.gov (United States)

Di Donato, Mariangela; van Wilderen, Luuk J G W; Van Stokkum, Ivo H M; Stuart, Thomas Cohen; Kennis, John T M; Hellingwerf, Klaas J; van Grondelle, Rienk; Groot, Marie Louise

2011-09-28

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 transfer through a 'proton-wire', formed by the chromophore (the proton donor), water molecule W22, Ser205 and Glu222 (the acceptor), on a picosecond time scale. To obtain a more refined view of this process, we have used a combined approach of time resolved mid-infrared spectroscopy and visible pump-dump-probe spectroscopy to resolve with atomic resolution how and how fast protons move through this wire. Our results indicate that absorption of light by GFP induces in 3 ps (10 ps in D(2)O) a shift of the equilibrium positions of all protons in the H-bonded network, leading to a partial protonation of Glu222 and to a so-called low barrier hydrogen bond (LBHB) for the chromophore's proton, giving rise to dual emission at 475 and 508 nm. This state is followed by a repositioning of the protons on the wire in 10 ps (80 ps in D(2)O), ultimately forming the fully deprotonated chromophore and protonated Glu222.

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)

Application of the aza-Diels-Alder reaction in the synthesis of natural products.

Science.gov (United States)

Cao, Min-Hui; Green, Nicholas J; Xu, Sheng-Zhen

2017-04-11

The Diels-Alder reaction that involves a nitrogen atom in the diene or dienophile is termed the aza-Diels-Alder reaction. As well as the powerful all-carbon Diels-Alder reaction, the aza-Diels-Alder reaction has also played an important role in the total synthesis of natural products. Herein, we review various natural products using an aza-Diels-Alder reaction as a key step to their total synthesis, and divide the syntheses into inter- and intra-molecular aza-Diels-Alder reactions and a retro-aza-Diels-Alder reaction. Inter- and intra-molecular aza-Diels-Alder reactions involve an imine as an electron deficient dienophile and an imine as an electron deficient azadiene. The significance of the aza-Diels-Alder reaction for the construction of a six-membered ring containing nitrogen is tremendous, but the development of asymmetric, in particular catalytic enantioselective intramolecular aza-Diels-Alder reaction in the total synthesis of natural products remains highly challenging, and will no doubt see enormous advances in the future.

alpha,beta-unsaturated 2-acyl imidazoles as a practical class of dienophiles for the DNA-Based catalytic asymmetric diels-alder reaction in water

NARCIS (Netherlands)

Boersma, A.J.; Feringa, B.L.; Roelfes, G.

2007-01-01

alpha,beta-Unsaturated 2-acyl imidazoles are a novel and practical class of dienophiles for the DNA-based catalytic asymmetric Diels-Alder reaction in water. The Diels-Alder products are obtained with very high diastereoselectivities and enantioselectivities in the range of 83-98%. The catalytic

Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

Science.gov (United States)

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

2014-06-16

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

Spin-isospin excitation of 3He with three-proton final state

Science.gov (United States)

Ishikawa, Souichi

2018-01-01

Spin-isospin excitation of the {}^3He nucleus by a proton-induced charge exchange reaction, {}^3He(p,n)ppp, at forward neutron scattering angle is studied in a plane wave impulse approximation (PWIA). In PWIA, cross sections of the reaction are written in terms of proton-neutron scattering amplitudes and response functions of the transition from {}3He to the three-proton state by spin-isospin transition operators. The response functions are calculated with realistic nucleon-nucleon potential models using a Faddeev three-body method. Calculated cross sections agree with available experimental data in substance. Possible effects arising from the uncertainty of proton-neutron amplitudes and three-nucleon interactions in the three-proton system are examined.

First Novozym 435 lipase-catalyzed Morita-Baylis-Hillman reaction in the presence of amides.

Science.gov (United States)

Tian, Xuemei; Zhang, Suoqin; Zheng, Liangyu

2016-03-01

The first Novozym 435 lipase-catalyzed Morita-Baylis-Hillman (MBH) reaction with amides as co-catalyst was realized. Results showed that neither Novozym 435 nor amide can independently catalyze the reaction. This co-catalytic system that used a catalytic amount of Novozym 435 with a corresponding amount of amide was established and optimized. The MBH reaction strongly depended on the structure of aldehyde substrate, amide co-catalyst, and reaction additives. The optimized reaction yield (43.4%) was achieved in the Novozym 435-catalyzed MBH reaction of 2, 4-dinitrobenzaldehyde and cyclohexenone with isonicotinamide as co-catalyst and β-cyclodextrin as additive only in 2 days. Although enantioselectivity of Novozym 435 was not found, the results were still significant because an MBH reaction using lipase as biocatalyst was realized for the first time. Copyright © 2015 Elsevier Inc. All rights reserved.

Chiral separation and enantioselective degradation of vinclozolin in soils.

Science.gov (United States)

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

2014-03-01

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

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.

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

Science.gov (United States)

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

2015-02-11

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

A new enantioselective CE method for determination of oxcarbazepine and licarbazepine after fungal biotransformation.

Science.gov (United States)

Bocato, Mariana Zuccherato; Bortoleto, Marcela Armelim; Pupo, Mônica Tallarico; de Oliveira, Anderson Rodrigo Moraes

2014-10-01

The present work describes, for the first time, the simultaneous separation of oxcarbazepine (OXC) and its active metabolite 10-hydroxy-10,11-dihydrocarbamazepine (licarbazepine, Lic) by chiral CE. The developed method was employed to monitor the enantioselective biotransformation of OXC into its active metabolite by fungi. The electrophoretic separations were performed using 10 mmol/L of a Tris-phosphate buffer solution (pH 2.5) containing 1% w/v of β-CD phosphate sodium salt (P-β-CD) as running electrolyte, -20 kV of applied voltage and a 15°C capillary temperature. The method was linear over the concentration range of 1000-30 000 ng/mL for OXC and 75-900 ng/mL for each Lic enantiomer (r ≥ 0.9952). Within-day precision and accuracy evaluated by RSD and relative errors, respectively, were lower than 15% for all analytes. The validated method was used to evaluate the enantioselective biotransformation of OXC, mediated by fungi, into its active metabolite Lic. This study showed that the fungi Glomerella cingulata (VA1) and Beuveria bassiana were able to enantioselectively metabolize the OXC into Lic after 360 h of incubation. Biotransformation by the fungus Beuveria bassiana showed 79% enantiomeric excess for (S)-(+)-Lic, while VA1 gave an enantiomeric excess of 100% for (S)-(+)-Lic. This study opens a new route to the drug (S)-(+)-licarbazepine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Czech Academy of Sciences Publication Activity Database

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

2016-01-01

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