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Sample records for asymmetric reactions forming

  1. Strong evidence for quasifission in asymmetric reactions forming {sup 202}Po

    SciTech Connect

    Rafiei, R.; Thomas, R. G.; Hinde, D. J.; Dasgupta, M.; Morton, C. R.; Gasques, L. R.; Brown, M. L.; Rodriguez, M. D.

    2008-02-15

    Fission fragment mass-angle correlations and mass ratio distributions have been measured for the reactions {sup 16}O+{sup 186}Os, {sup 24}Mg+{sup 178}Hf, {sup 34}S+{sup 168}Er, and {sup 48}Ti+{sup 154}Sm, forming the {sup 202}Po composite nucleus, at near barrier energies. Systematic analysis based on the expected dependence of the variance of the mass distribution on the angular momentum and temperature of the compound nucleus indicate that the two lighter systems evolve through true compound nucleus fission. Evidence of quasifission was observed for the two most mass-symmetric reactions, through strong mass-angle correlations for the {sup 48}Ti+{sup 154}Sm reaction and a broadened mass ratio distribution for the {sup 34}S+{sup 168}Er reaction. Furthermore, the increase in mass width at near barrier energies shows the influence of the alignment of statically deformed target nuclei.

  2. Diastereodivergent organocatalytic asymmetric vinylogous Michael reactions.

    PubMed

    Li, Xin; Lu, Min; Dong, Yun; Wu, Wenbin; Qian, Qingqing; Ye, Jinxing; Dixon, Darren J

    2014-07-24

    One of the major challenges of modern asymmetric catalysis is the ability to selectively control the formation of all diastereoisomers of reaction products possessing multiple stereocenters. Pioneers of such diastereodivergent catalytic asymmetric processes have focused on reactions where the newly formed stereogenic centres are proximal to the active carbonyl group. To date, however, diastereodivergent reactions at remote positions remain an unmet challenge. Herein, we describe a catalyst-controlled diastereodivergence in the formation of remote stereocenters in the direct vinylogous Michael reactions of β, γ-unsaturated butenolides to α, β-unsaturated ketones. The reactions are enabled by two complementary, non-enantiomeric multifunctional catalysts, which mutually activate and organise both reactants, affording either the syn- or anti-adduct with high diastereo- and enantioselectivity. These two catalytic systems are also applicable in the Mukaiyama-Michael reactions and tandem Michael-Michael reactions.

  3. Application of a C-C Bond-Forming Conjugate Addition Reaction in Asymmetric Dearomatization of β-Naphthols.

    PubMed

    Yang, Dongxu; Wang, Linqing; Kai, Ming; Li, Dan; Yao, Xiaojun; Wang, Rui

    2015-08-10

    A C-C bond-forming conjugate reaction was successfully applied to the enantioselective dearomatization of β-naphthols. A C(sp2)-C(sp3) bond is formed by using propargylic ketones as reactive partners. Good to excellent Z/E ratios and ee values were obtained by employing an in situ generated magnesium catalyst. Further transformations of the Z-configured C-C double bond in the products were achieved under mild reaction conditions. Moreover, the stereocontrolling element of this magnesium-catalyzed dearomatization reaction was explored by computational chemistry. PMID:26173841

  4. Asymmetric reactions in continuous flow

    PubMed Central

    Mak, Xiao Yin; Laurino, Paola

    2009-01-01

    Summary An overview of asymmetric synthesis in continuous flow and microreactors is presented in this review. Applications of homogeneous and heterogeneous asymmetric catalysis as well as biocatalysis in flow are discussed. PMID:19478913

  5. Theory and Modeling of Asymmetric Catalytic Reactions.

    PubMed

    Lam, Yu-Hong; Grayson, Matthew N; Holland, Mareike C; Simon, Adam; Houk, K N

    2016-04-19

    Modern density functional theory and powerful contemporary computers have made it possible to explore complex reactions of value in organic synthesis. We describe recent explorations of mechanisms and origins of stereoselectivities with density functional theory calculations. The specific functionals and basis sets that are routinely used in computational studies of stereoselectivities of organic and organometallic reactions in our group are described, followed by our recent studies that uncovered the origins of stereocontrol in reactions catalyzed by (1) vicinal diamines, including cinchona alkaloid-derived primary amines, (2) vicinal amidophosphines, and (3) organo-transition-metal complexes. Two common cyclic models account for the stereoselectivity of aldol reactions of metal enolates (Zimmerman-Traxler) or those catalyzed by the organocatalyst proline (Houk-List). Three other models were derived from computational studies described in this Account. Cinchona alkaloid-derived primary amines and other vicinal diamines are venerable asymmetric organocatalysts. For α-fluorinations and a variety of aldol reactions, vicinal diamines form enamines at one terminal amine and activate electrophilically with NH(+) or NF(+) at the other. We found that the stereocontrolling transition states are cyclic and that their conformational preferences are responsible for the observed stereoselectivity. In fluorinations, the chair seven-membered cyclic transition states is highly favored, just as the Zimmerman-Traxler chair six-membered aldol transition state controls stereoselectivity. In aldol reactions with vicinal diamine catalysts, the crown transition states are favored, both in the prototype and in an experimental example, shown in the graphic. We found that low-energy conformations of cyclic transition states occur and control stereoselectivities in these reactions. Another class of bifunctional organocatalysts, the vicinal amidophosphines, catalyzes the (3 + 2) annulation

  6. The Direct Catalytic Asymmetric Aldol Reaction

    PubMed Central

    Brindle, Cheyenne S.

    2013-01-01

    Asymmetric aldol reactions are a powerful method for the construction of carbon-carbon bonds in an enantioselective fashion. Historically this reaction has been performed in a stoichiometric fashion to control the various aspects of chemo-, diastereo-, regio- and enantioselectivity, however, a more atom economical approach would unite high selectivity with the use of only a catalytic amount of a chiral promoter. This critical review documents the development of direct catalytic asymmetric aldol methodologies, including organocatalytic and metal-based strategies. New methods have improved the reactivity, selectivity and substrate scope of the direct aldol reaction and enabled the synthesis of complex molecular targets PMID:20419212

  7. Catalytic Asymmetric 1,4-Addition Reactions of Simple Alkylnitriles.

    PubMed

    Yamashita, Yasuhiro; Sato, Io; Suzuki, Hirotsugu; Kobayashi, Shū

    2015-10-01

    The development of catalytic asymmetric carbon-carbon bond-forming reactions of alkylnitriles that do not have an activating group at the α-position, under proton-transfer conditions, is a challenging research topic. Here, we report catalytic asymmetric direct-type 1,4-addition reactions of alkylnitriles with α,β-unsaturated amides by using a catalytic amount of potassium hexamethyldisilazide (KHMDS) with a chiral macro crown ether. The desired reactions proceeded in high yields with good diastereo- and enantioselectivities. To our knowledge, this is the first example of catalytic asymmetric direct-type 1,4-addition reaction of alkylnitriles without any activating group at the α-position.

  8. Independence from the Sequence of Single-Electron Transfer of Photoredox Process in Redox-Neutral Asymmetric Bond-Forming Reaction.

    PubMed

    Kizu, Tomohito; Uraguchi, Daisuke; Ooi, Takashi

    2016-08-19

    A catalytic cycle initiated by the oxidative quenching of the excited photosensitizer (Ir*(ppy)3) is established for the enantioselective coupling between (N-arylamino)methanes and (N-methanesulfonyl)aldimines catalyzed by Ir-based photosensitizer and a chiral (arylamino)phosphonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate under visible light irradiation. This achievement clearly demonstrates the insensitivity of this redox-neutral asymmetric reaction to the sequence of the key redox events involved in the synergistic catalysis. PMID:27176596

  9. Organocatalytic Asymmetric Reactions of Epoxides: Recent Progress.

    PubMed

    Meninno, Sara; Lattanzi, Alessandra

    2016-03-01

    In this Minireview recent advances in the asymmetric reactions of meso and racemic epoxides promoted by organocatalysts is reviewed. Organic promoters, such as chiral phosphoric acids, amino- and peptidyl thioureas, and sulfinamides, have been successfully used for a variety of enantioselective transformations of epoxides under catalytic conditions, involving direct nucleophilic attack at the oxirane ring, base-catalysed β-eliminations and Brønsted acid catalysed 1,2-rearrangements. Accordingly, highly valuable enantioenriched 1,2-functionalised alcohols, carbonyl compounds and nitroepoxides are attainable. Dual activation of the reagents, provided by the organocatalysts, appears to be the most recurrent strategy, potentially suitable to face other unmet challenges in asymmetric ring-opening reactions of epoxides.

  10. [Development of new methods in asymmetric reactions and their applications].

    PubMed

    Node, Manabu

    2002-01-01

    Several novel methods using chiral reagents and biocatalysts for asymmetric reactions are described. Among those reactions, asymmetric reduction via a novel tandem Michael addition/Meerwein-Ponndorf-Verley reduction of acyclic alpha,beta-unsaturated ketones using a chiral mercapto alcohol, asymmetric synthesis of allene-1,3-dicarboxylate via crystallization induced asymmetric transformation, and improved asymmetric nitroolefination of lactones and lactames at alpha-carbon using new chiral reagents were developed. In the reactions using biocatalysts, asymmetric dealkoxycarbonylation of bicyclic beta-keto diesters having sigma-symmetry with lipase or esterase to give optically active beta-keto esters, the asymmetric reduction of bicyclic 1,3-diketones having sigma-symmetry with Baker's yeast to give optically active keto alcohols, and the asymmetric aldol reaction of glycine with threonine aldolase were also developed. The above mentioned products were effectively utilized as chiral building blocks for the asymmetric synthesis of natural products and drugs.

  11. Recent advances in copper-catalyzed asymmetric coupling reactions

    PubMed Central

    2015-01-01

    Summary Copper-catalyzed (or -mediated) asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C–C, C–N, C–O and other carbon–heteroatom bonds as well as for the construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C–C and carbon–heteroatom bonds. PMID:26734106

  12. Recent advances in copper-catalyzed asymmetric coupling reactions.

    PubMed

    Zhou, Fengtao; Cai, Qian

    2015-01-01

    Copper-catalyzed (or -mediated) asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C-C, C-N, C-O and other carbon-heteroatom bonds as well as for the construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C-C and carbon-heteroatom bonds. PMID:26734106

  13. Chromium-Catalyzed Asymmetric Dearomatization Addition Reactions of Halomethyl Heteroarenes.

    PubMed

    Tian, Qingshan; Bai, Jing; Chen, Bin; Zhang, Guozhu

    2016-04-15

    The first asymmetric dearomatization addition reaction of halomethyl arenes including benzofuran and benzothiophene was enabled by chromium catalysis. A variety of aldehydes served as suitable electrophiles under mild reaction conditions. Molecular complexities are quickly increased in a highly diastereo- and enantioselective manner.

  14. Asymmetric Aldol-Tishchenko Reaction of Sulfinimines.

    PubMed

    Foley, Vera M; McSweeney, Christina M; Eccles, Kevin S; Lawrence, Simon E; McGlacken, Gerard P

    2015-11-20

    Methods for the preparation of 1,3-amino alcohols and their derivatives containing two stereogenic centers usually involve a two-step installation of the chiral centers. An aldol-Tishchenko reaction of chiral sulfinimines which involves the first reported reduction of a C═N in this type of reaction is described. Two and even three chiral centers can be installed in one synthetic step, affording anti-1,3-amino alcohols in good diastereo- and enantioselectivity. PMID:26528888

  15. Asymmetric petasis reactions catalyzed by chiral biphenols.

    PubMed

    Lou, Sha; Schaus, Scott E

    2008-06-01

    Chiral biphenols catalyze the enantioselective Petasis reaction of alkenyl boronates, secondary amines, and ethyl glyoxylate. The reaction requires the use of 15 mol % of (S)-VAPOL as the catalyst, alkenyl boronates as nucleophiles, ethyl glyoxylate as the aldehyde component, and 3 A molecular sieves as an additive. The chiral alpha-amino ester products are obtained in good yields (71-92%) and high enantiomeric ratios (89:11-98:2). Mechanistic investigations indicate single ligand exchange of acyclic boronate with VAPOL and tetracoordinate boronate intermediates. PMID:18459782

  16. Computational Studies on Cinchona Alkaloid-Catalyzed Asymmetric Organic Reactions.

    PubMed

    Tanriver, Gamze; Dedeoglu, Burcu; Catak, Saron; Aviyente, Viktorya

    2016-06-21

    Remarkable progress in the area of asymmetric organocatalysis has been achieved in the last decades. Cinchona alkaloids and their derivatives have emerged as powerful organocatalysts owing to their reactivities leading to high enantioselectivities. The widespread usage of cinchona alkaloids has been attributed to their nontoxicity, ease of use, stability, cost effectiveness, recyclability, and practical utilization in industry. The presence of tunable functional groups enables cinchona alkaloids to catalyze a broad range of reactions. Excellent experimental studies have extensively contributed to this field, and highly selective reactions were catalyzed by cinchona alkaloids and their derivatives. Computational modeling has helped elucidate the mechanistic aspects of cinchona alkaloid catalyzed reactions as well as the origins of the selectivity they induce. These studies have complemented experimental work for the design of more efficient catalysts. This Account presents recent computational studies on cinchona alkaloid catalyzed organic reactions and the theoretical rationalizations behind their effectiveness and ability to induce selectivity. Valuable efforts to investigate the mechanisms of reactions catalyzed by cinchona alkaloids and the key aspects of the catalytic activity of cinchona alkaloids in reactions ranging from pharmaceutical to industrial applications are summarized. Quantum mechanics, particularly density functional theory (DFT), and molecular mechanics, including ONIOM, were used to rationalize experimental findings by providing mechanistic insights into reaction mechanisms. B3LYP with modest basis sets has been used in most of the studies; nonetheless, the energetics have been corrected with higher basis sets as well as functionals parametrized to include dispersion M05-2X, M06-2X, and M06-L and functionals with dispersion corrections. Since cinchona alkaloids catalyze reactions by forming complexes with substrates via hydrogen bonds and long

  17. Computational Studies on Cinchona Alkaloid-Catalyzed Asymmetric Organic Reactions.

    PubMed

    Tanriver, Gamze; Dedeoglu, Burcu; Catak, Saron; Aviyente, Viktorya

    2016-06-21

    Remarkable progress in the area of asymmetric organocatalysis has been achieved in the last decades. Cinchona alkaloids and their derivatives have emerged as powerful organocatalysts owing to their reactivities leading to high enantioselectivities. The widespread usage of cinchona alkaloids has been attributed to their nontoxicity, ease of use, stability, cost effectiveness, recyclability, and practical utilization in industry. The presence of tunable functional groups enables cinchona alkaloids to catalyze a broad range of reactions. Excellent experimental studies have extensively contributed to this field, and highly selective reactions were catalyzed by cinchona alkaloids and their derivatives. Computational modeling has helped elucidate the mechanistic aspects of cinchona alkaloid catalyzed reactions as well as the origins of the selectivity they induce. These studies have complemented experimental work for the design of more efficient catalysts. This Account presents recent computational studies on cinchona alkaloid catalyzed organic reactions and the theoretical rationalizations behind their effectiveness and ability to induce selectivity. Valuable efforts to investigate the mechanisms of reactions catalyzed by cinchona alkaloids and the key aspects of the catalytic activity of cinchona alkaloids in reactions ranging from pharmaceutical to industrial applications are summarized. Quantum mechanics, particularly density functional theory (DFT), and molecular mechanics, including ONIOM, were used to rationalize experimental findings by providing mechanistic insights into reaction mechanisms. B3LYP with modest basis sets has been used in most of the studies; nonetheless, the energetics have been corrected with higher basis sets as well as functionals parametrized to include dispersion M05-2X, M06-2X, and M06-L and functionals with dispersion corrections. Since cinchona alkaloids catalyze reactions by forming complexes with substrates via hydrogen bonds and long

  18. Asymmetric catalytic hydrogenation reactions in supercritical carbon dioxide

    SciTech Connect

    Burk, M.J.; Gross, M.F.; Feng, S.; Tumas, W.

    1995-08-09

    We demonstrate that asymmetric catalytic hydrogenation reactions can be conducted in supercritical CO{sub 2} and that, in some cases, higher enantioselectivities can be achieved in this solvent relative to conventional solvents. These preliminary studies effectively demonstrate the feasibility of conducting highly enantioselective hydrogenation reactions in supercritical CO{sub 2}. Importantly, we have shown that higher enantioselectivities may be achieved in supercritical CO{sub 2} relative to conventional solvents. 16 refs., 2 tabs.

  19. Asymmetric hollow nanorod formation through a partial galvanic replacement reaction.

    PubMed

    Seo, Daeha; Song, Hyunjoon

    2009-12-30

    An asymmetric single hollow structure was generated from Ag-Au-Ag heterometal nanorods by a partial galvanic replacement reaction for the first time. The C(2)-symmetry breaking took place because of the random generation of a single pit on only one end of the silver domain at an early stage of the reaction. Careful control of the reaction kinetics could also yield a double-hollow structure on both ends of the silver domain. The resulting single- and double-hollow nanorods exhibited characteristic extinctions in the near-IR range.

  20. Asymmetric Stetter reactions catalyzed by thiamine diphosphate-dependent enzymes.

    PubMed

    Kasparyan, Elena; Richter, Michael; Dresen, Carola; Walter, Lydia S; Fuchs, Georg; Leeper, Finian J; Wacker, Tobias; Andrade, Susana L A; Kolter, Geraldine; Pohl, Martina; Müller, Michael

    2014-12-01

    The intermolecular asymmetric Stetter reaction is an almost unexplored transformation for biocatalysts. Previously reported thiamine diphosphate (ThDP)-dependent PigD from Serratia marcescens is the first enzyme identified to catalyze the Stetter reaction of α,β-unsaturated ketones (Michael acceptor substrates) and α-keto acids. PigD is involved in the biosynthesis of the potent cytotoxic agent prodigiosin. Here, we describe the investigation of two new ThDP-dependent enzymes, SeAAS from Saccharopolyspora erythraea and HapD from Hahella chejuensis. Both show a high degree of homology to the amino acid sequence of PigD (39 and 51 %, respectively). The new enzymes were heterologously overproduced in Escherichia coli, and the yield of soluble protein was enhanced by co-expression of the chaperone genes groEL/ES. SeAAS and HapD catalyze intermolecular Stetter reactions in vitro with high enantioselectivity. The enzymes possess a characteristic substrate range with respect to Michael acceptor substrates. This provides support for a new type of ThDP-dependent enzymatic activity, which is abundant in various species and not restricted to prodigiosin biosynthesis in different strains. Moreover, PigD, SeAAS, and HapD are also able to catalyze asymmetric carbon-carbon bond formation reactions of aldehydes and α-keto acids, resulting in 2-hydroxy ketones.

  1. Direct Catalytic Asymmetric Mannich-Type Reaction of Alkylamides.

    PubMed

    Arteaga, Fernando Arteaga; Liu, Zijian; Brewitz, Lennart; Chen, Jianyang; Sun, Bo; Kumagai, Naoya; Shibasaki, Masakatsu

    2016-05-20

    Direct enolate formation coupled with subsequent enantioselective C-C bond formation remains a topic of intense interest in asymmetric catalysis. This methodology is achieved even with low acidic amides without an electron-withdrawing group at the α-position in the context of a Mannich-type reaction. Acetate-, propionate-, and butyrate-type 7-azaindoline amides served as enolate precursors to afford the desired Mannich adducts with high stereoselectivity, and ligand-enabled diastereo-divergency provided access to both anti/syn diastereomers. The facile transformation of the amide moiety ensures the synthetic utility of the Mannich adducts.

  2. Mass-asymmetric fission in the 40ca+142Nd reaction

    NASA Astrophysics Data System (ADS)

    Prasad, E.; Hinde, D. J.; Williams, E.; Dasgupta, M.; Carter, I. P.; Cook, K. J.; Jeung, D. Y.; Luong, D. H.; McNeil, S.; Palshetkar, C. S.; Rafferty, D. C.; Simenel, C.; Wakhle, A.; Ramachandran, K.; Khuyagbaatar, J.; Dullmann, Ch. E.; Lommel, B.; Kindler, B.

    2016-09-01

    Shell effects play a major role in fission. Mass-asymmetric fission observed in the spontaneous and low energy fission of actinide nuclei was explained by incorporating the fragment shell properties in liquid drop model. Asymmetric fission has also been observed in the low energy fission of neutron-deficient 180Hg nuclei in recent β-delayed fission experiments. This low-energy β-delayed fission has been explained in terms of strong shell effects in pre-scission configurations associated with the system after capture. Calculations predicted asymmetric fission for heavier Hg isotopes as well, at compound nuclear excitation energy as high as 40 MeV. To explore the evolution of fission fragment mass distribution as a function of neutron and proton numbers and also with excitation energy, fission fragment mass distributions have been measured for the 40Ca+142Nd reaction forming the compound nucleus 182Hg at energies around the capture barrier, using the Heavy Ion Accelerator Facility and CUBE spectrometer at the Australian National University. Mass-asymmetric fission is observed in this reaction at an excitation energy of 33.6 MeV. The results are consistent with the β-delayed fission measurements and indicate the presence of shell effects even at higher exciation energies.

  3. Asymmetric catalytic cascade reactions for constructing diverse scaffolds and complex molecules.

    PubMed

    Wang, Yao; Lu, Hong; Xu, Peng-Fei

    2015-07-21

    With the increasing concerns about chemical pollution and sustainability of resources, among the significant challenges facing synthetic chemists are the development and application of elegant and efficient methods that enable the concise synthesis of natural products, drugs, and related compounds in a step-, atom- and redox-economic manner. One of the most effective ways to reach this goal is to implement reaction cascades that allow multiple bond-forming events to occur in a single vessel. This Account documents our progress on the rational design and strategic application of asymmetric catalytic cascade reactions in constructing diverse scaffolds and synthesizing complex chiral molecules. Our research is aimed at developing robust cascade reactions for the systematic synthesis of a range of interesting molecules that contain structural motifs prevalent in natural products, pharmaceuticals, and biological probes. The strategies employed to achieve this goal can be classified into three categories: bifunctional base/Brønsted acid catalysis, covalent aminocatalysis/N-heterocyclic carbene catalysis, and asymmetric organocatalytic relay cascades. By the use of rationally designed substrates with properly reactive sites, chiral oxindole, chroman, tetrahydroquinoline, tetrahydrothiophene, and cyclohexane scaffolds were successfully assembled under bifunctional base/Brønsted acid catalysis from simple and readily available substances such as imines and nitroolefins. We found that some of these reactions are highly efficient since catalyst loadings as low as 1 mol % can promote the multistep sequences affording complex architectures with high stereoselectivities and yields. Furthermore, one of the bifunctional base/Brønsted acid-catalyzed cascade reactions for the synthesis of chiral cyclohexanes has been used as a key step in the construction of the tetracyclic core of lycorine-type alkaloids and the formal synthesis of α-lycorane. Guided by the principles of

  4. Synthesis of new asymmetric substituted boron amidines - reactions with CO and transfer hydrogenations of phenylacetylene.

    PubMed

    Cabrera, Alan R; Rojas, Rene S; Valderrama, Mauricio; Plüss, Pascal; Berke, Heinz; Daniliuc, Constantin G; Kehr, Gerald; Erker, Gerhard

    2015-12-01

    The syntheses of the new asymmetric substituted boron amidines [N'-(2,6-diisopropylphenyl)-N-(pentafluorophenyl)acetimidamide]bis(pentafluorophenyl)borate () and [N'-(2,6-diisopropylphenyl)-N-(4-cyanophenyl)acetimidamide]bis(pentafluorophenyl)borate () were achieved by reaction of one equivalent of HB(C6F5)2 and the respective amidines and . These adducts, bearing electron withdrawing groups, showed thermally induced H2 elimination forming the four-membered cyclic diazaborate derivatives and . These new species were characterized by spectroscopic methods. X-ray diffraction studies have been carried out on , and . To prevent undesired reactions at the nitrile group, one equivalent of B(C6F5)3 was added to yielding the -B(C6F5)3 nitrile adduct . Compound underwent thermally induced dehydrogenation to give the four-membered cyclic diazaborate derivative . CO was inserted into the ring systems of and forming the five-membered diazaborolone derivatives and . Phenylacetylene reacted stoichiometrically with the asymmetric substituted boron amidines , and to give styrene by double H transfer.

  5. Origins of the double asymmetric induction on proline-catalyzed aldol reactions.

    PubMed

    Calderón, Félix; Doyagüez, Elisa G; Cheong, Paul Ha-Yeon; Fernández-Mayoralas, Alfonso; Houk, K N

    2008-10-17

    Computational studies to elucidate the origin of the double asymmetric induction on proline-catalyzed aldol reaction have been performed using HF/6-31G(d) calculations. The computed transition structures explain the experimental data obtained. PMID:18811197

  6. Multidimensional steric parameters in the analysis of asymmetric catalytic reactions

    NASA Astrophysics Data System (ADS)

    Harper, Kaid C.; Bess, Elizabeth N.; Sigman, Matthew S.

    2012-05-01

    Although asymmetric catalysis is universally dependent on spatial interactions to impart specific chirality on a given substrate, examination of steric effects in these catalytic systems remains empirical. Previous efforts by our group and others have seen correlation between steric parameters developed by Charton and simple substituents in both substrate and ligand; however, more complex substituents were not found to be correlative. Here, we review and compare the steric parameters common in quantitative structure activity relationships (QSAR), a common method for pharmaceutical function optimization, and how they might be applied in asymmetric catalysis, as the two fields are undeniably similar. We re-evaluate steric/enantioselection relationships, which we previously analysed with Charton steric parameters, using the more sophisticated Sterimol parameters developed by Verloop and co-workers in a QSAR context. Use of these Sterimol parameters led to strong correlations in numerous processes where Charton parameters had previously failed. Sterimol parameterization also allows for greater mechanistic insight into the key elements of asymmetric induction within these systems.

  7. Studying Reaction Intermediates Formed at Graphenic Surfaces

    NASA Astrophysics Data System (ADS)

    Sarkar, Depanjan; Sen Gupta, Soujit; Narayanan, Rahul; Pradeep, Thalappil

    2014-03-01

    We report in-situ production and detection of intermediates at graphenic surfaces, especially during alcohol oxidation. Alcohol oxidation to acid occurs on graphene oxide-coated paper surface, driven by an electrical potential, in a paper spray mass spectrometry experiment. As paper spray ionization is a fast process and the time scale matches with the reaction time scale, we were able to detect the intermediate, acetal. This is the first observation of acetal formed in surface oxidation. The process is not limited to alcohols and the reaction has been extended to aldehydes, amines, phosphenes, sugars, etc., where reaction products were detected instantaneously. By combining surface reactions with ambient ionization and mass spectrometry, we show that new insights into chemical reactions become feasible. We suggest that several other chemical transformations may be studied this way. This work opens up a new pathway for different industrially and energetically important reactions using different metal catalysts and modified substrate.

  8. Propulsion of a molecular machine by asymmetric distribution of reaction products.

    PubMed

    Golestanian, Ramin; Liverpool, Tanniemola B; Ajdari, Armand

    2005-06-10

    A simple model for the reaction-driven propulsion of a small device is proposed as a model for (part of) a molecular machine in aqueous media. The motion of the device is driven by an asymmetric distribution of reaction products. The propulsive velocity of the device is calculated as well as the scale of the velocity fluctuations. The effects of hydrodynamic flow as well as a number of different scenarios for the kinetics of the reaction are addressed.

  9. Excitation of the dynamical dipole in the charge asymmetric reaction 16O + 116Sn

    NASA Astrophysics Data System (ADS)

    Corsi, A.; Wieland, O.; Kravchuk, V. L.; Bracco, A.; Camera, F.; Benzoni, G.; Blasi, N.; Brambilla, S.; Crespi, F. C. L.; Giussani, A.; Leoni, S.; Million, B.; Montanari, D.; Moroni, A.; Gramegna, F.; Lanchais, A.; Mastinu, P.; Brekiesz, M.; Kmiecik, M.; Maj, A.; Bruno, M.; D'Agostino, M.; Geraci, E.; Vannini, G.; Barlini, S.; Casini, G.; Chiari, M.; Nannini, A.; Ordine, A.; Di Toro, M.; Rizzo, C.; Colonna, M.; Baran, V.

    2009-08-01

    The γ-ray emission from the dynamical dipole formed in heavy-ion collisions during the process leading to fusion was measured for the N/Z asymmetric reaction 16O + 116Sn at beam energies of 8.1 and 15.6 MeV/nucleon. High-energy γ-rays and charged particles were measured in coincidence with the heavy recoiling residual nuclei. The data are compared with those from the N/Z symmetric reaction 64Ni + 68Zn at bombarding energies of 4.7 and 7.8 MeV/nucleon, leading to the same CN with the same excitation energies as calculated from kinematics. The measured yield of the high-energy γ-rays from the 16O-induced reaction is found to exceed that of the thermalized CN and the excess yield increases with bombarding energy. The data are in rather good agreement with the predictions for the dynamical dipole emission based on the Boltzmann-Nordheim-Vlasov model. In addition, a comparison with existing data in the same mass region is performed to extract information on the dipole moment dependence.

  10. Isospin effects on fragmentation in the asymmetric reactions induced by neutron-rich targets

    NASA Astrophysics Data System (ADS)

    Sharma, Arun

    2016-05-01

    To understand the isospin effects in terms of fragment's yield in the asymmetric reactions induced by neutron-rich targets, we perform a theoretical study using isospin-dependent quantum molecular dynamics (IQMD) model. Simulations are carried out for reactions of 16O+Br80,84,92 and 16O+Ag108,113,122. We envision that fragments's yield in the asymmetric collisions induced by neutron-rich targets is better candidate to study isospin effects via symmetry energy and nucleon-nucleon (nn) cross-sections. Also, pronounced effects of symmetry energy and cross-sections can be found at lower and higher beam energies, respectively.

  11. Asymmetrical quartz crystallographic fabrics formed during constrictional deformation

    NASA Astrophysics Data System (ADS)

    Sullivan, W. A.; Beane, R. J.

    2010-10-01

    Numerical simulations predict unique quartz crystallographic fabric patterns for plane strain, flattening, and constriction. Multiple studies support the predictions for plane strain and flattening. To test predictions for constriction, this paper analyzes five examples of quartz crystallographic fabrics from a 1-km-wide domain of L tectonites in the Pigeon Point high-strain zone, Klamath Mountains, California, U.S.A. These samples were deformed under greenschist- to amphibolite-facies conditions. Quartz c-axis fabrics are similar to the predicted double-girdle fabrics except that amphibolite-facies samples exhibit c-axis maxima and are distinctly asymmetrical about the elongation lineations. Activation of different slip systems combined with small deviations from pure constriction account for the c-axis maxima, and noncoaxial flow accounts for the fabric asymmetry. The simple-shear component is randomly oriented in geographic coordinates throughout the domain of L tectonites. These data confirm that numerical simulations predict the quartz c-axis fabric geometry developed during constriction for some deformation conditions, and they confirm the quartz a-axis patterns predicted for constriction for the first time. These data also demonstrate that the relationship between quartz crystallographic fabrics and strain geometry is not straightforward, and they indicate that a-axis fabrics may be more useful indicators of strain geometry variations.

  12. Development of catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium complexes.

    PubMed

    Tsubogo, Tetsu; Saito, Susumu; Seki, Kazutaka; Yamashita, Yasuhiro; Kobayashi, Shu

    2008-10-01

    Catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium species prepared from calcium isopropoxide and chiral bisoxazoline ligands have been developed. Glycine Schiff bases reacted with acrylic esters to afford 1,4-addition products, glutamic acid derivatives, in high yields with high enantioselectivities. During the investigation of the 1,4-addition reactions, we unexpectedly found that a [3 + 2] cycloaddition occurred in the reactions with crotonate derivatives, affording substituted pyrrolidine derivatives in high yields with high enantioselectivities. On the basis of this finding, we investigated asymmetric [3 + 2] cycloadditions, and it was revealed that several kinds of optically active substituted pyrrolidine derivatives containing contiguous stereogenic tertiary and quaternary carbon centers were obtained with high diastereo- and enantioselectivities. In addition, optically active pyrrolidine cores of hepatitis C virus RNA-dependent polymerase inhibitors and potential effective antiviral agents have been synthesized using this [3 + 2] cycloaddition reaction. NMR spectroscopic analysis and observation of nonamplification of enantioselectivity in nonlinear effect experiments suggested that a monomeric calcium species with an anionic ligand was formed as an active catalyst. A stepwise mechanism of the [3 + 2] cycloaddition, consisting of 1,4-addition and successive intramolecular Mannich-type reaction was suggested. Furthermore, modification of the Schiff base structure resulted in a modification of the reaction course from a [3 + 2] cycloaddition to a 1,4-addition, affording 3-substituted glutamic acid derivatives with high diasterero- and enantioselectivities.

  13. Development of catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium complexes.

    PubMed

    Tsubogo, Tetsu; Saito, Susumu; Seki, Kazutaka; Yamashita, Yasuhiro; Kobayashi, Shu

    2008-10-01

    Catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium species prepared from calcium isopropoxide and chiral bisoxazoline ligands have been developed. Glycine Schiff bases reacted with acrylic esters to afford 1,4-addition products, glutamic acid derivatives, in high yields with high enantioselectivities. During the investigation of the 1,4-addition reactions, we unexpectedly found that a [3 + 2] cycloaddition occurred in the reactions with crotonate derivatives, affording substituted pyrrolidine derivatives in high yields with high enantioselectivities. On the basis of this finding, we investigated asymmetric [3 + 2] cycloadditions, and it was revealed that several kinds of optically active substituted pyrrolidine derivatives containing contiguous stereogenic tertiary and quaternary carbon centers were obtained with high diastereo- and enantioselectivities. In addition, optically active pyrrolidine cores of hepatitis C virus RNA-dependent polymerase inhibitors and potential effective antiviral agents have been synthesized using this [3 + 2] cycloaddition reaction. NMR spectroscopic analysis and observation of nonamplification of enantioselectivity in nonlinear effect experiments suggested that a monomeric calcium species with an anionic ligand was formed as an active catalyst. A stepwise mechanism of the [3 + 2] cycloaddition, consisting of 1,4-addition and successive intramolecular Mannich-type reaction was suggested. Furthermore, modification of the Schiff base structure resulted in a modification of the reaction course from a [3 + 2] cycloaddition to a 1,4-addition, affording 3-substituted glutamic acid derivatives with high diasterero- and enantioselectivities. PMID:18783222

  14. Asymmetric Michael addition reactions of nitroalkanes to 2-furanones catalyzed by bifunctional thiourea catalysts.

    PubMed

    Bai, Zhushuang; Ji, Ling; Ge, Zemei; Wang, Xin; Li, Runtao

    2015-05-21

    The first bifunctional thiourea catalyzed asymmetric Michael addition reactions of nitroalkanes to 2-furanones are described. The highly functionalized γ-lactones with two or three consecutive stereogenic carbons were obtained in high yields (up to 99%), high diastereoselectivities (up to >20 : 1 dr) and enantioselectivities (up to >99% ee).

  15. Measurements of Dynamical Dipole in isospin asymmetric fusion reactions

    NASA Astrophysics Data System (ADS)

    Giaz, A.; Corsi, A.; Camera, F.; Bracco, A.; Crespi, F. C. L.; Leoni, S.; Nicolini, R.; Vandone, V.; Benzoni, G.; Blasi, N.; Brambilla, S.; Million, B.; Wieland, O.; Cinausero, M.; Degelier, M.; Gramegna, F.; Kravchuk, V. L.; Marchi, T.; Rizzi, V.; Bardelli, L.; Barlini, S.; Bini, M.; Carboni, S.; Casini, G.; Chiari, M.; Nannini, A.; Pasquali, G.; Piantelli, S.; Poggi, G.; Baiocco, G.; Bruno, M.; D'agostino, M.; Morelli, L.; Vannini, V.; Colonna, M.; Di Toro, M.; Rizzo, C.; Bednarcyk, P.; Ciemala, M.; Kmiecik, M.; Maj, A.; Mazurek, K.; Menczynski, W.; Alba, R.; Maiolino, C.; Santonocito, D.; Montanari, D.; Ordine, A.

    2012-05-01

    In heavy ion nuclear reactions the process leading to complete fusion is expected to produce pre-equilibrium γ-ray emission, if particular conditions are met. Indeed, when there is an N/Z asymmetry between projectile and target, charge equilibration takes place with a collective dipole oscillation, called Dynamical Dipole (DD), associated to a γ-ray emission. The existing experimental data concerning this pre-equilibrium γ-ray emission are still rather scarce and manly concentrated in the A≊132 mass region. The very preliminary results concerning the measurement of the DD γ-ray emission in the fusion reaction 16O (Elab=192 MeV) + 116Sn at 12 MeV/u will be presented and compared with the γ yield measured for the same reaction at 8.1 and 15.6 MeV/u. The present experiment aims at the measurement of the total emission yield of the DD at 12 MeV/u where the predicted theoretical yield does not completely reproduce the experimental data. The experiment has been performed at the INFN Legnaro Laboratories using the GARFIELD-HECTOR array.

  16. Synthesis of trifluoromethyl-containing vicinal diamines by asymmetric decarboxylative mannich addition reactions.

    PubMed

    Wu, Lingmin; Xie, Chen; Mei, Haibo; Dai, Yanling; Han, Jianlin; Soloshonok, Vadim A; Pan, Yi

    2015-03-20

    Herein is reported a study of asymmetric decarboxylative Mannich addition reactions between (Ss)-N-t-butylsulfinyl-3,3,3-trifluoroacetaldimine and Schiff bases derived from various aldehydes and lithium 2,2-diphenylglycinate. These reactions proceed with excellent diastereoselectivities and good chemical yields, providing a practical method for preparation of trifluoromethyl-containing vicinal diamines. The procedures can be conducted under convenient conditions, rendering this approach of high synthetic value.

  17. Asymmetrical ClO3 - Its possible formation from ClO and O2 and its possible reactions

    NASA Technical Reports Server (NTRS)

    Prasad, S. S.; Adams, W. M.

    1980-01-01

    An analysis of recent accurate experimental studies of Cl2-photosensitized O3 decomposition, in which O3 disappearance and OClO formation were directly monitored, suggests the possibility that the suppression of the quantum yield in the presence of O2 may be due to the formation of asymmetrical chlorine trioxide (ClO.O2). Other intermediaries, such as Cl2O2, which may also form in the system are not thought to explain the observations. In addition to its capacity to oxidize, which it shares with other peroxo compounds, asymmetrical ClO3 appears to undergo an interesting class of reactions in which the loosely bound O2 adduct is relatively easily displaced by reactive atoms and radicals such as chlorine.

  18. A One-Pot Tandem Strategy in Catalytic Asymmetric Vinylogous Aldol Reaction of Homoallylic Alcohols.

    PubMed

    Hou, Xufeng; Jing, Zhenzhong; Bai, Xiangbin; Jiang, Zhiyong

    2016-01-01

    Reported is a rationally-designed one-pot sequential strategy that allows homoallylic alcohols to be employed in a catalytic, asymmetric, direct vinylogous aldol reaction with a series of activated acyclic ketones, including trifluoromethyl ketones, γ-ketoesters, and α-keto phosphonates, in high yields (up to 95%) with excellent regio- and enantio-selectivity (up to 99% ee). This modular combination, including Jones oxidation and asymmetric organocatalysis, has satisfactory compatibility and reliability even at a 20 mmol scale, albeit without intermediary purification. PMID:27355935

  19. Asymmetric anti-selective Michael reaction of imidazole-modified ketones with trans-β-nitroalkenes.

    PubMed

    Yang, Dongxu; Wang, Linqing; Li, Dan; Han, Fengxia; Zhao, Depeng; Wang, Rui

    2015-01-19

    The successful application of imidazole-modified ketones in asymmetric anti-selective Michael reactions with trans-β-nitroalkenes is presented by employing a newly developed 3-bromothiophene-modified chiral diamine ligand. The corresponding conjugate adduct was submitted to further transformations with Grignard reagents to solve the problem of α-site selectivity of simple linear ketones. Additionally, the syn-selective product was obtained by treating the anti-selective adduct with a simple base. In this way, the site-specific products for both diastereomers in the asymmetric conjugate addition of simple ketones to nitroalkenes can be obtained. PMID:25446668

  20. Asymmetric synthesis of tetrahydroisoquinolines by enzymatic Pictet-Spengler reaction.

    PubMed

    Nishihachijo, Masakatsu; Hirai, Yoshinori; Kawano, Shigeru; Nishiyama, Akira; Minami, Hiromichi; Katayama, Takane; Yasohara, Yoshihiko; Sato, Fumihiko; Kumagai, Hidehiko

    2014-01-01

    Norcoclaurine synthase (NCS) catalyzes the stereoselective Pictet-Spengler reaction between dopamine and 4-hydroxyphenylacetaldehyde as the first step of benzylisoquinoline alkaloid synthesis in plants. Recent studies suggested that NCS shows relatively relaxed substrate specificity toward aldehydes, and thus, the enzyme can serve as a tool to synthesize unnatural, optically active tetrahydroisoquinolines. In this study, using an N-terminally truncated NCS from Coptis japonica expressed in Escherichia coli, we examined the aldehyde substrate specificity of the enzyme. Herein, we demonstrate the versatility of the enzyme by synthesizing 6,7-dihydroxy-1-phenethyl-1,2,3,4-tetrahydroisoquinoline and 6,7-dihydroxy-1-propyl-1,2,3,4-tetrahydroisoquinoline in molar yields of 86.0 and 99.6% and in enantiomer excess of 95.3 and 98.0%, respectively. The results revealed the enzyme is a promising catalyst that functions to stereoselectively produce various 1-substituted-1,2,3,4-tetrahydroisoquinolines. PMID:25036970

  1. Catalytic asymmetric direct-type 1,4-addition reactions of simple amides.

    PubMed

    Suzuki, Hirotsugu; Sato, Io; Yamashita, Yasuhiro; Kobayashi, Shū

    2015-04-01

    The development of catalytic asymmetric direct-type reactions of less acidic carbonyl compounds such as amides and esters has been a challenging theme in organic chemistry for decades. Here we describe the asymmetric direct 1,4-addition reactions of simple amides with α,β-unsaturated carbonyl compounds using a catalytic amount of a novel chiral catalyst consisting of a potassium base and a macrocyclic chiral crown ether. The desired 1,5-dicarbonyl compounds were obtained in high yields with excellent diastereo- and enantioselectivities. This is the first example of a highly enantioselective catalytic direct-type reaction of simple amides. In addition, the structure of the chiral potassium catalyst has been investigated by X-ray crystallographic, dynamic (1)H NMR, and MALDI-TOF MS analyses.

  2. Molybdenum-Catalyzed Asymmetric Allylic Alkylation of 3-Alkyloxindoles: Reaction Development and Applications

    PubMed Central

    Trost, Barry M.; Zhang, Yong

    2013-01-01

    We report a full account of our work towards the development of Mo-catalyzed asymmetric allylic alkylation reactions with 3-alkyloxindoles as nucleophiles. The reaction is complementary to the Pd-catalyzed reaction with regard to the scope of oxindole nucleophiles. A number of 3-alkyloxindoles were alkylated successfully under mild conditions to give products with excellent yields and good-to-excellent enantioselectivities. Applications of this method to the preparation of indoline alkaloids such as (−)-physostigmine, ent-(−)-debromoflustramine B, and the indolinoquinoline rings of communesin B are reported. PMID:21290436

  3. Binaphthyl-based chiral bifunctional organocatalysts for water mediated asymmetric List-Lerner-Barbas aldol reactions.

    PubMed

    Ashokkumar, Veeramanoharan; Chithiraikumar, Chinnadurai; Siva, Ayyanar

    2016-10-14

    Novel binaphthyl-based chiral bifunctional organocatalysts were designed, synthesized and successfully applied to the asymmetric List-Lerner-Barbas aldol reaction in the presence of water. These organocatalysts were found to be effective catalysts for the reactions of symmetrical, unsymmetrical and cyclic ketones with different aldehydes to give the corresponding aldol products with higher yields (up to 98%) and very good ee's up to 99%. The catalytic system leads to higher yields and selectivities than the previously reported well-known proline based organocatalysts. In addition to the effect of solvent, additives, catalyst concentration, temperature and the substrate scope of the reactions were also investigated. PMID:27604169

  4. Asymmetric Electrophilic α-Amination of Silyl Enol Ether Derivatives via the Nitrosocarbonyl Hetero-ene Reaction.

    PubMed

    Sandoval, David; Samoshin, Andrey V; Read de Alaniz, Javier

    2015-09-18

    The first example of a general asymmetric nitrosocarbonyl hetero-ene reaction is described. The procedure uses a copper-catalyzed aerobic oxidation of a commercially available chiral nitrosocarbonyl precursor (EleNOr) and is operationally simple. The transformation is both high yielding and highly diastereoselective for a range of silyl enol ether derivatives. A variety of synthetically useful postfunctionalization reactions are presented along with a mechanistic rationale that can be used as a predictive model for future asymmetric reactions with nitrosocarbonyl intermediates.

  5. Total Synthesis of Anti-Influenza Agents Zanamivir and Zanaphosphor via Asymmetric Aza-Henry Reaction.

    PubMed

    Lin, Long-Zhi; Fang, Jim-Min

    2016-09-01

    The potent anti-influenza agents, zanamivir and its phosphonate congener, are synthesized by using a nitro group as the latent amino group at C4 for asymmetric aza-Henry reaction with a chiral sulfinylimine, which is derived from inexpensive d-glucono-δ-lactone to establish the essential nitrogen-containing substituent at C5. This method provides an efficient way to construct the densely substituted dihydropyran core of zanamivir and zanaphosphor without using the hazardous azide reagent. PMID:27541804

  6. anti-Selective Asymmetric Henry Reaction Catalyzed by a Heterobimetallic Cu-Sm-Aminophenol Sulfonamide Complex.

    PubMed

    Li, Yang; Deng, Ping; Zeng, Youmao; Xiong, Yan; Zhou, Hui

    2016-04-01

    A novel heterobimetallic Cu/Sm/aminophenol sulfonamide complex has been developed by a convenient one-pot method for the anti-selective asymmetric Henry reaction. The corresponding anti-β-nitro alcohols are obtained in up to 99% yield, >30:1 dr, and 98% ee. The results of control experiments and ESI-MS analysis of the complex indicate that the monomeric bimetallic Cu/Sm/1 complex would be the active species.

  7. Direct visualization of a cycloaddition reaction on frozen asymmetric Si dimers at room temperature

    NASA Astrophysics Data System (ADS)

    Baik, Jaeyoon; Ihm, Kyuwook; Ha, Taekyun; An, Ki-Seok; Ahn, Joung Real; Park, Chong-Yun

    2016-07-01

    We firstly report an experimental visualization of a cycloaddition reaction on RT frozen asymmetric Si dimers. The frozen Si dimers with a local c(4 × 2) order were prepared by pinning flip-flopping Si dimers by using molecules. This RT pristine c(4 × 2) structure was used to determine what Si atom of an asymmetric Si dimer bonds to a molecule at the initial stage of the RT cycloaddition reaction, which has been a long-standing puzzling issue. This made it possible to compare directly experimental cycloaddition reactions with theoretical ones. As a prototype for the experiment, a 1,3-butadiene molecule adsorbed between Si dimer rows was used. The 1,3-butadiene molecule was found to prefer a symmetric Si pair on the frozen Si dimers, i.e., two electrophilic lower atoms of asymmetric Si dimers. This result is consistent with the theoretical prediction that a 1,3-diene molecule prefers a symmetric Si pair on the Si(001)c(4 × 2) surface. This experimental approach can also be applied to other studies for the adsorption of a molecule on a Si(001) surface at room temperature.

  8. Biodiesel forming reactions using heterogeneous catalysis

    NASA Astrophysics Data System (ADS)

    Liu, Yijun

    Biodiesel synthesis from biomass provides a means for utilizing effectively renewable resources, a way to convert waste vegetable oils and animal fats to a useful product, a way to recycle carbon dioxide for a combustion fuel, and production of a fuel that is biodegradable, non-toxic, and has a lower emission profile than petroleum-diesel. Free fatty acid (FFA) esterification and triglyceride (TG) transesterification with low molecular weight alcohols constitute the synthetic routes to prepare biodiesel from lipid feedstocks. This project was aimed at developing a better understanding of important fundamental issues involved in heterogeneous catalyzed biodiesel forming reactions using mainly model compounds, representing part of on-going efforts to build up a rational base for assay, design, and performance optimization of solid acids/bases in biodiesel synthesis. As FFA esterification proceeds, water is continuously formed as a byproduct and affects reaction rates in a negative manner. Using sulfuric acid (as a catalyst) and acetic acid (as a model compound for FFA), the impact of increasing concentrations of water on acid catalysis was investigated. The order of the water effect on reaction rate was determined to be -0.83. Sulfuric acid lost up to 90% activity as the amount of water present increased. The nature of the negative effect of water on esterification was found to go beyond the scope of reverse hydrolysis and was associated with the diminished acid strength of sulfuric acid as a result of the preferential solvation by water molecules of its catalytic protons. The results indicate that as esterification progresses and byproduct water is produced, deactivation of a Bronsted acid catalyst like H2SO4 occurs. Using a solid composite acid (SAC-13) as an example of heterogeneous catalysts and sulfuric acid as a homogeneous reference, similar reaction inhibition by water was demonstrated for homogeneous and heterogeneous catalysis. This similarity together with

  9. Mechanistic insights into a BINOL-derived phosphoric acid-catalyzed asymmetric Pictet-Spengler reaction.

    PubMed

    Overvoorde, Lois M; Grayson, Matthew N; Luo, Yi; Goodman, Jonathan M

    2015-03-01

    The reaction of tryptamine and (2-oxocyclohexyl)acetic acid can be catalyzed by 3,3'-bis(triphenylsilyl)-1,1'-bi-2-naphthol phosphoric acid to give an asymmetric β-carboline. This reaction was first studied by Holloway et al. ( Org. Lett. 2010 , 12 , 4720 - 4723 ), but their mechanistic work did not explain the high stereoselectivity achieved. This study uses density functional theory and hybrid quantum mechanics/molecular mechanics calculations to investigate this reaction and provide a model to explain its outcome. The step leading to diastereo- and enantioselectivity is an asymmetric Pictet-Spengler reaction involving an N-acyliminium ion bound to the catalyst in a bidentate fashion. This interaction occurs via hydrogen bonds between the two terminal oxygen atoms of the catalyst phosphate group and the hydrogen atoms at N and C2 of the substrate indole group. These bonds hold the transition structure rigidly and thus allow the catalyst triphenylsilyl groups to influence the enantioselectivity. PMID:25654215

  10. Generalized closed-form model for analysis of asymmetric shaped charges

    NASA Astrophysics Data System (ADS)

    Mahdian, A.; Liaghat, G. H.; Ghayour, M.

    2013-03-01

    This paper presents a model that has less constraints than similar models and explains the collapse phenomenon in any desired order of geometrical asymmetries and in the presence of symmetric and asymmetric general-form wave fronts. It seems that, in this model, a complete generalized form of the classical jet formation theory has been developed. Available models that describe the symmetric jet and slug formation phenomenon are very good in such conditions. But the liner and confinement asymmetries, detonation wave front asymmetries, and other specifications, such as manufacturing tolerances, can affect the collapse and the behavior of the jet and slug. Some proposed models that describe asymmetric cases are not closed-form models or are only applicable for limited conditions, such as small asymmetries and a planar wave front. With the presented model, effects of concave, plane, and convex wave fronts on the off-axis velocity of the jet, other parameters of the jet and slug, and effects of an asymmetric wave front on jet formation for a completely symmetric liner and confinement geometry can be evaluated.

  11. Asymmetric Cooperative Catalysis in a Three-Component Reaction: Mechanism and Origin of Enantio- and Diastereoselectivities.

    PubMed

    Kisan, Hemanta K; Sunoj, Raghavan B

    2016-08-01

    Mechanistic insights gained through density functional theory (DFT M06 and B3LYP) computations on a three-component cooperative asymmetric catalytic reaction between a diazo ester, a carbamate, and an imine, catalyzed by dirhodium acetate and chiral phosphoric acid (Brønsted acid), are presented. The addition of the dirhodium-bound enol to the imine yielding an α,β-diamino ester is energetically more preferred over a potentially competitive protonation of the same enol leading to an α-amino ester. PMID:27447290

  12. Assembling long heteroduplexes by asymmetric polymerase chain reaction and annealing the resulting single-stranded DNAs.

    PubMed

    Wang, Mugui; Wei, Chuchu; Ye, Xiufen; Liu, Jianping; Zhang, Cuicui; Chen, Hao; Zhang, Xiaobo; Tu, Jumin

    2015-04-15

    We developed an effective protocol for generating high-purity heteroduplexes via annealing single-stranded DNAs (ssDNAs) derived from plasmid DNA by asymmetric polymerase chain reaction (A-PCR). With the addition of dimethyl sulfoxide, a one-step A-PCR procedure can generate ssDNAs stably at a range of reaction temperatures. Several annealing buffers can anneal two ssDNAs into heteroduplexes effectively. We further developed a simple strategy to create d(GATC) hemimethylated heteroduplexes by annealing fully methylated homoduplexes in the presence of excessive unmethylated ssDNAs. The constructed heteroduplexes have been well tested as substrates for mismatch repair in Escherichia coli and, thus, can be used in various biotechnology applications. PMID:25575760

  13. tert-Butanesulfinamides as Nitrogen Nucleophiles in Carbon-Nitrogen Bond Forming Reactions.

    PubMed

    Ramirez Hernandez, Johana; Chemla, Fabrice; Ferreira, Franck; Jackowski, Olivier; Oble, Julie; Perez-Luna, Alejandro; Poli, Giovanni

    2016-01-01

    The use of tert-butanesulfinamides as nitrogen nucleophiles in carbon-nitrogen bond forming reactions is reviewed. This field has grown in the shadow of the general interest in N-tert-butanesulfinyl imines for asymmetric synthesis and occupies now an important place in its own right in the chemistry of the chiral amine reagent tert-butanesulfinamide. This article provides an overview of the area and emphasizes recent contributions wherein the tert-butanesulfinamides act as chiral auxiliaries or perform as nitrogen donors in metal-catalyzed amination reactions. PMID:26931222

  14. Rich Phase Behavior of Sphere-Forming Asymmetric ABA'C Block Copolymer Melts

    NASA Astrophysics Data System (ADS)

    Chanpuriya, Sid; Arora, Akash; Kim, Kyungtae; Dorfman, Kevin; Bates, Frank

    Motivated by self-consistent field theory simulations, the effect of ABA' corona block length asymmetry on the phase behavior of ABA'C-type tetrablock terpolymers has been examined. The chosen model system, poly(styrene)- b-poly(isoprene)- b-poly(styrene)- b-poly(ethylene oxide) (SIS'O), has been characterized using a combination of small-angle X-ray scattering, transmission electron microscopy, and dynamic mechanical spectroscopy. Asymmetric SIS'O tetrablocks reveal a rich variety of sphere-forming phases over compositions and molecular weights where symmetric SISO polymers formed only hexagonally oriented cylinders. These include FCC, HCP, and complex symmetries such as the Frank-Kasper σ and A15 phases. NSF Award 1333669.

  15. On stabilization of scattering resonances in recombination reaction that forms ozone

    NASA Astrophysics Data System (ADS)

    Ivanov, Mikhail V.; Babikov, Dmitri

    2016-04-01

    Calculations of energy transfer in the recombination reaction that forms ozone are carried out within the framework of the mixed quantum/classical theory and using the dimensionally reduced 2D-model of ozone molecule, with bending motion neglected. Recombination rate coefficients are obtained at room temperature for symmetric and asymmetric isotopomers of singly and doubly substituted isotopologues. The processes of resonance formation, spontaneous decay, collisional dissociation, and stabilization by bath gas (Ar) are all characterized and taken into account within the steady-state approximation for kinetics. The focus is on stabilization step, where the mysterious isotopic η-effect was thought to originate from. Our results indicate no difference in cross sections for stabilization of scattering resonances in symmetric and asymmetric isotopomers. As practical results, the general and simple analytic models for stabilization and dissociation cross sections are presented, which can be applied to resonances in any ozone molecule, symmetric or asymmetric, singly or doubly substituted. Present calculations show some isotope effect that looks similar to the experimentally observed η-effect, and the origin of this phenomenon is in the rates of formation/decay of scattering resonances, determined by their widths, that are somewhat larger in asymmetric isotopomers than in their symmetric analogues. However, the approximate two-dimensional model used here is insufficient for consistent and reliable description of all features of the isotopic effect in ozone. Calculations using an accurate 3D model are still needed.

  16. On stabilization of scattering resonances in recombination reaction that forms ozone.

    PubMed

    Ivanov, Mikhail V; Babikov, Dmitri

    2016-04-21

    Calculations of energy transfer in the recombination reaction that forms ozone are carried out within the framework of the mixed quantum/classical theory and using the dimensionally reduced 2D-model of ozone molecule, with bending motion neglected. Recombination rate coefficients are obtained at room temperature for symmetric and asymmetric isotopomers of singly and doubly substituted isotopologues. The processes of resonance formation, spontaneous decay, collisional dissociation, and stabilization by bath gas (Ar) are all characterized and taken into account within the steady-state approximation for kinetics. The focus is on stabilization step, where the mysterious isotopic η-effect was thought to originate from. Our results indicate no difference in cross sections for stabilization of scatteringresonances in symmetric and asymmetric isotopomers. As practical results, the general and simple analytic models for stabilization and dissociation cross sections are presented, which can be applied to resonances in any ozone molecule, symmetric or asymmetric, singly or doubly substituted. Present calculations show some isotope effect that looks similar to the experimentally observed η-effect, and the origin of this phenomenon is in the rates of formation/decay of scatteringresonances, determined by their widths, that are somewhat larger in asymmetric isotopomers than in their symmetric analogues. However, the approximate two-dimensional model used here is insufficient for consistent and reliable description of all features of the isotopic effect in ozone. Calculations using an accurate 3D model are still needed.

  17. On stabilization of scattering resonances in recombination reaction that forms ozone.

    PubMed

    Ivanov, Mikhail V; Babikov, Dmitri

    2016-04-21

    Calculations of energy transfer in the recombination reaction that forms ozone are carried out within the framework of the mixed quantum/classical theory and using the dimensionally reduced 2D-model of ozone molecule, with bending motion neglected. Recombination rate coefficients are obtained at room temperature for symmetric and asymmetric isotopomers of singly and doubly substituted isotopologues. The processes of resonance formation, spontaneous decay, collisional dissociation, and stabilization by bath gas (Ar) are all characterized and taken into account within the steady-state approximation for kinetics. The focus is on stabilization step, where the mysterious isotopic η-effect was thought to originate from. Our results indicate no difference in cross sections for stabilization of scatteringresonances in symmetric and asymmetric isotopomers. As practical results, the general and simple analytic models for stabilization and dissociation cross sections are presented, which can be applied to resonances in any ozone molecule, symmetric or asymmetric, singly or doubly substituted. Present calculations show some isotope effect that looks similar to the experimentally observed η-effect, and the origin of this phenomenon is in the rates of formation/decay of scatteringresonances, determined by their widths, that are somewhat larger in asymmetric isotopomers than in their symmetric analogues. However, the approximate two-dimensional model used here is insufficient for consistent and reliable description of all features of the isotopic effect in ozone. Calculations using an accurate 3D model are still needed. PMID:27389214

  18. New directing groups for metal-catalyzed asymmetric carbon-carbon bond-forming processes: stereoconvergent alkyl-alkyl Suzuki cross-couplings of unactivated electrophiles.

    PubMed

    Wilsily, Ashraf; Tramutola, Francesco; Owston, Nathan A; Fu, Gregory C

    2012-04-01

    The ability of two common protected forms of amines (carbamates and sulfonamides) to serve as directing groups in Ni-catalyzed Suzuki reactions has been exploited in the development of catalytic asymmetric methods for cross-coupling unactivated alkyl electrophiles. Racemic secondary bromides and chlorides undergo C-C bond formation in a stereoconvergent process in good ee at room temperature in the presence of a commercially available Ni complex and chiral ligand. Structure-enantioselectivity studies designed to elucidate the site of binding to Ni (the oxygen of the carbamate and of the sulfonamide) led to the discovery that sulfones also serve as useful directing groups for asymmetric Suzuki cross-couplings of racemic alkyl halides. To our knowledge, this investigation provides the first examples of the use of sulfonamides or sulfones as effective directing groups in metal-catalyzed asymmetric C-C bond-forming reactions. A mechanistic study established that transmetalation occurs with retention of stereochemistry and that the resulting Ni-C bond does not undergo homolysis in subsequent stages of the catalytic cycle.

  19. Non-cross-linked polystyrene-supported 2-imidazolidinone chiral auxiliary: synthesis and application in asymmetric alkylation reactions

    PubMed Central

    Nguyen, Quynh Pham Bao

    2013-01-01

    Summary Asymmetric alkylation reactions using non-cross-linked polystyrene (NCPS)-supported 2-imidazolidinone chiral auxiliaries were successfully investigated with excellent diastereocontrol (>99% de). The recovery and the recycling of this soluble polymer-supported chiral auxiliary were achieved in order to produce highly optical pure carboxylic acids. PMID:24204423

  20. Metal-ligand binding affinity vs reactivity: qualitative studies in Rh(I)-catalyzed asymmetric ring-opening reactions.

    PubMed

    Tsui, Gavin Chit; Dougan, Patrick; Lautens, Mark

    2013-06-01

    Rh(I)-catalyzed asymmetric ring opening (ARO) of oxabenzonorbornadiene is used as a model system to qualitatively study reactions involving multiple metal-ligand interactions. The key feature of this approach is the use of product ee as an indicator to quickly gain important information such as the relative ligand binding affinity and relative reactivity of catalysts.

  1. From a Sequential to a Concurrent Reaction in Aqueous Medium: Ruthenium-Catalyzed Allylic Alcohol Isomerization and Asymmetric Bioreduction.

    PubMed

    Ríos-Lombardía, Nicolás; Vidal, Cristian; Liardo, Elisa; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier

    2016-07-18

    The ruthenium-catalyzed redox isomerization of allylic alcohols was successfully coupled with the enantioselective enzymatic ketone reduction (mediated by KREDs) in a concurrent process in aqueous medium. The overall transformation, formally the asymmetric reduction of allylic alcohols, took place with excellent conversions and enantioselectivities, under mild reaction conditions, employing commercially and readily available catalytic systems, and without external coenzymes or cofactors. Optimization resulted in a multistep approach and a genuine cascade reaction where the metal catalyst and biocatalyst coexist from the beginning.

  2. Design of chiral urea-quaternary ammonium salt hybrid catalysts for asymmetric reactions of glycine Schiff bases†

    PubMed Central

    Tiffner, Maximilian; Novacek, Johanna; Busillo, Alfonso; Gratzer, Katharina; Massa, Antonio; Waser, Mario

    2015-01-01

    Bifunctional chiral urea-containing quaternary ammonium salts can be straightforwardly synthesised in good yield and with high structural diversity via a scalable and operationally simple highly telescoped sequence starting from trans-1,2-cyclohexanediamine. These novel hybrid catalysts were systematically investigated for their potential to control glycine Schiff bases in asymmetric addition reactions. It was found that Michael addition reactions and the herein presented aldol-initiated cascade reaction can be carried out to provide enantiomeric ratios up to 95 : 5 and good yields under mild conditions at room temperature. PMID:26504516

  3. High-throughput methods for the development of new catalytic asymmetric reactions.

    PubMed

    Traverse, John F; Snapper, Marc L

    2002-10-01

    Chiral, single enantiomer pharmaceuticals have become increasingly more important. Therefore, research aimed at providing new methods for their selective preparation has taken on an even greater importance. One of the most efficient strategies for the synthesis of non-racemic, chiral molecules is asymmetric catalysis. There are many variables involved in the discovery of a new catalytic asymmetric transformation; hence, methods for the rapid screening of large numbers of catalysts have been developed. Herein, these techniques and strategies for the rapid discovery of novel asymmetric catalysts are reviewed.

  4. Synthesis of novel Schiff base ligands from gluco- and galactochloraloses for the Cu(II) catalyzed asymmetric Henry reaction.

    PubMed

    Alkan, Sevda; Telli, Fatma Ç; Salman, Yeşim; Astley, Stephen T

    2015-04-30

    A series of chiral Schiff base ligands has been prepared using aminochloralose derivatives of glucose and galactose. These ligands were used as catalysts in the asymmetric Henry reaction in the presence of Cu(II) ions giving yields of up to 95%. An interesting solvent dependency on enantiomeric control was observed with the best enantiomeric excesses (up to 91%) being obtained in the presence of water. PMID:25742867

  5. Noncovalent immobilization of ionic-tagged box-Cu(OAc)2 complex and its application in asymmetric Henry reaction.

    PubMed

    Li, Zhi-Huai; Zhou, Zhi-Ming; Hao, Xiao-Yan; Zhang, Jun; Dong, Xiao; Liu, Ying-Qiang

    2012-12-01

    Immobilized Cu(OAc)(2)-bis(oxazolines) via hydrogen bonding by SBA-15 was applied to asymmetric Henry reaction, and good enantioselectivities were obtained (up to 83% ee) between 2-methoxybenzaldehyde and CH(3)NO(2) in isopropyl alcohol (iPrOH). The catalyst could be reused seven times without any obvious loss in enantioselectivity. For the first time, this facile and clean immobilization method is applied to the use of bis(oxazolines) complexes. PMID:23001750

  6. Preparation of Poly(ionic liquid)s-Supported Recyclable Organocatalysts for the Asymmetric Nitroaldol (Henry) Reaction.

    PubMed

    Großeheilmann, Julia; Bandomir, Jenny; Kragl, Udo

    2015-12-21

    A novel strategy for the embedding of quinine-based organocatalysts in polymerized ionic liquids-based hydrogels is presented. With this technique, the encapsulated organocatalyst was successfully recovered and reused for four cycles without any loss of enantioselectivity (up to 91% ee) for the asymmetric nitroaldol (Henry) reaction. In this study, high catalyst leaching was significantly reduced (<0.01%) by controlling the water content. After catalyst removal, evaporation of the solvent affords the product in 98% purity without any further purification.

  7. Characteristic form of boost-invariant and cylindrically asymmetric hydrodynamic equations

    SciTech Connect

    Chojnacki, Mikolaj; Florkowski, Wojciech

    2006-09-15

    It is shown that the boost-invariant and cylindrically asymmetric hydrodynamic equations for baryon-free matter may be reduced to only two coupled partial differential equations. In the case where the system exhibits the crossover phase transition, the standard numerical methods may be applied to solve these equations and the proposed scheme allows for a very convenient analysis of the cylindrically asymmetric hydrodynamic expansion.

  8. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

    NASA Astrophysics Data System (ADS)

    Lewis, Alan M.; Manolopoulos, David E.; Hore, P. J.

    2014-07-01

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene triad containing considerably more nuclear spins which has recently been used to establish a "proof of principle" for the operation of a chemical compass [K. Maeda, K. B. Henbest, F. Cintolesi, I. Kuprov, C. T. Rodgers, P. A. Liddell, D. Gust, C. R. Timmel, and P. J. Hore, Nature (London) 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C.+PF.- radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical.

  9. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions.

    PubMed

    Lewis, Alan M; Manolopoulos, David E; Hore, P J

    2014-07-28

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene triad containing considerably more nuclear spins which has recently been used to establish a "proof of principle" for the operation of a chemical compass [K. Maeda, K. B. Henbest, F. Cintolesi, I. Kuprov, C. T. Rodgers, P. A. Liddell, D. Gust, C. R. Timmel, and P. J. Hore, Nature (London) 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C(·+)PF(·-) radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical. PMID:25084885

  10. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

    SciTech Connect

    Lewis, Alan M.; Manolopoulos, David E.; Hore, P. J.

    2014-07-28

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene triad containing considerably more nuclear spins which has recently been used to establish a “proof of principle” for the operation of a chemical compass [K. Maeda, K. B. Henbest, F. Cintolesi, I. Kuprov, C. T. Rodgers, P. A. Liddell, D. Gust, C. R. Timmel, and P. J. Hore, Nature (London) 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C{sup ·+}PF{sup ·−} radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical.

  11. Chiral N,N'-Dioxide-Scandium(III)-Catalyzed Asymmetric Dearomatization of 2-Naphthols through an Amination Reaction.

    PubMed

    Lian, Xiangjin; Lin, Lili; Wang, Guojin; Liu, Xiaohua; Feng, Xiaoming

    2015-11-23

    A catalytic asymmetric dearomatization of 2-naphthols with azodicarboxylates has been accomplished by using a N,N'-dioxide-scandium(III) complex as a chiral catalyst. A number of optically active β-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained in up to 99 % yield and up to 99 % ee under mild reaction conditions. The reaction could be scaled up to a gram-scale with the yield and ee maintained. Based on these experiments and on previous reports, a possible transition state was proposed.

  12. Chiral N,N'-Dioxide-Scandium(III)-Catalyzed Asymmetric Dearomatization of 2-Naphthols through an Amination Reaction.

    PubMed

    Lian, Xiangjin; Lin, Lili; Wang, Guojin; Liu, Xiaohua; Feng, Xiaoming

    2015-11-23

    A catalytic asymmetric dearomatization of 2-naphthols with azodicarboxylates has been accomplished by using a N,N'-dioxide-scandium(III) complex as a chiral catalyst. A number of optically active β-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained in up to 99 % yield and up to 99 % ee under mild reaction conditions. The reaction could be scaled up to a gram-scale with the yield and ee maintained. Based on these experiments and on previous reports, a possible transition state was proposed. PMID:26449515

  13. From a Sequential to a Concurrent Reaction in Aqueous Medium: Ruthenium-Catalyzed Allylic Alcohol Isomerization and Asymmetric Bioreduction.

    PubMed

    Ríos-Lombardía, Nicolás; Vidal, Cristian; Liardo, Elisa; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier

    2016-07-18

    The ruthenium-catalyzed redox isomerization of allylic alcohols was successfully coupled with the enantioselective enzymatic ketone reduction (mediated by KREDs) in a concurrent process in aqueous medium. The overall transformation, formally the asymmetric reduction of allylic alcohols, took place with excellent conversions and enantioselectivities, under mild reaction conditions, employing commercially and readily available catalytic systems, and without external coenzymes or cofactors. Optimization resulted in a multistep approach and a genuine cascade reaction where the metal catalyst and biocatalyst coexist from the beginning. PMID:27258838

  14. Organocatalytic Domino Oxa-Michael/1,6-Addition Reactions: Asymmetric Synthesis of Chromans Bearing Oxindole Scaffolds.

    PubMed

    Zhao, Kun; Zhi, Ying; Shu, Tao; Valkonen, Arto; Rissanen, Kari; Enders, Dieter

    2016-09-19

    An asymmetric organocatalytic domino oxa-Michael/1,6-addition reaction of ortho-hydroxyphenyl-substituted para-quinone methides and isatin-derived enoates has been developed. In the presence of 5 mol % of a bifunctional thiourea organocatalyst, this scalable domino reaction affords 4-phenyl-substituted chromans bearing spiro-connected oxindole scaffolds and three adjacent stereogenic centers in good to excellent yields (up to 98 %) and with very high stereoselectivities (up to >20:1 d.r., >99 % ee). PMID:27600477

  15. Organocatalytic Domino Oxa-Michael/1,6-Addition Reactions: Asymmetric Synthesis of Chromans Bearing Oxindole Scaffolds.

    PubMed

    Zhao, Kun; Zhi, Ying; Shu, Tao; Valkonen, Arto; Rissanen, Kari; Enders, Dieter

    2016-09-19

    An asymmetric organocatalytic domino oxa-Michael/1,6-addition reaction of ortho-hydroxyphenyl-substituted para-quinone methides and isatin-derived enoates has been developed. In the presence of 5 mol % of a bifunctional thiourea organocatalyst, this scalable domino reaction affords 4-phenyl-substituted chromans bearing spiro-connected oxindole scaffolds and three adjacent stereogenic centers in good to excellent yields (up to 98 %) and with very high stereoselectivities (up to >20:1 d.r., >99 % ee).

  16. Mechanistic Study of the Asymmetric Carbonyl-Ene Reaction between Alkyl Enol Ethers and Isatin Catalyzed by the N,N'-Dioxide-Mg(OTf)2 Complex.

    PubMed

    Wang, Junming; Su, Zhishan; Yang, Na; Hu, Changwei

    2016-08-01

    The mechanism and origin of the stereoselectivity of the asymmetric carbonyl-ene reaction between N-methyl-protected isatin and 2-methyloxypropene catalyzed by the N,N'-dioxide-Mg(OTf)2 complex were investigated by DFT and ONIOM methods. The background reaction occurred via a two-stage, one-step mechanism with a high activation barrier of 30.4 kcal mol(-1) at the B3LYP-D3(BJ)/6-311G**(SMD, CH2Cl2)//B3LYP/6-31G*(SMD, CH2Cl2) level at 303 K. Good linear correlations between the global nucleophilicity index (N) and the activation energy barrier (ΔG(⧧)) were found. The chiral N,N'-Mg(II) complex catalyst could enhance the electrophilicity of the isatin substrate by forming hexacoordinate Mg(II) reactive species. The substituent at the ortho positions of aniline combined with the aliphatic ring of the backbone in the chiral N,N'-dioxide ligand played an important role in the construction of a favorable "pocket-like" chiral environment (chiral pocket) around the Mg(II) center, directing the preferential orientation of the incoming substrate. An unfavorable steric arrangement in the re-face attack pathway translated into a more destabilizing activation strain of the ene substrate, enhancing enantiodifferentiation of two competing pathways for the desired R product. This work also suggested a new phosphine ligand (N-L1) for the formation of the Mg(II) complex catalyst for the asymmetric carbonyl-ene reaction. The chiral environment and Lewis acidity of the Mg(II) complex could be fine-tuned by introduction of P-donor units into the ligand for highly efficient asymmetric catalysis. PMID:27400326

  17. A practical new chiral controller for asymmetric Diels-Alder and alkylation reactions.

    PubMed

    Sarakinos, G; Corey, E J

    1999-12-01

    [formula: see text] The enantiomerically pure hydroxy sulfones (+)- and (-)-2 have been prepared from 1,2-epoxycyclohexane by a simple and practical procedure. The acrylate esters of these alcohols undergo BCl3-catalyzed Diels-Alder reactions with a variety of dienes at -78 to -55 degrees C in CH2Cl2 or C7H8 with high dienophile face selectivity (Table 1). The chiral esters so formed are readily cleaved with recovery of the controllers (+)- or (-)-2. Esters of (+)- and (-)-2 can be converted to Z-potassium enolates and alkylated with high face selectivity. PMID:10836034

  18. Uranium oxidation: characterization of oxides formed by reaction with water

    SciTech Connect

    Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

    1983-04-27

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures.

  19. Catalytic asymmetric direct Mannich reaction: a powerful tool for the synthesis of alpha,beta-diamino acids.

    PubMed

    Arrayás, Ramón Gómez; Carretero, Juan C

    2009-07-01

    Optically active alpha,beta-diamino acids are very attractive targets in organic synthesis because of their wide-ranging biological significance and high versatility as synthetic building blocks. Efficient synthesis of such non-proteinogenic amino acid derivatives must face the challenge of generating two contiguous stereocenters with complete diastereo- and enantiocontrol in flexible, acyclic molecules. The catalytic asymmetric direct Mannich reaction has provided elegant and efficient solutions for the stereocontrolled assembly of both syn- and anti-alpha,beta-diamino acid derivatives, including those with a alpha-tetrasubstituted carbon stereocenter, with the aid of either organometallic or purely organic chiral catalysts (or the combination of both). This tutorial review highlights progress in this area, which has recently been boosted through two complementary strategies: the direct Mannich reaction of glycine ester Schiff bases with imines and the direct aza-Henry reaction between nitro compounds and imines. PMID:19551174

  20. Core-structure-inspired asymmetric addition reactions: enantioselective synthesis of dihydrobenzoxazinone- and dihydroquinazolinone-based anti-HIV agents.

    PubMed

    Li, Shen; Ma, Jun-An

    2015-11-01

    Dihydrobenzoxazinones and dihydroquinazolinones are the core units present in many anti-HIV agents, such as Efavirenz, DPC 961, DPC 963, and DPC 083. All these molecules contain a trifluoromethyl moiety at the quaternary stereogenic carbon center with S configuration. The enantioselective addition of carbon nucleophiles to ketones or cyclic ketimines could serve as a key step to access these molecules. This tutorial review provides an overview of significant advances in the synthesis of dihydrobenzoxazinone- and dihydroquinazolinone-based anti-HIV agents and relative analogues, with an emphasis on asymmetric addition reactions for the establishment of the CF3-containing quaternary carbon centers.

  1. Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

    PubMed Central

    Jouffroy, Matthieu; Gramage-Doria, Rafael; Sémeril, David; Oberhauser, Werner; Toupet, Loïc

    2014-01-01

    Summary The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki–Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine) complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon–carbon bond forming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the study dealing with the Mizoroki–Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2. PMID:25383109

  2. Oil-in-Oil Emulsions Stabilized by Asymmetric Polymersomes Formed by AC + BC Block Polymer Co-Assembly.

    PubMed

    Asano, Itaru; So, Soonyong; Lodge, Timothy P

    2016-04-13

    We demonstrate a facile route to asymmetric polymersomes by blending AC and BC block copolymers in oil-in-oil emulsions containing polystyrene (PS) and polybutadiene (PB) in chloroform (CHCl3). Polymersomes were prepared by mixing polystyrene-b-poly(ethylene oxide) (SO) and polybutadiene-b-poly(ethylene oxide) (BO) in the oil-in-oil emulsion, where the droplets and continuous phase are PS- and PB-rich, respectively. The polymersome structure was directly visualized using dye-labeled SO and BO with confocal fluorescence microscopy; SO and BO with a high O block fraction co-assemble to produce asymmetric polymersomes. As the O block is insoluble in both PS and PB, we infer that the detailed structure of the polymersomes is a bilayer in which the S and B blocks face the PS-inner and PB-outer phases, respectively, while the common O blocks form the core membrane. This structure is only observed for sufficiently long O blocks. It is remarkable that although all the polymers are soluble in CHCl3, such elaborate structures are created by straightforward co-assembly. These asymmetric polymersomes should provide robust bilayer membranes around emulsion droplets, leading to stable nanoscopic dispersions of two fluids. PMID:27046136

  3. Oil-in-Oil Emulsions Stabilized by Asymmetric Polymersomes Formed by AC + BC Block Polymer Co-Assembly.

    PubMed

    Asano, Itaru; So, Soonyong; Lodge, Timothy P

    2016-04-13

    We demonstrate a facile route to asymmetric polymersomes by blending AC and BC block copolymers in oil-in-oil emulsions containing polystyrene (PS) and polybutadiene (PB) in chloroform (CHCl3). Polymersomes were prepared by mixing polystyrene-b-poly(ethylene oxide) (SO) and polybutadiene-b-poly(ethylene oxide) (BO) in the oil-in-oil emulsion, where the droplets and continuous phase are PS- and PB-rich, respectively. The polymersome structure was directly visualized using dye-labeled SO and BO with confocal fluorescence microscopy; SO and BO with a high O block fraction co-assemble to produce asymmetric polymersomes. As the O block is insoluble in both PS and PB, we infer that the detailed structure of the polymersomes is a bilayer in which the S and B blocks face the PS-inner and PB-outer phases, respectively, while the common O blocks form the core membrane. This structure is only observed for sufficiently long O blocks. It is remarkable that although all the polymers are soluble in CHCl3, such elaborate structures are created by straightforward co-assembly. These asymmetric polymersomes should provide robust bilayer membranes around emulsion droplets, leading to stable nanoscopic dispersions of two fluids.

  4. Analysis of quasifission competition in fusion reactions forming heavy nuclei

    NASA Astrophysics Data System (ADS)

    Hammerton, Kalee; Kohley, Zachary; Morrissey, Dave; Wakhle, Aditya; Stiefel, Krystin; Hinde, David; Dasgupta, Mahananda; Williams, Elizabeth; Simenel, Cedric; Carter, Ian; Cook, Kaitlin; Jeung, Dongyun; Luong, Duc Huy; McNeil, Steven; Palshetkar, Chandani; Rafferty, Dominic

    2015-10-01

    Heavy-ion fusion reactions have provided a mechanism for the production of superheavy elements allowing for the extension of both the periodic table and chart of the nuclides. However, fusion of the projectile and target, forming a compound nucleus, is hindered by orders of magnitude by the quasifission process in heavy systems. In order to fully understand this mechanism, and make accurate predictions for superheavy element production cross sections, a clear description of the interplay between the fusion-fission and quasifission reaction channels is necessary. The mass-angle distributions of fragments formed in 8 different Cr + W reactions were measured at the Australia National University in order to explore the N/Z dependence of the quasifission process. Two sets of data were measured: one at a constant energy relative to the fusion barrier and one at a constant compound nucleus excitation energy. The results of this analysis will provide insight into the effect of using more neutron-rich beams in superheavy element production reactions.

  5. Enhancement and Suppression of Fusion in Reactions Forming Heavy Nuclei

    SciTech Connect

    Hinde, D. J.

    2006-08-14

    A new framework for comparing fusion probabilities in reactions forming heavy elements is presented, that eliminates both theoretical and experimental uncertainties, and gives new insights into systematic behavior. This should help in predicting favorable reactions to form new heavy nuclei. The framework is firstly applied to the formation of isotopes of Thorium, where it is found that production yields follow a simple systematic behavior. The data consistently show that fusion is inhibited (presumably by quasi-fission) by about a factor of 10 for projectiles ranging from Ar to Sn, with little dependence on shell structure in the projectile, target or compound nuclei. Application to formation of isotopes of Nobelium shows much more drastic changes in fusion probability as a function of entrance-channel conditions.

  6. Cinchona Urea-Catalyzed Asymmetric Sulfa-Michael Reactions: The Brønsted Acid-Hydrogen Bonding Model.

    PubMed

    Grayson, Matthew N; Houk, K N

    2016-07-27

    The cinchona alkaloid-derived urea-catalyzed asymmetric conjugate addition of aromatic thiols to cycloalkenones was studied using density functional theory (DFT). Deprotonation of the thiol gives a protonated amine that activates the electrophile by Brønsted acid catalysis, while the urea group binds the nucleophilic thiolate by hydrogen bonding. These results demonstrate the generality of the Brønsted acid-hydrogen bonding transition state (TS) model for cinchona alkaloid catalysis that we recently showed to be favored over Wynberg's widely accepted ion pair-hydrogen bonding model and represent the first detailed mechanistic study of a cinchona urea-catalyzed reaction. The conformation of the catalyst methoxy group has a strong effect on the TS, an effect overlooked in previous mechanistic studies of reactions catalyzed by cinchona alkaloids.

  7. Transition from Asymmetric to Symmetric Fission in the 235U(n,f) Reaction

    SciTech Connect

    Younes, W; Becker, J A; Bernstein, L A; Garrett, P E; McGrath, C A; McNabb, D P; Nelson, R O; Johns, G D; Wilburn, W S; Drake, D M

    2001-07-19

    Prompt {gamma} rays from the neutron-induced fission of {sup 235}U have been studied using the GEANIE spectrometer situated at the LANSCE/WNR ''white'' neutron facility. Gamma-ray production cross sections for 29 ground-state-band transitions in 18 even-even fission fragments were obtained as a function of incident neutron energy, using the time-of-flight technique. Independent yields were deduced from these cross sections and fitted with standard formulations of the fragment charge and mass distributions to study the transition from asymmetric to symmetric fission. The results are interpreted in the context of the disappearance of shell structure at high excitation energies.

  8. Possibilities of synthesis of unknown isotopes of superheavy nuclei with charge numbers Z > 108 in asymmetric actinide-based complete fusion reactions

    NASA Astrophysics Data System (ADS)

    Hong, Juhee; Adamian, G. G.; Antonenko, N. V.

    2016-10-01

    The possibilities of production of new isotopes of superheavy nuclei with charge numbers Z = 109-114 in various asymmetric hot fusion reactions are studied for the first time. The excitation functions of the formation of these isotopes in the xn evaporation channels are predicted and the optimal conditions for the synthesis are proposed. The products of the suggested reactions can fill a gap of unknown isotopes between the isotopes of the heaviest nuclei obtained in cold and hot complete fusion reactions.

  9. Zirconium fluoride glass - Surface crystals formed by reaction with water

    NASA Technical Reports Server (NTRS)

    Doremus, R. H.; Bansal, N. P.; Bradner, T.; Murphy, D.

    1984-01-01

    The hydrated surfaces of a zirconium barium fluoride glass, which has potential for application in optical fibers and other optical elements, were observed by scanning electron microscopy. Crystalline zirconium fluoride was identified by analysis of X-ray diffraction patterns of the surface crystals and found to be the main constituent of the surface material. It was also found that hydrated zirconium fluorides form only in highly acidic fluoride solutions. It is possible that the zirconium fluoride crystals form directly on the glass surface as a result of its depletion of other ions. The solubility of zirconium fluoride is suggested to be probably much lower than that of barium fluoride (0.16 g/100 cu cm at 18 C). Dissolution was determined to be the predominant process in the initial stages of the reaction of the glass with water. Penetration of water into the glass has little effect.

  10. The Construction of All-Carbon Quaternary Stereocenters by Use of Pd-Catalyzed Asymmetric Allylic Alkylation Reactions in Total Synthesis

    PubMed Central

    Hong, Allen Y.

    2014-01-01

    All-carbon quaternary stereocenters have posed significant challenges in the synthesis of complex natural products. These important structural motifs have inspired the development of broadly applicable palladium-catalyzed asymmetric allylic alkylation reactions of unstabilized non-biased enolates for the synthesis of enantioenriched α-quaternary products. This microreview outlines key considerations in the application of palladium-catalyzed asymmetric allylic alkylation reactions and presents recent total syntheses of complex natural products that have employed these powerful transformations for the direct, catalytic, enantioselective construction of all-carbon quaternary stereocenters. PMID:24944521

  11. Asymmetric Synthesis of α-Amino 1,3-Dithianes via Chiral N-Phosphonyl Imine-based Umpolung Reaction

    PubMed Central

    Kattamuri, Padmanabha V.; Ai, Teng; Pindi, Suresh; Sun, Yinwei; Gu, Peng; Shi, Min; Li, Guigen

    2011-01-01

    A series of α-amino-1,3-dithianes have been synthesized via the asymmetric Umpolung reaction of 2-lithio-1,3-dithianes with chiral N-phosphonyl imines in good chemical yields (up to 82%) and good to excellent diastereoselectivities (>99:1). The addition manner by which chiral N-phosphonyl imines are slowly added into the solution of 2-lithio-1,3-dithiane was found to be crucial for achieving excellent diastereoselectivity. The current synthesis was proven to follow the GAP chemistry (Group-Assistant-Purification chemistry) process which avoids traditional purification techniques of chromatography or recrystallization, i.e., the pure chiral α-amino-1,3-dithianes attached with the chiral N-phosphonyl group were readily obtained by washing the solid crude products with hexane or the mixture of hexane-ethyl acetate. PMID:21405041

  12. Chirality imprinting and direct asymmetric reaction screening using a stereodynamic Brønsted/Lewis acid receptor

    NASA Astrophysics Data System (ADS)

    Bentley, Keith W.; Proano, Daysi; Wolf, Christian

    2016-08-01

    Molecular recognition, activation and dynamic self-assembly with Brønsted and Lewis acids play a central role across the chemical sciences including catalysis, crystal engineering, supramolecular architectures and drug design. Despite this general advance, the utilization of the corresponding binding motifs for fast and robust quantitative chemosensing of chiral compounds in a complicate matrix has remained challenging. Here we show that a stereodynamic probe carrying complementary boronic acid and urea units achieves this goal with hydroxy carboxylic acids. Synergistic dual-site binding and instantaneous chirality imprinting result in characteristic ultraviolet and CD readouts that allow instantaneous determination of the absolute configuration, enantiomeric excess and concentration of the target compound even in complex mixtures. The robustness and practicality of this strategy for high-throughput screening purposes is demonstrated. Comprehensive sensing of only 0.5 mg of a crude reaction mixture of an asymmetric reduction eliminates cumbersome work-up protocols and minimizes analysis time, labour and waste production.

  13. Lithium amide assisted asymmetric Mannich-type reactions of menthyl acetate with PMP-aldimines.

    PubMed

    Hata, Seiji; Iguchi, Mayu; Iwasawa, Tetsuo; Yamada, Ken-ichi; Tomioka, Kiyoshi

    2004-05-27

    A lithium enolate of menthyl acetate added to PMP-imines, in the presence of an equimolar amount of lithium diisopropylamide, affords the Mannich-type addition products in high stereoselectivity. [reaction--see text

  14. Nitrated Confined Imidodiphosphates Enable a Catalytic Asymmetric Oxa-Pictet-Spengler Reaction.

    PubMed

    Das, Sayantani; Liu, Luping; Zheng, Yiying; Alachraf, M Wasim; Thiel, Walter; De, Chandra Kanta; List, Benjamin

    2016-08-01

    The development of a highly enantioselective catalytic oxa-Pictet-Spengler reaction has proven a great challenge for chemical synthesis. We now report the first example of such a process, which was realized by utilizing a nitrated confined imidodiphosphoric acid catalyst. Our approach provides substituted isochroman derivatives from both aliphatic and aromatic aldehydes with high yields and excellent enantioselectivities. DFT calculations provide insight into the reaction mechanism. PMID:27457383

  15. Tandem Bond-Forming Reactions of 1-Alkynyl Ethers.

    PubMed

    Minehan, Thomas G

    2016-06-21

    Electron-rich alkynes, such as ynamines, ynamides, and ynol ethers, are functional groups that possess significant potential in organic chemistry for the formation of carbon-carbon bonds. While the synthetic utility of ynamides has recently been expanded considerably, 1-alkynyl ethers, which possess many of the reactivity features of ynamides, have traditionally been far less investigated because of concerns about their stability. Like ynamides, ynol ethers are relatively unhindered to approach by functional groups present in the same or different molecules because of their linear geometry, and they can potentially form up to four new bonds in a single transformation. Ynol ethers also possess unique reactivity features that make them complementary to ynamides. Research over the past decade has shown that ynol ethers formed in situ from stable precursors engage in a variety of useful carbon-carbon bond-forming processes. Upon formation at -78 °C, allyl alkynyl ethers undergo a rapid [3,3]-sigmatropic rearrangement to form allyl ketene intermediates, which may be trapped with alcohol or amine nucleophiles to form γ,δ-unsaturated carboxylic acid derivatives. The process is stereospecific, takes place in minutes at cryogenic temperatures, and affords products containing (quaternary) stereogenic carbon atoms. Trapping of the intermediate allyl ketene with carbonyl compounds, epoxides, or oxetanes instead leads to complex α-functionalized β-, γ-, or δ-lactones, respectively. [3,3]-Sigmatropic rearrangement of benzyl alkynyl ethers also takes place at temperatures ranging from -78 to 60 °C to afford substituted 2-indanones via intramolecular carbocyclization of the ketene intermediate. tert-Butyl alkynyl ethers containing pendant di- and trisubstituted alkenes and enol ethers are stable to chromatographic isolation and undergo a retro-ene/[2 + 2] cycloaddition reaction upon mild thermolysis (90 °C) to afford cis-fused cyclobutanones and donor

  16. Demonstration of asymmetric electron conduction in pseudosymmetrical photosynthetic reaction centre proteins in an electrical circuit

    NASA Astrophysics Data System (ADS)

    Kamran, Muhammad; Friebe, Vincent M.; Delgado, Juan D.; Aartsma, Thijs J.; Frese, Raoul N.; Jones, Michael R.

    2015-03-01

    Photosynthetic reaction centres show promise for biomolecular electronics as nanoscale solar-powered batteries and molecular diodes that are amenable to atomic-level re-engineering. In this work the mechanism of electron conduction across the highly tractable Rhodobacter sphaeroides reaction centre is characterized by conductive atomic force microscopy. We find, using engineered proteins of known structure, that only one of the two cofactor wires connecting the positive and negative termini of this reaction centre is capable of conducting unidirectional current under a suitably oriented bias, irrespective of the magnitude of the bias or the applied force at the tunnelling junction. This behaviour, strong functional asymmetry in a largely symmetrical protein-cofactor matrix, recapitulates the strong functional asymmetry characteristic of natural photochemical charge separation, but it is surprising given that the stimulus for electron flow is simply an externally applied bias. Reasons for the electrical resistance displayed by the so-called B-wire of cofactors are explored.

  17. Nonbonded, attractive cation-pi interactions in azide-mediated asymmetric ring expansion reactions.

    PubMed

    Katz, Christopher E; Ribelin, Timothy; Withrow, Donna; Basseri, Yashar; Manukyan, Anna K; Bermudez, Amy; Nuera, Christian G; Day, Victor W; Powell, Douglas R; Poutsma, Jennifer L; Aubé, Jeffrey

    2008-05-01

    The influence of attractive, nonbonded interactions on the reactions of 1,2- and 1,3-hydroxyalkyl azides with ketones has been investigated through experimental and computational means. A series of 1,3-hydroxyalkyl azides bearing electronically tuned aromatic groups at the 2 position were prepared and reacted along with several derivatives designed to conformationally restrict the rotational orientation of the aromatic substituent. These studies showed that a cation-pi interaction between an aryl moiety and an N2(+) leaving group plays a role in determining the stereoselectivity of these reactions. A series of ab initio calculations supported this hypothesis. A computational and experimental analysis suggested a primarily steric model for the analogous reactions of substituted 2-azido-1-ethanol analogues. PMID:18396910

  18. Demonstration of asymmetric electron conduction in pseudosymmetrical photosynthetic reaction centre proteins in an electrical circuit

    PubMed Central

    Kamran, Muhammad; Friebe, Vincent M.; Delgado, Juan D.; Aartsma, Thijs J.; Frese, Raoul N.; Jones, Michael R.

    2015-01-01

    Photosynthetic reaction centres show promise for biomolecular electronics as nanoscale solar-powered batteries and molecular diodes that are amenable to atomic-level re-engineering. In this work the mechanism of electron conduction across the highly tractable Rhodobacter sphaeroides reaction centre is characterized by conductive atomic force microscopy. We find, using engineered proteins of known structure, that only one of the two cofactor wires connecting the positive and negative termini of this reaction centre is capable of conducting unidirectional current under a suitably oriented bias, irrespective of the magnitude of the bias or the applied force at the tunnelling junction. This behaviour, strong functional asymmetry in a largely symmetrical protein–cofactor matrix, recapitulates the strong functional asymmetry characteristic of natural photochemical charge separation, but it is surprising given that the stimulus for electron flow is simply an externally applied bias. Reasons for the electrical resistance displayed by the so-called B-wire of cofactors are explored. PMID:25751412

  19. Analysis of the role of neutron transfer in asymmetric fusion reactions at subbarrier energies

    SciTech Connect

    Ogloblin, A. A.; Zhang, H. Q.; Lin, C. J.; Jia, H. M.; Khlebnikov, S. V.; Kuzmin, E. A.; Danilov, A. N.; Demyanova, A. S.; Trzaska, W. H.; Xu, X. X.; Yang, F.; Sargsyan, V. V. Adamian, G. G.; Antonenko, N. V.; Scheid, W.

    2015-12-15

    The excitation functions were measured for the {sup 28}Si + {sup 208}Pb complete-fusion (capture) reaction at deep subbarrier energies. The results were compared with the cross sections predicted within the quantum diffusion approach. The role of neutron transfer in the case of positive Q values in the {sup 28}Si + {sup 124}Sn, {sup 208}Pb; {sup 30}Si + {sup 124}Sn, {sup 208}Pb; {sup 20}Ne + {sup 208}Pb; {sup 40}Ca + {sup 96}Zr; and {sup 134}Te + {sup 40}Ca complete-fusion (capture) reactions is discussed.

  20. Asymmetrical clustering by sex in free-forming groups: an observational field study.

    PubMed

    Kramer-Moore, Daniela

    2010-08-01

    464 observations were carried out in public places of 3- or 4-person, mixed sex, free-forming groups who spontaneously divided into subgroups. An analysis of sex composition of the subgroups showed that significantly more single-sex subgroups were formed than expected by chance. This was significantly more pronounced among women than among men. Several explanations were considered.

  1. (Salen)Mn(III) Catalyzed Asymmetric Epoxidation Reactions by Hydrogen Peroxide in Water: A Green Protocol

    PubMed Central

    Ballistreri, Francesco Paolo; Gangemi, Chiara M. A.; Pappalardo, Andrea; Tomaselli, Gaetano A.; Toscano, Rosa Maria; Trusso Sfrazzetto, Giuseppe

    2016-01-01

    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%). PMID:27420047

  2. Interfacial thiol-ene photoclick reactions for forming multilayer hydrogels.

    PubMed

    Shih, Han; Fraser, Andrew K; Lin, Chien-Chi

    2013-03-13

    Interfacial visible light-mediated thiol-ene photoclick reactions were developed for preparing step-growth hydrogels with multilayer structures. The effect of a noncleavage type photoinitiator eosin-Y on visible-light-mediated thiol-ene photopolymerization was first characterized using in situ photorheometry, gel fraction, and equilibrium swelling ratio. Next, spectrophotometric properties of eosin-Y in the presence of various relevant macromer species were evaluated using ultraviolet-visible light (UV-vis) spectrometry. It was determined that eosin-Y was able to reinitiate the thiol-ene photoclick reaction, even after light exposure. Because of its small molecular weight, most eosin-Y molecules readily leached out from the hydrogels. The diffusion of residual eosin-Y from preformed hydrogels was exploited for fabricating multilayer step-growth hydrogels. Interfacial hydrogel coating was formed via the same visible-light-mediated gelation mechanism without adding fresh initiator. The thickness of the thiol-ene gel coating could be easily controlled by adjusting visible light exposure time, eosin-Y concentration initially loaded in the core gel, or macromer concentration in the coating solution. The major benefits of this interfacial thiol-ene coating system include its simplicity and cytocompatibility. The formation of thiol-ene hydrogels and coatings neither requires nor generates any cytotoxic components. This new gelation chemistry may have great utilities in controlled release of multiple sensitive growth factors and encapsulation of multiple cell types for tissue regeneration. PMID:23384151

  3. Interfacial thiol-ene photoclick reactions for forming multilayer hydrogels.

    PubMed

    Shih, Han; Fraser, Andrew K; Lin, Chien-Chi

    2013-03-13

    Interfacial visible light-mediated thiol-ene photoclick reactions were developed for preparing step-growth hydrogels with multilayer structures. The effect of a noncleavage type photoinitiator eosin-Y on visible-light-mediated thiol-ene photopolymerization was first characterized using in situ photorheometry, gel fraction, and equilibrium swelling ratio. Next, spectrophotometric properties of eosin-Y in the presence of various relevant macromer species were evaluated using ultraviolet-visible light (UV-vis) spectrometry. It was determined that eosin-Y was able to reinitiate the thiol-ene photoclick reaction, even after light exposure. Because of its small molecular weight, most eosin-Y molecules readily leached out from the hydrogels. The diffusion of residual eosin-Y from preformed hydrogels was exploited for fabricating multilayer step-growth hydrogels. Interfacial hydrogel coating was formed via the same visible-light-mediated gelation mechanism without adding fresh initiator. The thickness of the thiol-ene gel coating could be easily controlled by adjusting visible light exposure time, eosin-Y concentration initially loaded in the core gel, or macromer concentration in the coating solution. The major benefits of this interfacial thiol-ene coating system include its simplicity and cytocompatibility. The formation of thiol-ene hydrogels and coatings neither requires nor generates any cytotoxic components. This new gelation chemistry may have great utilities in controlled release of multiple sensitive growth factors and encapsulation of multiple cell types for tissue regeneration.

  4. Chiral modification of copper exchanged zeolite-Y with cinchonidine and its application in the asymmetric Henry reaction.

    PubMed

    Deka, Jogesh; Satyanarayana, L; Karunakar, G V; Bhattacharyya, Pradip Kr; Bania, Kusum K

    2015-12-28

    Chirally modified Cu(2+) exchanged zeolite-Y was synthesized by direct adsorption of cinchonidine under ambient conditions. The chirally modified materials were characterized using various spectrochemical and physicochemical techniques viz. BET, FTIR, MAS ((1)H and (13)C NMR), XPS, SEM, cyclic voltammetry and PXRD. Characteristic peaks of cinchonidine observed in the supported materials confirmed the adsorption of cinchonidine and its coordination with the Cu(2+) active site on copper exchanged zeolite-Y. (13)C SSNMR and XPS analysis however confirmed for the half encapsulation process, only the quinoline ring of cinchonidine gets coordinated to the internal metal sites via the N atom while the quinuclidine moiety extends out of the host surface. Cinchonidine supported Cu(2+)-Y zeolites were found to exhibit good catalytic performance in the asymmetric Henry reaction. (1)H SSNMR studies also confirmed the protonation of the N atom of the quinuclidine ring during the course of the Henry reaction. Heterogeneous chiral catalysts were effective for up to two consecutive cycles. Leaching of cinchonidine after the second cycle was found to have a negative result in the catalytic performance.

  5. Mechanism and electronic effects in nitrogen ylide-promoted asymmetric aziridination reaction.

    PubMed

    Rajeev, Ramanan; Sunoj, Raghavan B

    2011-04-01

    The mechanism and stereoselectivity of the aziridination reaction between guanidinium ylide and a series of para-substituted benzaldehydes have been studied by using density functional theory methods. The mechanistic details and analyses of the key elementary steps involved in (a) the addition of nitrogen ylide to benzaldehydes and (b) subsequent fragmentation of the resulting oxaspirocyclic intermediate are presented. The relative energies of important transition states and intermediates are found to be useful toward rationalizing reported diastereoselective product formation. The relative energies of the key transition states could be rationalized on the basis of the differences in steric, electrostatic, and other stabilizing weak interactions. The deformation analysis of the transition state geometries exhibited good correlation with the predicted activation barriers. The changes in cis/trans diastereoselectivity preferences upon changes in the electron donating/withdrawing abilities of the para substituents on benzaldehyde are identified as arising due to vital differences in the preferred pathways. The large value of reaction constant (ρ > 4.8) estimated from the slope of good linear Hammett plots indicated high sensitivity to the electronic nature of substituents on benzaldehyde. The formation of trans-aziridine in the case of strong electron donating groups and cis-aziridines with weakly electron donating/withdrawing group has been explained by the likely changes in the mechanistic course of the reaction. In general, the predicted trends are found to be in good agreement with the earlier experimental reports.

  6. Asymmetric Ring Opening/Cyclization/Retro-Mannich Reaction of Cyclopropyl Ketones with Aryl 1,2-Diamines for the Synthesis of Benzimidazole Derivatives.

    PubMed

    Xia, Yong; Lin, Lili; Chang, Fenzhen; Liao, Yuting; Liu, Xiaohua; Feng, Xiaoming

    2016-09-26

    A highly efficient asymmetric ring-opening/cyclization/retro-Mannich reaction of cyclopropyl ketones with aryl 1,2-diamines has been realized using a chiral N,N'-dioxide/Sc(III) catalyst. Benzimidazoles containing chiral side chains were generated under mild reaction conditions in excellent outcomes (up to 99 % yield and 97 % ee). This method also provides efficient access to chiral benzimidazole-substituted amide and cycloheptene derivatives. PMID:27376785

  7. Asymmetric crystallization during cooling and heating in model glass-forming systems

    NASA Astrophysics Data System (ADS)

    Wang, Minglei; Zhang, Kai; Li, Zhusong; Liu, Yanhui; Schroers, Jan; Shattuck, Mark D.; O'Hern, Corey S.

    2015-03-01

    We perform molecular dynamics (MD) simulations of the crystallization process in binary Lennard-Jones systems during heating and cooling to investigate atomic-scale crystallization kinetics in glass-forming materials. For the cooling protocol, we prepared equilibrated liquids above the liquidus temperature Tl and cooled each sample to zero temperature at rate Rc. For the heating protocol, we first cooled equilibrated liquids to zero temperature at rate Rp and then heated the samples to temperature T >Tl at rate Rh. We measured the critical heating and cooling rates Rh* and Rc*, below which the systems begin to form a substantial fraction of crystalline clusters during the heating and cooling protocols. We show that Rh*>Rc* and that the asymmetry ratio Rh*/Rc* includes an intrinsic contribution that increases with the glass-forming ability (GFA) of the system and a preparation-rate dependent contribution that increases strongly as Rp→Rc* from above. We also show that the predictions from classical nucleation theory (CNT) can qualitatively describe the dependence of the asymmetry ratio on the GFA and preparation rate Rp from the MD simulations and results for the asymmetry ratio measured in Zr- and Au-based bulk metallic glasses (BMG). This work emphasizes the need for and benefits of an improved understanding of crystallization processes in BMGs and other glass-forming systems.

  8. Asymmetric crystallization during cooling and heating in model glass-forming systems.

    PubMed

    Wang, Minglei; Zhang, Kai; Li, Zhusong; Liu, Yanhui; Schroers, Jan; Shattuck, Mark D; O'Hern, Corey S

    2015-03-01

    We perform molecular dynamics (MD) simulations of the crystallization process in binary Lennard-Jones systems during heating and cooling to investigate atomic-scale crystallization kinetics in glass-forming materials. For the cooling protocol, we prepared equilibrated liquids above the liquidus temperature Tl and cooled each sample to zero temperature at rate Rc. For the heating protocol, we first cooled equilibrated liquids to zero temperature at rate Rp and then heated the samples to temperature T>Tl at rate Rh. We measured the critical heating and cooling rates Rh* and Rc*, below which the systems begin to form a substantial fraction of crystalline clusters during the heating and cooling protocols. We show that Rh*>Rc* and that the asymmetry ratio Rh*/Rc* includes an intrinsic contribution that increases with the glass-forming ability (GFA) of the system and a preparation-rate dependent contribution that increases strongly as Rp→Rc* from above. We also show that the predictions from classical nucleation theory (CNT) can qualitatively describe the dependence of the asymmetry ratio on the GFA and preparation rate Rp from the MD simulations and results for the asymmetry ratio measured in Zr- and Au-based bulk metallic glasses (BMG). This work emphasizes the need for and benefits of an improved understanding of crystallization processes in BMGs and other glass-forming systems.

  9. A Ruthenium/Phosphoramidite-Catalyzed Asymmetric Interrupted Metallo-ene Reaction.

    PubMed

    Trost, Barry M; Ryan, Michael C

    2016-03-01

    Allylic chlorides prepared from commercially available trans-1,4-dichloro-2-butene were converted to trans-disubstituted 5- and 6-membered ring systems with perfect diastereoselectivity and high enantioselectivity under chiral ruthenium catalysis. These products contain stereodefined secondary and tertiary alcohols that originate from the trapping of an alkylruthenium intermediate with adventitious water. Key to the success of this transformation was the development of a new BINOL-based phosphoramidite ligand containing bulky substitution at its 3- and 3'-positions. As a demonstration of product utility, diastereoselective Friedel-Crafts reactions were performed on the chiral benzylic alcohols in high yield and stereoselectivity. PMID:26899551

  10. Bifunctional Brønsted Base Catalyzes Direct Asymmetric Aldol Reaction of α-Keto Amides.

    PubMed

    Echave, Haizea; López, Rosa; Palomo, Claudio

    2016-03-01

    The first enantioselective direct cross-aldol reaction of α-keto amides with aldehydes, mediated by a bifunctional ureidopeptide-based Brønsted base catalyst, is described. The appropriate combination of a tertiary amine base and an aminal, and urea hydrogen-bond donor groups in the catalyst structure promoted the exclusive generation of the α-keto amide enolate which reacted with either non-enolizable or enolizable aldehydes to produce highly enantioenriched polyoxygenated aldol adducts without side-products resulting from dehydration, α-keto amide self-condensation, aldehyde enolization, and isotetronic acid formation.

  11. Catalytic Asymmetric Synthesis of 3-Hydroxy-3-trifluoromethyl Benzofuranones via Tandem Friedel-Crafts/Lactonization Reaction.

    PubMed

    Ren, Hai; Wang, Pan; Wang, Lijia; Tang, Yong

    2015-10-01

    A highly enantioselective and regioselective chiral Lewis acid catalyzed tandem Friedel-Crafts/lactonization reaction is reported, providing direct access to plenty of 3-hydroxy-3-trifluoromethyl benzofuran-2-ones in up to 94% yields with up to >99% ee. Mechanistic study reveals that the interactions between the phenolic hydroxyl group and trifluoropyruvate are the most likely contributing factor to the high enantio- and regioselectivity. Optically pure (-)-BHFF can be obtained in gram-scale with 0.05 mol % catalyst, demonstrating the potentially utility of this method in medicinal chemistry. PMID:26400069

  12. Bifunctional Brønsted Base Catalyzes Direct Asymmetric Aldol Reaction of α-Keto Amides.

    PubMed

    Echave, Haizea; López, Rosa; Palomo, Claudio

    2016-03-01

    The first enantioselective direct cross-aldol reaction of α-keto amides with aldehydes, mediated by a bifunctional ureidopeptide-based Brønsted base catalyst, is described. The appropriate combination of a tertiary amine base and an aminal, and urea hydrogen-bond donor groups in the catalyst structure promoted the exclusive generation of the α-keto amide enolate which reacted with either non-enolizable or enolizable aldehydes to produce highly enantioenriched polyoxygenated aldol adducts without side-products resulting from dehydration, α-keto amide self-condensation, aldehyde enolization, and isotetronic acid formation. PMID:26835655

  13. Dynamical Dipole and Equation of State in N/Z Asymmetric Fusion Reactions

    NASA Astrophysics Data System (ADS)

    Giaz, Agnese; Corsi, Anna; Camera, Franco; Wieland, Oliver; Kravchuk, Vladimir L.; Barlini, Sandro; Alba, Rosa; Bednarczyk, P.; Bracco, Angela; Baiocco, Giorgio; Bardelli, Luigi; Benzoni, Giovanna; Bini, M.; Blasi, Nives; Brambilla, Sergio; Bruno, Mauro; Casini, Giovanni; Ciemala, Michal; Cinausero, Marco; Chiari, M.; Colonna, Maria; Crespi, Fabio Celso Luigi; D'Agostino, Michela; Degerlier, Meltem; Di Toro, Massimo; Gramegna, Fabiana; Kmiecik, Maria; Leoni, Silvia; Maiolino, C.; Maj, Adam; Marchi, Tommaso; Mazurek, K.; Meczynski, W.; Million, Benedicte; Montanari, Daniele; Morelli, Luca; Nannini, Adriana; Nicolini, Roberto; Pasquali, G.; Piantelli, S.; Ordine, A.; Poggi, Giacomo; Rizzi, V.; Rizzo, Carmelo; Santonocito, Domenico; Vandone, Valeria; Vannini, G.

    2014-03-01

    In heavy ion reactions, in the case of N/Z asymmetry between projectile and target, the process leading to complete fusion is expected to produce pre-equilibrium dipole γ-ray emission. It is generated during the charge equilibration process and it is known as Dynamical Dipole. A new measurement of the dynamical dipole emission was performed by studying 16O + 116Sn at 12 MeV/u. These data, together with those measured at 8.1 MeV/u and 15.6 MeV/u for the same reaction, provide the dependence on the Dynamical Dipole total emission yield with beam energy and they can be compared with theoretical expectations. The experimental results show a weak increase of the Dynamical Dipole total yield with beam energies and are in agreement with the prediction of a theoretical model based on the Boltzmann-Nordheim-Vlasov (BNV) approach. The measured trend with beam energy does not confirm the rise and fall behavior previously reported for the same fused compound but with a much higher dipole moment.

  14. Intracellular microRNA profiles form in the Xenopus laevis oocyte that may contribute to asymmetric cell division

    PubMed Central

    Sidova, Monika; Sindelka, Radek; Castoldi, Mirco; Benes, Vladimir; Kubista, Mikael

    2015-01-01

    Asymmetric distribution of fate determinants within cells is an essential biological strategy to prepare them for asymmetric division. In this work we measure the intracellular distribution of 12 maternal microRNAs (miRNA) along the animal-vegetal axis of the Xenopus laevis oocyte using qPCR tomography. We find the miRNAs have distinct intracellular profiles that resemble two out of the three profiles we previously observed for mRNAs. Our results suggest that miRNAs in addition to proteins and mRNAs may have asymmetric distribution within the oocyte and may contribute to asymmetric cell division as cell fate determinants. PMID:26059897

  15. Diphenylprolinol silyl ether catalyzed asymmetric Michael reaction of nitroalkanes and β,β-disubstituted α,β-unsaturated aldehydes for the construction of all-carbon quaternary stereogenic centers.

    PubMed

    Hayashi, Yujiro; Kawamoto, Yuya; Honda, Masaki; Okamura, Daichi; Umemiya, Shigenobu; Noguchi, Yuka; Mukaiyama, Takasuke; Sato, Itaru

    2014-09-15

    The asymmetric Michael reaction of nitroalkanes and β,β-disubstituted α,β-unsaturated aldehydes was catalyzed by diphenylprolinol silyl ether to afford 1,4-addition products with an all-carbon quaternary stereogenic center with excellent enantioselectivity. The reaction is general for β-substituents such as β-aryl and β-alkyl groups, and both nitromethane and nitroethane can be employed. The addition of nitroethane is considered a synthetic equivalent of the asymmetric Michael reaction of ethyl and acetyl substituents by means of radical denitration and Nef reaction, respectively. The short asymmetric synthesis of (S)-ethosuximide with a quaternary carbon center was accomplished by using the present asymmetric Michael reaction as the key step. The reaction mechanism that involves the E/Z isomerization of α,β-unsaturated aldehydes, the retro-Michael reaction, and the different reactivity between nitromethane and nitroethane is discussed.

  16. Enzymatic desymmetrising redox reactions for the asymmetric synthesis of biaryl atropisomers.

    PubMed

    Staniland, Samantha; Yuan, Bo; Giménez-Agulló, Nelson; Marcelli, Tommaso; Willies, Simon C; Grainger, Damian M; Turner, Nicholas J; Clayden, Jonathan

    2014-10-01

    Atropisomeric biaryls carrying ortho-hydroxymethyl and formyl groups were made enantioselectively by desymmetrisation of dialdehyde or diol substrates. The oxidation of the symmetrical diol substrates was achieved using a variant of galactose oxidase (GOase), and the reduction of the dialdehydes using a panel of ketoreductases. Either M or P enantiomers of the products could be formed, with absolute configurations assigned by time-dependent DFT calculations of circular dichroism spectra. The differing selectivities observed with different biaryl structures offer an insight into the detailed structure of the active site of the GOase enzyme.

  17. Enzymatic Desymmetrising Redox Reactions for the Asymmetric Synthesis of Biaryl Atropisomers

    PubMed Central

    Staniland, Samantha; Yuan, Bo; Giménez-Agulló, Nelson; Marcelli, Tommaso; Willies, Simon C; Grainger, Damian M; Turner, Nicholas J; Clayden, Jonathan

    2014-01-01

    Atropisomeric biaryls carrying ortho-hydroxymethyl and formyl groups were made enantioselectively by desymmetrisation of dialdehyde or diol substrates. The oxidation of the symmetrical diol substrates was achieved using a variant of galactose oxidase (GOase), and the reduction of the dialdehydes using a panel of ketoreductases. Either M or P enantiomers of the products could be formed, with absolute configurations assigned by time-dependent DFT calculations of circular dichroism spectra. The differing selectivities observed with different biaryl structures offer an insight into the detailed structure of the active site of the GOase enzyme. PMID:25156181

  18. Chirality imprinting and direct asymmetric reaction screening using a stereodynamic Brønsted/Lewis acid receptor.

    PubMed

    Bentley, Keith W; Proano, Daysi; Wolf, Christian

    2016-01-01

    Molecular recognition, activation and dynamic self-assembly with Brønsted and Lewis acids play a central role across the chemical sciences including catalysis, crystal engineering, supramolecular architectures and drug design. Despite this general advance, the utilization of the corresponding binding motifs for fast and robust quantitative chemosensing of chiral compounds in a complicate matrix has remained challenging. Here we show that a stereodynamic probe carrying complementary boronic acid and urea units achieves this goal with hydroxy carboxylic acids. Synergistic dual-site binding and instantaneous chirality imprinting result in characteristic ultraviolet and CD readouts that allow instantaneous determination of the absolute configuration, enantiomeric excess and concentration of the target compound even in complex mixtures. The robustness and practicality of this strategy for high-throughput screening purposes is demonstrated. Comprehensive sensing of only 0.5 mg of a crude reaction mixture of an asymmetric reduction eliminates cumbersome work-up protocols and minimizes analysis time, labour and waste production. PMID:27549926

  19. Chirality imprinting and direct asymmetric reaction screening using a stereodynamic Brønsted/Lewis acid receptor

    PubMed Central

    Bentley, Keith W.; Proano, Daysi; Wolf, Christian

    2016-01-01

    Molecular recognition, activation and dynamic self-assembly with Brønsted and Lewis acids play a central role across the chemical sciences including catalysis, crystal engineering, supramolecular architectures and drug design. Despite this general advance, the utilization of the corresponding binding motifs for fast and robust quantitative chemosensing of chiral compounds in a complicate matrix has remained challenging. Here we show that a stereodynamic probe carrying complementary boronic acid and urea units achieves this goal with hydroxy carboxylic acids. Synergistic dual-site binding and instantaneous chirality imprinting result in characteristic ultraviolet and CD readouts that allow instantaneous determination of the absolute configuration, enantiomeric excess and concentration of the target compound even in complex mixtures. The robustness and practicality of this strategy for high-throughput screening purposes is demonstrated. Comprehensive sensing of only 0.5 mg of a crude reaction mixture of an asymmetric reduction eliminates cumbersome work-up protocols and minimizes analysis time, labour and waste production. PMID:27549926

  20. Organic Reaction Mechanisms in the Sixth Form Part 2.

    ERIC Educational Resources Information Center

    Simpson, Peter

    1989-01-01

    Presents the mechanistic ideas underlying reactions between nucleophiles and carbonyl compounds as well as some popular misconceptions. Relates reactions of carboxylic acid derivatives to those of aldehydes and ketones. Discusses leaving group ability and the ability of carbonyl oxygen to accept a negative charge. (Author/MVL)

  1. The Friedel-Crafts Reaction - A Sixth Form Project

    ERIC Educational Resources Information Center

    Hodson, D.

    1973-01-01

    Suggests that the Friedel-Crafts reaction, used for synthesizing a wide range of aromatic compounds, is an ideal vehicle for extended senior high school project work in chemistry. Provides a theoretical discussion of the reaction, suggests a number of suitable investigations, and outlines the experimental details. (JR)

  2. Diastereo- and enantioselective construction of a bispirooxindole scaffold containing a tetrahydro-β-carboline moiety through an organocatalytic asymmetric cascade reaction.

    PubMed

    Dai, Wei; Lu, Han; Li, Xin; Shi, Feng; Tu, Shu-Jiang

    2014-09-01

    The first catalytic asymmetric construction of a new class of bispirooxindole scaffold-containing tetrahydro-β-carboline moiety has been established through chiral phosphoric acid-catalyzed three-component cascade Michael/Pictet-Spengler reactions of isatin-derived 3-indolylmethanols, isatins, and amino-ester, which afforded structurally complex and diverse bispirooxindoles with one quaternary and one tetrasubstituted stereogenic centers in excellent stereoselectivities (all >95:5 diastereomeric ratio (d.r.), up to 98:2 enantiomeric ratio (e.r.)). This intriguing class of chiral bispirooxindoles integrated the two important structures of tetrahydro-β-carboline and bispirooxindole, both of them possessing significant bioactivities. This approach also combined the merits of asymmetric organocatalysis and multicomponent tandem reaction, which provided a unique strategy for the preparation of structurally rigid bispiro-architectures with concomitant creation of multiple quaternary stereogenic centers. PMID:25056997

  3. Organocatalytic asymmetric Henry reaction of 1H-pyrrole-2,3-diones with bifunctional amine-thiourea catalysts bearing multiple hydrogen-bond donors

    PubMed Central

    Zhang, Ming-Liang; Yue, Deng-Feng; Wang, Zhen-Hua; Luo, Yuan; Zhang, Xiao-Mei

    2016-01-01

    Summary For the first time, a catalytic asymmetric Henry reaction of 1H-pyrrole-2,3-diones was achieved with a chiral bifunctional amine-thiourea as a catalyst possessing multiple hydrogen-bond donors. With this developed method, a range of 3-hydroxy-3-nitromethyl-1H-pyrrol-2(3H)-ones bearing quaternary stereocenters were obtained in acceptable yield (up to 75%) and enantioselectivity (up to 73% ee). PMID:26977188

  4. Self-assembled polymersomes formed by symmetric, asymmetric and side-chain-tethered coil-rod-coil triblock copolymers.

    PubMed

    Lin, Yung-Lung; Chang, Hung-Yu; Sheng, Yu-Jane; Tsao, Heng-Kwong

    2014-03-21

    Self-assembly behaviors of coil-rod-coil copolymers in selective solvents are explored by dissipative particle dynamics. The morphological phase diagram as a function of rod length and coil length shows five distinct types of aggregates, including spherical micelles, worm-like micelles, disk-like aggregates, honeycomb structures, and polymersomes. Small polymersomes are formed at rather poor alignment associated with monolayered rod domains. Some of the rods are even lying perpendicular to the radial direction. For symmetric copolymers (CmRxCm), the condition of vesicle formation is restricted to short coil and rod lengths. To favor the formation of CRC-polymersomes, two architecture modifications are adopted. One is to increase the coil length asymmetrically to be CmRxCn, where n > m. The other one is to tether a T-block onto the middle of the rod-block as Cm(RxTy)Cm copolymers. For those CRC-polymersomes, structural, transport, and mechanical properties of the vesicular membrane are determined, including membrane thickness, area density of coil blocks, order parameter, solvent permeability, frequency of flip-flop, membrane tension, and stretching and bending moduli. The influences of the coil length (n) and tethered block length (y) on membrane properties are examined. Finally, the mechanism of membrane fusion between CRC-polymersomes is investigated. The fusion process involves four stages and in the contact region the rods lying perpendicular to the radial direction of the polymersome play the key role. The encounter of two vesicles may result in a fused, hemifused, or non-fused polymersome. The final fate is determined by the competition between membrane tension and the steric barrier of the coil corona. The fusion outcome may change if the tension is altered by manipulating the lumen pressure.

  5. Self-assembled polymersomes formed by symmetric, asymmetric and side-chain-tethered coil-rod-coil triblock copolymers.

    PubMed

    Lin, Yung-Lung; Chang, Hung-Yu; Sheng, Yu-Jane; Tsao, Heng-Kwong

    2014-03-21

    Self-assembly behaviors of coil-rod-coil copolymers in selective solvents are explored by dissipative particle dynamics. The morphological phase diagram as a function of rod length and coil length shows five distinct types of aggregates, including spherical micelles, worm-like micelles, disk-like aggregates, honeycomb structures, and polymersomes. Small polymersomes are formed at rather poor alignment associated with monolayered rod domains. Some of the rods are even lying perpendicular to the radial direction. For symmetric copolymers (CmRxCm), the condition of vesicle formation is restricted to short coil and rod lengths. To favor the formation of CRC-polymersomes, two architecture modifications are adopted. One is to increase the coil length asymmetrically to be CmRxCn, where n > m. The other one is to tether a T-block onto the middle of the rod-block as Cm(RxTy)Cm copolymers. For those CRC-polymersomes, structural, transport, and mechanical properties of the vesicular membrane are determined, including membrane thickness, area density of coil blocks, order parameter, solvent permeability, frequency of flip-flop, membrane tension, and stretching and bending moduli. The influences of the coil length (n) and tethered block length (y) on membrane properties are examined. Finally, the mechanism of membrane fusion between CRC-polymersomes is investigated. The fusion process involves four stages and in the contact region the rods lying perpendicular to the radial direction of the polymersome play the key role. The encounter of two vesicles may result in a fused, hemifused, or non-fused polymersome. The final fate is determined by the competition between membrane tension and the steric barrier of the coil corona. The fusion outcome may change if the tension is altered by manipulating the lumen pressure. PMID:24651905

  6. Quality check of spontaneous adverse drug reaction reporting forms of different countries.

    PubMed

    Bandekar, M S; Anwikar, S R; Kshirsagar, N A

    2010-11-01

    Adverse drug reactions (ADRs) are considered as one of the leading causes of death among hospitalized patients. Thus reporting of adverse drug reactions become an important phenomenon. Spontaneous adverse drug reaction reporting form is an essential component and a major tool of the pharmacovigilance system of any country. This form is a tool to collect information of ADRs which helps in establishing the causal relationship between the suspected drug and the reaction. As different countries have different forms, our aim was to study, analyze the suspected adverse drug reaction reporting form of different countries, and assess if these forms can capture all the data regarding the adverse drug reaction. For this analysis we identified 18 points which are essential to make a good adverse drug reaction report, enabling proper causality assessment of adverse reaction to generate a safety signal. Adverse drug reaction reporting forms of 10 different countries were collected from the internet and compared for 18 points like patient information, information about dechallenge-rechallenge, adequacy of space and columns to capture necessary information required for its causality assessment, etc. Of the ADR forms that we analyzed, Malaysia was the highest scorer with 16 out of 18 points. This study reveals that there is a need to harmonize the ADR reporting forms of all the countries because there is a lot of discrepancy in data captured by the existing ADR reporting forms as the design of these forms is different for different countries. These incomplete data obtained result in inappropriate causality assessment.

  7. Direct Reaction of Amides with Nitric Oxide To Form Diazeniumdiolates

    PubMed Central

    2015-01-01

    We report the apparently unprecedented direct reaction of nitric oxide (NO) with amides to generate ions of structure R(C=O)NH–N(O)=NO–, with examples including R = Me (1a) or 3-pyridyl (1b). The sodium salts of both released NO in pH 7.4 buffer, with 37 °C half-lives of 1–3 min. As NO-releasing drug candidates, diazeniumdiolated amides would have the advantage of generating only 1 equiv of base on hydrolyzing exhaustively to NO, in contrast to their amine counterparts, which generate 2 equiv of base. PMID:25210948

  8. Toward an understanding of the unexpected regioselective hetero-Diels-Alder reactions of asymmetric tetrazines with electron-rich ethylenes: a DFT study.

    PubMed

    Domingo, Luis R; Picher, M Teresa; Sáez, José A

    2009-04-01

    The regioselective hetero-Diels-Alder (HDA) reaction of asymmetric tetrazines (TTZs) with electron-rich (ER) ethylenes has been studied with use of DFT methods at the B3LYP/6-31G* level of theory. The reaction is a domino process that comprises three consecutive reactions: (i) a HDA reaction between the TTZ and the ER ethylene; (ii) a retro-Diels-Alder reaction with loss of nitrogen; and (iii) a beta-hydrogen elimination with formation of the final pyridazines. The first polar HDA reaction, which is associated to the nucleophilic attack of the ER ethylene to the electrophilically activated TTZ, is the rate and regioselectivity determining step of the domino process. The unexpected regioselectivity of these HDA reactions is explained within the polar cycloaddition model by using the conceptual DFT. Although the nucleophilic attack of the ER ethylene over the para position relative to the methylsulfinyl substituent could favor the charge transfer, it is energetically more unfavorable because it diminishes the electron density at the electronegative TTZ core.

  9. Asymmetric exponential amplification reaction on a toehold/biotin featured template: an ultrasensitive and specific strategy for isothermal microRNAs analysis

    PubMed Central

    Chen, Jun; Zhou, Xueqing; Ma, Yingjun; Lin, Xiulian; Dai, Zong; Zou, Xiaoyong

    2016-01-01

    The sensitive and specific analysis of microRNAs (miRNAs) without using a thermal cycler instrument is significant and would greatly facilitate biological research and disease diagnostics. Although exponential amplification reaction (EXPAR) is the most attractive strategy for the isothermal analysis of miRNAs, its intrinsic limitations of detection efficiency and inevitable non-specific amplification critically restrict its use in analytical sensitivity and specificity. Here, we present a novel asymmetric EXPAR based on a new biotin/toehold featured template. A biotin tag was used to reduce the melting temperature of the primer/template duplex at the 5′ terminus of the template, and a toehold exchange structure acted as a filter to suppress the non-specific trigger of EXPAR. The asymmetric EXPAR exhibited great improvements in amplification efficiency and specificity as well as a dramatic extension of dynamic range. The limit of detection for the let-7a analysis was decreased to 6.02 copies (0.01 zmol), and the dynamic range was extended to 10 orders of magnitude. The strategy enabled the sensitive and accurate analysis of let-7a miRNA in human cancer tissues with clearly better precision than both standard EXPAR and RT-qPCR. Asymmetric EXPAR is expected to have an important impact on the development of simple and rapid molecular diagnostic applications for short oligonucleotides. PMID:27257058

  10. Podand-based dimeric chromium(III)-salen complex for asymmetric Henry reaction: cooperative catalysis promoted by complexation of alkali metal ions.

    PubMed

    Ouyang, Guang-Hui; He, Yan-Mei; Fan, Qing-Hua

    2014-12-01

    A new kind of podand-based dimeric salen ligand was synthesized, and its association with potassium cations was investigated by (1) H NMR spectroscopy. The corresponding Cr(III) -salen dimer was assembled by a supramolecular host-guest self-assembly process and was then used as a catalyst in highly efficient and enantioselective asymmetric Henry reactions. Regulation by KBArF (BArF =[3,5-(CF3 )2 C6 H3 ]4 B) led to remarkable improvements in yield (by up to 58 %) and enantioselectivity (for example, from 80 % ee to 96 % ee). PMID:25346533

  11. Asymmetric synthesis of bicyclic dihydropyrans via organocatalytic inverse-electron-demand oxo-Diels-Alder reactions of enolizable aliphatic aldehydes.

    PubMed

    Li, Jun-Long; Yang, Kai-Chuan; Li, Yi; Li, Qiang; Zhu, Hong-Ping; Han, Bo; Peng, Cheng; Zhi, Yong-Gang; Gou, Xiao-Jun

    2016-08-23

    A highly enantioselective organocatalytic inverse-electron-demand oxo-Diels-Alder reaction involving aqueous acetaldehyde has been discovered. The reaction, in which cyclic enones serve as dienes in the presence of readily available secondary amine catalysts, allows facile construction of optically active bicyclic dihydropyrans. Other typical enolizable aliphatic aldehydes can also serve as competent dienophiles in the reaction. PMID:27436351

  12. Cell-sized asymmetric lipid vesicles facilitate the investigation of asymmetric membranes

    NASA Astrophysics Data System (ADS)

    Kamiya, Koki; Kawano, Ryuji; Osaki, Toshihisa; Akiyoshi, Kazunari; Takeuchi, Shoji

    2016-09-01

    Asymmetric lipid giant vesicles have been used to model the biochemical reactions in cell membranes. However, methods for producing asymmetric giant vesicles lead to the inclusion of an organic solvent layer that affects the mechanical and physical characteristics of the membrane. Here we describe the formation of asymmetric giant vesicles that include little organic solvent, and use them to investigate the dynamic responses of lipid molecules in the vesicle membrane. We formed the giant vesicles via the inhomogeneous break-up of a lipid microtube generated by applying a jet flow to an asymmetric planar lipid bilayer. The asymmetric giant vesicles showed a lipid flip-flop behaviour in the membrane, superficially similar to the lipid flip-flop activity observed in apoptotic cells. In vitro synthesis of membrane proteins into the asymmetric giant vesicles revealed that the lipid asymmetry in bilayer membranes improves the reconstitution ratio of membrane proteins. Our asymmetric giant vesicles will be useful in elucidating lipid–lipid and lipid–membrane protein interactions involved in the regulation of cellular functions.

  13. Cell-sized asymmetric lipid vesicles facilitate the investigation of asymmetric membranes.

    PubMed

    Kamiya, Koki; Kawano, Ryuji; Osaki, Toshihisa; Akiyoshi, Kazunari; Takeuchi, Shoji

    2016-09-01

    Asymmetric lipid giant vesicles have been used to model the biochemical reactions in cell membranes. However, methods for producing asymmetric giant vesicles lead to the inclusion of an organic solvent layer that affects the mechanical and physical characteristics of the membrane. Here we describe the formation of asymmetric giant vesicles that include little organic solvent, and use them to investigate the dynamic responses of lipid molecules in the vesicle membrane. We formed the giant vesicles via the inhomogeneous break-up of a lipid microtube generated by applying a jet flow to an asymmetric planar lipid bilayer. The asymmetric giant vesicles showed a lipid flip-flop behaviour in the membrane, superficially similar to the lipid flip-flop activity observed in apoptotic cells. In vitro synthesis of membrane proteins into the asymmetric giant vesicles revealed that the lipid asymmetry in bilayer membranes improves the reconstitution ratio of membrane proteins. Our asymmetric giant vesicles will be useful in elucidating lipid-lipid and lipid-membrane protein interactions involved in the regulation of cellular functions. PMID:27554415

  14. Cell-sized asymmetric lipid vesicles facilitate the investigation of asymmetric membranes

    NASA Astrophysics Data System (ADS)

    Kamiya, Koki; Kawano, Ryuji; Osaki, Toshihisa; Akiyoshi, Kazunari; Takeuchi, Shoji

    2016-09-01

    Asymmetric lipid giant vesicles have been used to model the biochemical reactions in cell membranes. However, methods for producing asymmetric giant vesicles lead to the inclusion of an organic solvent layer that affects the mechanical and physical characteristics of the membrane. Here we describe the formation of asymmetric giant vesicles that include little organic solvent, and use them to investigate the dynamic responses of lipid molecules in the vesicle membrane. We formed the giant vesicles via the inhomogeneous break-up of a lipid microtube generated by applying a jet flow to an asymmetric planar lipid bilayer. The asymmetric giant vesicles showed a lipid flip-flop behaviour in the membrane, superficially similar to the lipid flip-flop activity observed in apoptotic cells. In vitro synthesis of membrane proteins into the asymmetric giant vesicles revealed that the lipid asymmetry in bilayer membranes improves the reconstitution ratio of membrane proteins. Our asymmetric giant vesicles will be useful in elucidating lipid-lipid and lipid-membrane protein interactions involved in the regulation of cellular functions.

  15. Asymmetric Catalytic Enantio- and Diastereoselective Boron Conjugate Addition Reactions of α-Functionalized α,β-Unsaturated Carbonyl Substrates.

    PubMed

    Xie, Jian-Bo; Lin, Siqi; Qiao, Shuo; Li, Guigen

    2016-08-01

    An efficient catalytic system has been established for the asymmetric boron conjugate addition of B2pin2 onto α-functionalized (involving C, N, O, and Cl) α,β-unsaturated carbonyls under mild, neutral conditions involving Cu[(S)-(R)-ppfa]Cl, AgNTf2, and alcohols. The dual additives of AgNTf2 and alcohols were found to play crucial roles for achieving high catalytic activity and enantio- and diastereoselectivity (up to 98% ee and 70:1 dr).

  16. Formation of quaternary stereogenic centers by copper-catalyzed asymmetric conjugate addition reactions of alkenylaluminums to trisubstituted enones.

    PubMed

    Müller, Daniel; Alexakis, Alexandre

    2013-11-01

    Alkenylaluminums undergo asymmetric copper-catalyzed conjugate addition (ACA) to β-substituted enones allowing the formation of stereogenic all-carbon quaternary centers. Phosphinamine-copper complexes proved to be particularly active and selective compared with phosphoramidite ligands. After extensive optimization, high enantioselectivities (up to 96% ee) were obtained for the addition of alkenylalanes to β-substituted enones. Two strategies for the generation of the requisite alkenylaluminums were explored allowing for the introduction of aryl- and alkyl-substituted alkenyl nucleophiles. Moreover, alkyl-substituted phosphinamine (SimplePhos) ligands were identified for the first time as highly efficient ligands for the Cu-catalyzed ACA.

  17. Entrance channel dependence of quasifission in reactions forming {sup 220}Th

    SciTech Connect

    Thomas, R. G.; Hinde, D. J.; Duniec, D.; Zenke, F.; Dasgupta, M.; Brown, M. L.; Evers, M.; Gasques, L. R.; Rodriguez, M. D.; Diaz-Torres, A.

    2008-03-15

    Mass-angle correlations of binary fragments produced in {sup 16}O+{sup 204}Pb, {sup 34}S+{sup 186}W, and {sup 48,50}Ti+{sup 166,170}Er reactions have been measured for a range of bombarding energies around their Coulomb barriers. At above-barrier energies, the width of the mass distributions for the fission-like fragments in the {sup 50}Ti+{sup 170}Er reaction are found to be higher than those from the same compound system at similar excitation energies populated via the more mass asymmetric entrance channel reaction {sup 34}S+{sup 186}W, which in turn is higher than those for the {sup 16}O+{sup 204}Pb system. The width of the mass distributions of the Ti+Er systems is found to increase with decreasing bombarding energies, in contrast with those of the {sup 16}O+{sup 204}Pb and {sup 34}S+{sup 186}W systems, which show a monotonic reduction in mass widths. This may be associated with the elongated contact configuration at sub-barrier energies.

  18. Tropospheric reactions of the haloalkyl radicals formed from hydroxyl radical reaction with a series of alternative fluorocarbons

    NASA Technical Reports Server (NTRS)

    Atkinson, Roger

    1990-01-01

    In the present assessment, the hydrogen containing halocarbons being considered as alternatives to the the presently used chlorofluorocarbons are the hydrochlorofluorocarbons (HCFCs) 123 (CF3CHCl2), 141b (CFCl2CH3), 142b (CF2ClCH3), 22 (CHF2Cl) and 124 (CF3CHFCl) and the hydrofluorocarbons (HFCs) 134a (CF3CH2F), 152a (CHF2CH3) and 125 (CF3CHF2). All of these HCFCs and HFCs will react with the hydroxyl (OH) radical in the troposphere, giving rise to haloalkyl radicals which then undergo a complex series of reactions in the troposphere. These reactions of the haloalkyl radicals formed from the initial OH radical reactions with the HCFCs and HFCs under tropospheric conditions are the focus here.

  19. A-T linker adapter polymerase chain reaction for determining flanking sequences by rescuing inverse PCR or thermal asymmetric interlaced PCR products.

    PubMed

    Trinh, Quoclinh; Zhu, Pengyu; Shi, Hui; Xu, Wentao; Hao, Junran; Luo, Yunbo; Huang, Kunlun

    2014-12-01

    The polymerase chain reaction (PCR)-based genome walking method has been extensively used to isolate unknown flanking sequences, whereas nonspecific products are always inevitable. To resolve these problems, we developed a new strategy to isolate the unknown flanking sequences by combining A-T linker adapter PCR with inverse PCR (I-PCR) or thermal asymmetric interlaced PCR (TAIL-PCR). The result showed that this method can be efficiently achieved with the flanking sequence from the Arabidopsis mutant and papain gene. Our study provides researchers with an additional method for determining genomic DNA flanking sequences to identify the target band from bulk of bands and to eliminate the cloning step for sequencing.

  20. Asymmetric synthesis of α-amino-1,3-dithianes via chiral N-phosphonyl imine-based Umpolung reaction without using chromatography and recrystallization.

    PubMed

    Kattamuri, Padmanabha V; Ai, Teng; Pindi, Suresh; Sun, Yinwei; Gu, Peng; Shi, Min; Li, Guigen

    2011-04-15

    A series of α-amino-1,3-dithianes have been synthesized via the asymmetric Umpolung reaction of 2-lithio-1,3-dithianes with chiral N-phosphonyl imines in good chemical yields (up to 82%) and good to excellent diastereoselectivities (>99:1). The manner by which chiral N-phosphonyl imines are slowly added into the solution of 2-lithio-1,3-dithiane was found to be crucial for achieving excellent diastereoselectivity. The current synthesis was proven to follow the GAP chemistry (group-assistant-purification chemistry) process, which avoids traditional purification techniques of chromatography or recrystallization, i.e., the pure chiral α-amino-1,3-dithianes attached with the chiral N-phosphonyl group were readily obtained by washing the solid crude products with hexane or a mixture of hexane-ethyl acetate.

  1. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 3: Michael addition reactions and miscellaneous transformations.

    PubMed

    Aceña, José Luis; Sorochinsky, Alexander E; Soloshonok, Vadim

    2014-09-01

    The major goal of this review is a critical discussion of the literature data on asymmetric synthesis of α-amino acids via Michael addition reactions involving Ni(II)-complexes of amino acids. The material covered is divided into two conceptually different groups dealing with applications of: (a) Ni(II)-complexes of glycine as C-nucleophiles and (b) Ni(II)-complexes of dehydroalanine as Michael acceptors. The first group is significantly larger and consequently subdivided into four chapters based on the source of stereocontrolling element. Thus, a chiral auxiliary can be used as a part of nucleophilic glycine Ni(II) complex, Michael acceptor or both, leading to the conditions of matching vs. mismatching stereochemical preferences. The particular focus of the review is made on the practical aspects of the methodology under discussion and mechanistic considerations.

  2. Configurationally Stable, Enantioenriched Organometallic Nucleophiles in Stereospecific Pd-Catalyzed Cross-Coupling Reactions: An Alternative Approach to Asymmetric Synthesis

    PubMed Central

    Wang, Chao-Yuan; Derosaa, Joseph

    2015-01-01

    Several research groups have recently developed methods to employ configurationally stable, enantioenriched organometallic nucleophiles in stereospecific Pd-catalyzed cross-coupling reactions. By establishing the absolute configuration of a chiral alkyltin or alkylboron nucleophile prior to its use in cross-coupling reactions, new stereogenic centers may be rapidly and reliably generated with preservation of the known initial stereochemistry. While this area of research is still in its infancy, such stereospecific cross-coupling reactions may emerge as simple, general methods to access diverse, optically active products from common enantioenriched organometallic building blocks. This minireview highlights recent progress towards the development of general, stereospecific Pd-catalyzed cross-coupling reactions using configurationally stable organometallic nucleophiles. PMID:26388985

  3. Mechanistic Studies Lead to Dramatically Improved Reaction Conditions for the Cu-Catalyzed Asymmetric Hydroamination of Olefins.

    PubMed

    Bandar, Jeffrey S; Pirnot, Michael T; Buchwald, Stephen L

    2015-11-25

    Enantioselective copper(I) hydride (CuH)-catalyzed hydroamination has undergone significant development over the past several years. To gain a general understanding of the factors governing these reactions, kinetic and spectroscopic studies were performed on the CuH-catalyzed hydroamination of styrene. Reaction profile analysis, rate order assessment, and Hammett studies indicate that the turnover-limiting step is regeneration of the CuH catalyst by reaction with a silane, with a phosphine-ligated copper(I) benzoate as the catalyst resting state. Spectroscopic, electrospray ionization mass spectrometry, and nonlinear effect studies are consistent with a monomeric active catalyst. With this insight, targeted reagent optimization led to the development of an optimized protocol with an operationally simple setup (ligated copper(II) precatalyst, open to air) and short reaction times (<30 min). This improved protocol is amenable to a diverse range of alkene and alkyne substrate classes. PMID:26522837

  4. N,N'-dioxide-scandium(III)-catalyzed asymmetric Aza-Friedel-Crafts reaction of sesamol with aldimines.

    PubMed

    Bai, Sha; Liao, Yuting; Lin, Lili; Luo, Weiwei; Liu, Xiaohua; Feng, Xiaoming

    2014-11-01

    A highly efficient aza-Friedel-Crafts reaction of sesamol with aldimines has been realized by using a chiral N,N'-dioxide-scandium(III) complex as the catalyst. A series of corresponding bioactive chiral α-amino-sesamols were obtained in moderate to good yields (up to 97%) with excellent enantioselectivities (up to 97% ee). Furthermore, the control experiments were conducted to provide fundamental insights into the mechanism of the reaction.

  5. Asymmetric synthesis of anti-1,2-amino alcohols via the Borono-Mannich reaction: a formal synthesis of (-)-swainsonine.

    PubMed

    Au, Christopher W G; Pyne, Stephen G

    2006-09-01

    Chiral alpha-hydroxy aldehydes generated in situ by the ADH reaction of vinyl sulfones undergo a borono-Mannich reaction with beta-styrenyl boronic acid and primary amines to give anti-1,2-amino alcohols in high enantiomeric purities (83-95% ee). This new method allows much more rapid access to these valuable chiral building blocks that has been used in a short formal synthesis (10 synthetic steps from 4-penten-1-ol) of (-)-swainsonine.

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

    PubMed

    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.

  7. Bond-forming reactions of molecular dications as a new route to polyaromatic hydrocarbons.

    PubMed

    Roithova, Jana; Schröder, Detlef

    2006-04-01

    Mass-selected CmHn2+ dications of medium size (m = 6-14, n = 6-10) undergo bond-forming reactions in the presence of acetylene with Cm+2Hn2+ + H2 as the major product channel. These unprecedented reactions of organic dications offer a feasible route for the formation of polycyclic aromatic hydrocarbons under extreme conditions, such as in interstellar clouds.

  8. Catalytic Asymmetric Reactions of 4‐Substituted Indoles with Nitroethene: A Direct Entry to Ergot Alkaloid Structures

    PubMed Central

    Romanini, Simone; Galletti, Emilio; Caruana, Lorenzo; Mazzanti, Andrea; Himo, Fahmi

    2015-01-01

    Abstract A domino Friedel–Crafts/nitro‐Michael reaction between 4‐substituted indoles and nitroethene is presented. The reaction is catalyzed by BINOL‐derived phosphoric acid catalysts, and delivers the corresponding 3,4‐ring‐fused indoles with very good results in terms of yields and diastereo‐ and enantioselectivities. The tricyclic benzo[cd]indole products bear a nitro group at the right position to serve as precursors of ergot alkaloids, as demonstrated by the formal synthesis of 6,7‐secoagroclavine from one of the adducts. DFT calculations suggest that the outcome of the reaction stems from the preferential evolution of a key nitronic acid intermediate through a nucleophilic addition pathway, rather than to the expected “quenching” through protonation. PMID:26486074

  9. Secondary organic aerosol-forming reactions of glyoxal with amino acids.

    PubMed

    De Haan, David O; Corrigan, Ashley L; Smith, Kyle W; Stroik, Daniel R; Turley, Jacob J; Lee, Frances E; Tolbert, Margaret A; Jimenez, Jose L; Cordova, Kyle E; Ferrell, Grant R

    2009-04-15

    Glyoxal, the simplest and most abundant alpha-dicarbonyl compound in the atmosphere, is scavenged by clouds and aerosol, where it reacts with nucleophiles to form low-volatility products. Here we examine the reactions of glyoxal with five amino acids common in clouds. When glyoxal and glycine, serine, aspartic acid or ornithine are present at concentrations as low as 30/microM in evaporating aqueous droplets or bulk solutions, 1,3-disubstituted imidazoles are formed in irreversible second-order reactions detected by nuclear magnetic resonance (NMR), aerosol mass spectrometry (AMS) and electrospray ionization mass spectrometry (ESI-MS). In contrast, glyoxal reacts with arginine preferentially at side chain amino groups, forming nonaromatic five-membered rings. All reactions were accompanied by browning. The uptake of 45 ppb glyoxal by solid-phase glycine aerosol at 50% RH was also studied and found to cause particle growth and the production of imidazole measured by scanning mobility particle sizing and AMS, respectively, with a glyoxal uptake coefficient alpha = 0.0004. Comparison of reaction kinetics in bulk and in drying droplets shows that conversion of glyoxal dihydrate to monohydrate accelerates the reaction by over 3 orders of magnitude, allowing these reactions to occur at atmospheric conditions.

  10. Millimeter and Submillimeter Studies of O(^1D) Insertion Reactions to Form Molecules of Astrophysical Interest

    NASA Astrophysics Data System (ADS)

    Hays, Brian; Wehres, Nadine; Deprince, Bridget Alligood; Roy, Althea A. M.; Laas, Jacob; Widicus Weaver, Susanna L.

    2015-06-01

    While both the number of detected interstellar molecules and their chemical complexity continue to increase, understanding of the processes leading to their formation is lacking. Our research group combines laboratory spectroscopy, observational astronomy, and astrochemical modeling for an interdisciplinary examination of the chemistry of star and planet formation. This talk will focus on our laboratory studies of O(^1D) insertion reactions with organic molecules to produce molecules of astrophysical interest. By employing these reactions in a supersonic expansion, we are able to produce interstellar organic reaction intermediates that are unstable under terrestrial conditions; we then probe the products using millimeter and submillimeter spectroscopy. We benchmarked this setup using the well-studied O(^1D) + methane reaction to form methanol. After optimizing methanol production, we moved on to study the O(^1D) + ethylene reaction to form vinyl alcohol (CH_2CHOH), and the O(^1D) + methyl amine reaction to form aminomethanol (NH_2CH_2OH). Vinyl alcohol measurements have now been extended up to 450 GHz, and the associated spectral analysis is complete. A possible detection of aminomethanol has also been made, and continued spectral studies and analysis are underway. We will present the results from these experiments and discuss future applications of these molecular and spectroscopic techniques.

  11. Secondary organic aerosol-forming reactions of glyoxal with amino acids.

    PubMed

    De Haan, David O; Corrigan, Ashley L; Smith, Kyle W; Stroik, Daniel R; Turley, Jacob J; Lee, Frances E; Tolbert, Margaret A; Jimenez, Jose L; Cordova, Kyle E; Ferrell, Grant R

    2009-04-15

    Glyoxal, the simplest and most abundant alpha-dicarbonyl compound in the atmosphere, is scavenged by clouds and aerosol, where it reacts with nucleophiles to form low-volatility products. Here we examine the reactions of glyoxal with five amino acids common in clouds. When glyoxal and glycine, serine, aspartic acid or ornithine are present at concentrations as low as 30/microM in evaporating aqueous droplets or bulk solutions, 1,3-disubstituted imidazoles are formed in irreversible second-order reactions detected by nuclear magnetic resonance (NMR), aerosol mass spectrometry (AMS) and electrospray ionization mass spectrometry (ESI-MS). In contrast, glyoxal reacts with arginine preferentially at side chain amino groups, forming nonaromatic five-membered rings. All reactions were accompanied by browning. The uptake of 45 ppb glyoxal by solid-phase glycine aerosol at 50% RH was also studied and found to cause particle growth and the production of imidazole measured by scanning mobility particle sizing and AMS, respectively, with a glyoxal uptake coefficient alpha = 0.0004. Comparison of reaction kinetics in bulk and in drying droplets shows that conversion of glyoxal dihydrate to monohydrate accelerates the reaction by over 3 orders of magnitude, allowing these reactions to occur at atmospheric conditions. PMID:19475956

  12. [Inflammatory and autoimmune reactions in different forms of nervous system functioning disorders].

    PubMed

    Otman, I N; Zozulya, S A; Sarmanova, Z V; Klushnik, T P

    2015-01-01

    Parameters of innate (the leukocyte elastase (LE) and alpha1-proteinase inhibitor (α-1-PI) activity) and adaptive immunity (the level of autoantibodies to neuroantigens nerve growth factor (NGF) and myelin basic protein (MPB)) were studied over time in the blood serum of 107 children with perinatal hypoxic-ischemic encephalopathy; 188 children with autism spectrum disorder; 108 patients with schizophrenia. The correlations between immunological parameters and clinical status assessment in all groups of patients using psychometric scales were analyzed. The involvement of innate immunity, i.e. inflammatory reactions, in pathogenesis of all analyzed forms of nervous system functioning disorders was confirmed. The activation of adaptive immunity, i.e. autoimmune reactions, was found only in the group of patients with the most severe forms of nervous system functioning endogenous disorders. The results indicate that the inflammatory and autoimmune reactions are pathogenic mechanism of all studied forms of nervous system functioning disorders. PMID:26852601

  13. Organosulfur compounds: electrophilic reagents in transition-metal-catalyzed carbon-carbon bond-forming reactions.

    PubMed

    Dubbaka, Srinivas Reddy; Vogel, Pierre

    2005-12-01

    Transition-metal-catalyzed carbon-carbon bond-forming reactions are among the most powerful methods in organic synthesis and play a crucial role in modern materials science and medicinal chemistry. Recent developments in the area of ligands and additives permit the cross-coupling of a large variety of reactants, including inexpensive and readily available sulfonyl chlorides. Their desulfitative carbon-carbon cross-coupling reactions (Negishi, Stille, carbonylative Stille, Suzuki-Miyaura, and Sonogashira-Hagihara-type cross-couplings and Mizoroki-Heck-type arylations) are reviewed together with carbon-carbon cross-coupling reactions with other organosulfur compounds as electrophilic reagents.

  14. Transition-Metal-Catalyzed Laboratory-Scale Carbon–Carbon Bond-Forming Reactions of Ethylene

    PubMed Central

    Saini, Vaneet; Stokes, Benjamin J.; Sigman, Matthew S.

    2014-01-01

    Ethylene, the simplest alkene, is the most abundantly synthesized organic molecule by volume. It is readily incorporated into transitionmetal–catalyzed carbon-carbon bond-forming reactions through migratory insertions into alkylmetal intermediates. Because of its D2h symmetry, only one insertion outcome is possible. This limits byproduct formation and greatly simplifies analysis. As described within this Minireview, many carbon–carbon bond-forming reactions incorporate a molecule (or more) of ethylene at ambient pressure and temperature. In many cases, a useful substituted alkene is incorporated into the product. PMID:24105881

  15. Catalytic asymmetric hetero-Diels-Alder reactions of enones with isatins to access functionalized spirooxindole tetrahydropyrans: scope, derivatization, and discovery of bioactives.

    PubMed

    Cui, Hai-Lei; Chouthaiwale, Pandurang V; Yin, Feng; Tanaka, Fujie

    2016-02-01

    The development of concise methods for the synthesis of functionalized small molecules is important in the search for new bioactive molecules. To contribute to this, we have developed oxa-hetero-Diels-Alder reactions of enones with isatins catalyzed by amine-based catalyst systems. Various spirooxindole tetrahydropyranones were synthesized either in enantiomerically enriched forms or as racemic forms depending on the catalyst system. The reaction products were further transformed at the ketone carbonyl group and the indole nitrogen. Using these reactions, functionalized spirooxindole tetrahydropyran derivatives with functional groups in four directions in a three-dimensional space were concisely obtained. From these synthesized compounds, an inhibitor of human ion channel Nav1.7 with μM-level activity was identified, indicating that the developed reaction methods are useful for providing molecules for the discovery of new biofunctional molecules.

  16. Asymmetric pathways in the electrochemical conversion reaction of NiO as battery electrode with high storage capacity.

    PubMed

    Boesenberg, Ulrike; Marcus, Matthew A; Shukla, Alpesh K; Yi, Tanghong; McDermott, Eamon; Teh, Pei Fen; Srinivasan, Madhavi; Moewes, Alexander; Cabana, Jordi

    2014-01-01

    Electrochemical conversion reactions of transition metal compounds create opportunities for large energy storage capabilities exceeding modern Li-ion batteries. However, for practical electrodes to be envisaged, a detailed understanding of their mechanisms is needed, especially vis-à-vis the voltage hysteresis observed between reduction and oxidation. Here, we present such insight at scales from local atomic arrangements to whole electrodes. NiO was chosen as a simple model system. The most important finding is that the voltage hysteresis has its origin in the differing chemical pathways during reduction and oxidation. This asymmetry is enabled by the presence of small metallic clusters and, thus, is likely to apply to other transition metal oxide systems. The presence of nanoparticles also influences the electrochemical activity of the electrolyte and its degradation products and can create differences in transport properties within an electrode, resulting in localized reactions around converted domains that lead to compositional inhomogeneities at the microscale.

  17. Asymmetric pathways in the electrochemical conversion reaction of NiO as battery electrode with high storage capacity

    SciTech Connect

    Boesenberg, Ulrike; Marcus, Matthew A.; Shukla, Alpesh K.; Yi, Tanghong; McDermott, Eamon; Teh, Pei Fen; Srinivasan, Madhavi; Moewes, Alexander; Cabana, Jordi

    2014-11-20

    Electrochemical conversion reactions of transition metal compounds create opportunities for large energy storage capabilities exceeding modern Li-ion batteries. However, for practical electrodes to be envisaged, a detailed understanding of their mechanisms is needed, especially vis-à-vis the voltage hysteresis observed between reduction and oxidation. Here, we present such insight at scales from local atomic arrangements to whole electrodes. NiO was chosen as a simple model system. The most important finding is that the voltage hysteresis has its origin in the differing chemical pathways during reduction and oxidation. This asymmetry is enabled by the presence of small metallic clusters and, thus, is likely to apply to other transition metal oxide systems. Lastly, the presence of nanoparticles also influences the electrochemical activity of the electrolyte and its degradation products and can create differences in transport properties within an electrode, resulting in localized reactions around converted domains that lead to compositional inhomogeneities at the microscale.

  18. Asymmetric pathways in the electrochemical conversion reaction of NiO as battery electrode with high storage capacity

    PubMed Central

    Boesenberg, Ulrike; Marcus, Matthew A.; Shukla, Alpesh K.; Yi, Tanghong; McDermott, Eamon; Teh, Pei Fen; Srinivasan, Madhavi; Moewes, Alexander; Cabana, Jordi

    2014-01-01

    Electrochemical conversion reactions of transition metal compounds create opportunities for large energy storage capabilities exceeding modern Li-ion batteries. However, for practical electrodes to be envisaged, a detailed understanding of their mechanisms is needed, especially vis-à-vis the voltage hysteresis observed between reduction and oxidation. Here, we present such insight at scales from local atomic arrangements to whole electrodes. NiO was chosen as a simple model system. The most important finding is that the voltage hysteresis has its origin in the differing chemical pathways during reduction and oxidation. This asymmetry is enabled by the presence of small metallic clusters and, thus, is likely to apply to other transition metal oxide systems. The presence of nanoparticles also influences the electrochemical activity of the electrolyte and its degradation products and can create differences in transport properties within an electrode, resulting in localized reactions around converted domains that lead to compositional inhomogeneities at the microscale. PMID:25410966

  19. One-pot multiple reactions: asymmetric synthesis of 2,6-cis-disubstituted piperidine alkaloids from chiral aziridine.

    PubMed

    Yadav, Nagendra Nath; Choi, Jihye; Ha, Hyun-Joon

    2016-07-01

    A divergent, new, and highly stereoselective synthesis of cis-2,6-disubstituted piperidine natural products including isosolenopsins, deoxocassine, and spectaline was achieved from chiral aziridine decorated with appropriate alkyl chains for isosolenopsins or alkynyl groups for deoxocassine and spectaline at C2. The characteristic feature of this synthesis is one-pot sequential reactions under atmospheric hydrogen including the reduction of alkyne (for deoxocassine and spectaline), reductive ring-opening of aziridine, debenzylation, and intramolecular reductive amination in high yields. The prerequisite aziridines were elaborated from commercially available (2S)-hydroxymethylaziridine through oxidation, Wittig olefination, and the Grignard reaction for isosolenopsins or substrate-controlled lithium alkynylate addition for deoxocassine and spectaline. PMID:27189444

  20. Direct Catalytic Asymmetric Mannich Reaction with Dithiomalonates as Excellent Mannich Donors: Organocatalytic Synthesis of (R)-Sitagliptin.

    PubMed

    Bae, Han Yong; Kim, Mun Jong; Sim, Jae Hun; Song, Choong Eui

    2016-08-26

    In this study, dithiomalonates (DTMs) were demonstrated to be exceptionally efficient Mannich donors in terms of reactivity and stereoselectivity in cinchona-based-squaramide-catalyzed enantioselective Mannich reactions of diverse imines or α-amidosulfones as imine surrogates. Owing to the superior reactivity of DTMs as compared to conventional malonates, the catalyst loading could be reduced to 0.1 mol % without the erosion of enantioselectivity (up to 99 % ee). Furthermore, by the use of a DTM, even some highly challenging primary alkyl α-amidosulfones were smoothly converted into the desired adducts with excellent enantioselectivity (up to 97 % ee), whereas the use of a malonate or monothiomalonate resulted in no reaction under identical conditions. The synthetic utility of the chiral Mannich adducts obtained from primary alkyl substrates was highlighted by the organocatalytic, coupling-reagent-free synthesis of the antidiabetic drug (-)-(R)-sitagliptin. PMID:27486059

  1. Asymmetric pathways in the electrochemical conversion reaction of NiO as battery electrode with high storage capacity.

    PubMed

    Boesenberg, Ulrike; Marcus, Matthew A; Shukla, Alpesh K; Yi, Tanghong; McDermott, Eamon; Teh, Pei Fen; Srinivasan, Madhavi; Moewes, Alexander; Cabana, Jordi

    2014-01-01

    Electrochemical conversion reactions of transition metal compounds create opportunities for large energy storage capabilities exceeding modern Li-ion batteries. However, for practical electrodes to be envisaged, a detailed understanding of their mechanisms is needed, especially vis-à-vis the voltage hysteresis observed between reduction and oxidation. Here, we present such insight at scales from local atomic arrangements to whole electrodes. NiO was chosen as a simple model system. The most important finding is that the voltage hysteresis has its origin in the differing chemical pathways during reduction and oxidation. This asymmetry is enabled by the presence of small metallic clusters and, thus, is likely to apply to other transition metal oxide systems. The presence of nanoparticles also influences the electrochemical activity of the electrolyte and its degradation products and can create differences in transport properties within an electrode, resulting in localized reactions around converted domains that lead to compositional inhomogeneities at the microscale. PMID:25410966

  2. Base-dependent stereodivergent intramolecular aza-Michael reaction: asymmetric synthesis of 1,3-disubstituted isoindolines.

    PubMed

    Fustero, Santos; Herrera, Lidia; Lázaro, Ruben; Rodríguez, Elsa; Maestro, Miguel A; Mateu, Natalia; Barrio, Pablo

    2013-08-26

    The nucleophilic addition (A(N)) / intramolecular aza-Michael reaction (IMAMR) process on Ellman's tert-butylsulfinyl imines, bearing a Michael acceptor in the ortho position, is studied. This reaction affords 1,3-disubstituted isoindolines with a wide range of substituents in good yields and diastereoselectivities. Interestingly, careful choice of the base for the aza-Michael step allows either the cis or the trans diastereoisomers to be exclusively obtained. This stereodivergent cyclization has enabled the synthesis of C2-symmetric bisacetate-substituted isoindolines. In addition, bisacetate isoindolines bearing two well-differentiated ester moieties are also noteworthy because they may allow for the orthogonal synthesis of β,β'-dipeptides using a single nitrogen atom as a linchpin.

  3. Synthesis of chiral biphenol-based diphosphonite ligands and their application in palladium-catalyzed intermolecular asymmetric allylic amination reactions.

    PubMed

    Shi, Ce; Chien, Chih-Wei; Ojima, Iwao

    2011-02-01

    A library of new 2,2'-bis(diphenylphosphinoyloxy)-1,1'-binaphthyl (binapo)-type chiral diphosphonite ligands was designed and synthesized based on chiral 3,3',5,5',6,6'-hexasubstituted biphenols. These bop ligands have exhibited excellent efficiency in a palladium-catalyzed intermolecular allylic amination reaction, which provides a key intermediate for the total synthesis of Strychnos indole alkaloids with enantiopurities of up to 96% ee. PMID:21254441

  4. 1,6-asymmetric induction in boron-mediated aldol reactions: application to a practical total synthesis of (+)-discodermolide.

    PubMed

    Paterson, Ian; Delgado, Oscar; Florence, Gordon J; Lyothier, Isabelle; Scott, Jeremy P; Sereinig, Natascha

    2003-01-01

    By relying solely on substrate-based stereocontrol, a practical total synthesis of the microtubule-stabilizing anticancer agent (+)-discodermolide has been realized. This exploits a novel aldol bond construction with 1,6-stereoinduction from the boron enolate of (Z)-enone 3 in addition to aldehyde 2. The 1,3-diol 7 is employed as a common building block for the C(1)-C(5), C(9)-C(16), and C(17)-C(24) subunits. [reaction--see text

  5. Theoretical Studies on the Asymmetric Baeyer-Villiger Oxidation Reaction of 4-Phenylcyclohexanone with m-Chloroperoxobenzoic Acid Catalyzed by Chiral Scandium(III)-N,N'-Dioxide Complexes.

    PubMed

    Yang, Na; Su, Zhishan; Feng, Xiaoming; Hu, Changwei

    2015-05-01

    The mechanism and enantioselectivity of the asymmetric Baeyer-Villiger oxidation reaction between 4-phenylcyclohexanone and m-chloroperoxobenzoic acid (m-CPBA) catalyzed by Sc(III) -N,N'-dioxide complexes were investigated theoretically. The calculations indicated that the first step, corresponding to the addition of m-CPBA to the carbonyl group of 4-phenylcyclohexanone, is the rate-determining step (RDS) for all the pathways studied. The activation barrier of the RDS for the uncatalyzed reaction was predicted to be 189.8 kJ mol(-1) . The combination of an Sc(III) -N,N'-dioxide complex and the m-CBA molecule can construct a bifunctional catalyst in which the Lewis acidic Sc(III) center activates the carbonyl group of 4-phenylcyclohexanone while m-CBA transfers a proton, which lowers the activation barrier of the addition step (RDS) to 86.7 kJ mol(-1) . The repulsion between the m-chlorophenyl group of m-CPBA and the 2,4,6-iPr3 C6 H2 group of the N,N'-dioxide ligand, as well as the steric hindrance between the phenyl group of 4-phenylcyclohexanone and the amino acid skeleton of the N,N'-dioxide ligand, play important roles in the control of the enantioselectivity.

  6. The Role of Grain Surface Reactions in the Chemistry of Star Forming Regions

    NASA Technical Reports Server (NTRS)

    Kress, M. E.; Tielens, A. G. G. M.; Roberge, W. G.

    1998-01-01

    The importance of reactions at the surfaces of dust grains has long been recognized to be one of the two main chemical processes that form molecules in cold, dark interstellar clouds where simple, saturated (fully-hydrogenated) molecules such as H2 water, methanol, H2CO, H2S, ammonia and CH4 are present in quantities far too high to be consistent with their extremely low gas phase formation rates. In cold dark regions of interstellar space, dust grains provide a substrate onto which gas-phase species can accrete and react. Grains provide a "third body" or a sink for the energy released in the exothermic reactions that form chemical bonds. In essence, the surfaces of dust grains open up alternative reaction pathways to form observed molecules whose abundances cannot be explained with gas-phase chemistry alone. This concept is taken one step further in this work: instead of merely acting as a substrate onto which radicals and molecules may physically adsorb, some grains may actively participate in the reaction itself, forming chemical bonds with the accreting species. Until recently, surface chemical reactions had not been thought to be important in warm circumstellar media because adspecies rapidly desorb from grains at very low temperatures; thus, the residence times of molecules and radicals on the surface of grains at all but the lowest temperatures are far too short to allow these reactions to occur. However, if the adspecies could adsorb more strongly, via a true chemical bond with surfaces of some dust grains, then grain surface reactions will play an important role in warm circumstellar regions as well. In this work, the surface-catalyzed reaction CO + 3 H2 yields CH4 + H2O is studied in the context that it may be very effective at converting the inorganic molecule CO into the simplest organic compound, methane. H2 and CO are the most abundant molecules in space, and the reaction converting them to methane, while kinetically inhibited in the gas phase under

  7. Reactions to Discrimination, Stigmatization, Ostracism, and Other Forms of Interpersonal Rejection

    PubMed Central

    Richman, Laura Smart; Leary, Mark R.

    2009-01-01

    This article describes a new model that provides a framework for understanding people’s reactions to threats to social acceptance and belonging as they occur in the context of diverse phenomena such as rejection, discrimination, ostracism, betrayal, and stigmatization. People’s immediate reactions are quite similar across different forms of rejection in terms of negative affect and lowered self-esteem. However, following these immediate responses, people’s reactions are influenced by construals of the rejection experience that predict 3 distinct motives for prosocial, antisocial, and socially avoidant behavioral responses. The authors describe the relational, contextual, and dispositional factors that affect which motives determine people’s reactions to a rejection experience and the ways in which these 3 motives may work at cross-purposes. The multimotive model accounts for the myriad ways in which responses to rejection unfold over time and offers a basis for the next generation of research on interpersonal rejection. PMID:19348546

  8. Eliciting Students' Understandings of Chemical Reactions Using Two Forms of Essay Questions during a Learning Cycle.

    ERIC Educational Resources Information Center

    Cavallo, Ann M. L.; McNeely, Jack C.; Marek, Edmund A.

    2003-01-01

    Examines 9th grade students' explanations of chemical reactions using two forms of open-ended essay questions, those providing students with key terms to be used as "anchors" on which to base their essay, and those that do not provide terms. Results indicate that more misunderstandings were elicited by the use of key terms as compared to the…

  9. A polystyrene-supported 9-amino(9-deoxy)epi quinine derivative for continuous flow asymmetric Michael reactions.

    PubMed

    Izquierdo, Javier; Ayats, Carles; Henseler, Andrea H; Pericàs, Miquel A

    2015-04-14

    A polystyrene (PS)-supported 9-amino(9-deoxy)epi quinine derivative catalyzes Michael reactions affording excellent levels of conversion and enantioselectivity using different nucleophiles and structurally diverse enones. The highly recyclable, immobilized catalyst has been used to implement a single-pass, continuous flow process (residence time: 40 min) that can be operated for 21 hours without significant decrease in conversion and with improved enantioselectivity with respect to batch operation. The flow process has also been used for the sequential preparation of a small library of enantioenriched Michael adducts.

  10. Morphology of melt-rich channels formed during reaction infiltration experiments on partially molten mantle rocks

    NASA Astrophysics Data System (ADS)

    Pec, Matej; Holtzman, Benjamin; Zimmerman, Mark; Kohlstedt, David

    2016-04-01

    Geochemical, geophysical and geological observations suggest that melt extraction from the partially molten mantle occurs by some sort of channelized flow. Melt-solid reactions can lead to melt channelization due to a positive feedback between melt flow and reaction. If a melt-solid reaction increases local permeability, subsequent flow is increased as well and promotes further reaction. This process can lead to the development of high-permeability channels which emerge from background flow. In nature, anastomozing tabular dunite bodies within peridotitic massifs are thought to represent fossilized channels that formed by reactive flow. The conditions under which such channels can emerge are treated by the reaction infiltration instability (RII) theory (e.g. Szymczak and Ladd 2014). In this contribution, we report the results of a series of Darcy type experiments designed to study the development of channels due to RII in mantle lithologies (Pec et al. 2015). We sandwiched a partially molten rock between a melt source and a porous sink and annealed it at high-pressures (P = 300 MPa) and high-temperatures (T = 1200° or 1250° C) under a controlled pressure gradient (∇P = 0-100 MPa/mm) for up to 5 hours. The partially molten rock is formed by 50:50 mixtures of San Carlos olivine (Ol, Fo ˜ 88) and clinopyroxene (Cpx) with either 4, 10 or 20 vol% of alkali basalt added. The source and sink are disks of alkali basalt and porous alumina, respectively. During the experiments, silica undersaturated melt from the melt source dissolves Cpx and precipitates an iron rich Ol (Fo ˜ 82) thereby forming a Cpx-free reaction layer at the melt source - partially molten rock interface. The melt fraction in the reaction layer increases significantly (40% melt) compared to the protolith, confirming that the reaction increases the permeability of the partially molten rock. In experiments annealed under a low pressure gradient (and hence slow melt flow velocity) the reaction layer is

  11. Asymmetric pathways in the electrochemical conversion reaction of NiO as battery electrode with high storage capacity

    DOE PAGESBeta

    Boesenberg, Ulrike; Marcus, Matthew A.; Shukla, Alpesh K.; Yi, Tanghong; McDermott, Eamon; Teh, Pei Fen; Srinivasan, Madhavi; Moewes, Alexander; Cabana, Jordi

    2014-11-20

    Electrochemical conversion reactions of transition metal compounds create opportunities for large energy storage capabilities exceeding modern Li-ion batteries. However, for practical electrodes to be envisaged, a detailed understanding of their mechanisms is needed, especially vis-à-vis the voltage hysteresis observed between reduction and oxidation. Here, we present such insight at scales from local atomic arrangements to whole electrodes. NiO was chosen as a simple model system. The most important finding is that the voltage hysteresis has its origin in the differing chemical pathways during reduction and oxidation. This asymmetry is enabled by the presence of small metallic clusters and, thus, ismore » likely to apply to other transition metal oxide systems. Lastly, the presence of nanoparticles also influences the electrochemical activity of the electrolyte and its degradation products and can create differences in transport properties within an electrode, resulting in localized reactions around converted domains that lead to compositional inhomogeneities at the microscale.« less

  12. Design, synthesis, and applications of potential substitutes of t-Bu-phosphinooxazoline in Pd-catalyzed asymmetric transformations and their use for the improvement of the enantioselectivity in the Pd-catalyzed allylation reaction of fluorinated allyl enol carbonates.

    PubMed

    Bélanger, Étienne; Pouliot, Marie-France; Courtemanche, Marc-André; Paquin, Jean-François

    2012-01-01

    The design, synthesis, and applications of potential substitutes of t-Bu-PHOX in asymmetric catalysis is reported. The design relies on the incorporation of geminal substituents at C5 in combination with a substituent at C4 other than t-butyl (i-Pr, i-Bu, or s-Bu). Most of these new members of the PHOX ligand family behave similarly in terms of stereoinduction to t-Bu-PHOX in three palladium-catalyzed asymmetric transformations. Electronically modified ligands were also prepared and used to improve the enantioselectivity in the Pd-catalyzed allylation reaction of fluorinated allyl enol carbonates.

  13. Water-regolith-energy Interaction in Landscape Evolution and Its Influence on Forming Asymmetric Landscape: An Example from the Shale Hills Critical Zone Observatory of Central Pennsylvania

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Slingerland, R. L.; Shi, Y.; Duffy, C.; West, N.

    2015-12-01

    Shale Hills Critical Zone Observatory (SSHCZO) is a 0.08 km2 first order experimental research catchment with relatively homogeneous bedrock, regolith and tectonic uplift, but with an asymmetric slope and thickness of regolith on the north- and south-facing hillslopes. In this paper, we use a hydrological-morphodynamic model (LE-PIHM), which links bedrock, soil, surface and subsurface water flow, plant, energy, and seasonal climate, to address the influence of water-regolith-energy interaction on soil creep process, the possible factors causing slope asymmetry and the spatial distribution of regolith transport at the SSHCZO. Two non-dimensional parameters were used to explore the competitive relationship between regolith diffusion and advection forming self-organized channel spacing, relief and slope length at steady state. Model simulation under seasonal meteorological forcing shows spatial variations of hillslope sediment fluxes. An experimental study using Beryllium 10 at the SSHCZO (West et al 2013) showed that a south-facing planar slope had a greater diffusion flux rate than a planar on north-facing slope. The model confirms this relationship in general although there are significant local variations. The largest regolith transport rate by overland flow (advection) occurs at the junctions of main channel and swales. The model simulation further suggests that north-south differences in diffusive flux may be a result of asymmetric solar insolation which affects freeze-thaw frequency and sediment transport through the process of soil creep. This study demonstrates the value of physically-based distributed landscape evolution model on estimating spatial distribution of regolith transport and highlights the critical transition zone.

  14. Cognitive appraisals, emotional reactions, and their associations with three forms of peer-victimization.

    PubMed

    Anderson, Shayron; Hunter, Simon C

    2012-11-01

    Victimized students' cognitive appraisals (perceived threat, control) are related to emotional reactions. Furthermore, psychosocial wellbeing is differentially associated with from of victimization (direct vs. indirect), suggesting that emotional reactions to direct and indirect victimization may also differ. The present study therefore evaluated appraisals and emotional reactions within the context of verbal, physical, and indirect victimization experiences, testing a mediational model which considers appraisals to mediate the effect of victimization upon emotional reaction. Participants were 146 students (44% male) aged 10-13 years attending mainstream schools in Scotland (UK). Self-report measures assessed peer-victimization (physical, verbal, indirect), appraisal (control, threat) and emotional reaction (anger, sadness). All forms of victimization were positively associated with both emotions. Threat appraisals were positively associated with all forms of victimization and control appraisals were negatively associated with physical victimization. The relationships between appraisals and emotions varied according to victimization type. The effects of victimization upon emotions were not mediated via appraisals. These results extend our understanding of the relationships between victimization and affect. PMID:23079361

  15. Intermediates Formed in the Reactions of Organocuprates with α,β-Unsaturated Nitriles.

    PubMed

    Putau, Aliaksei; Brand, Harald; Koszinowski, Konrad

    2016-08-26

    Conjugate additions of organocuprates are of outstanding importance for organic synthesis. To improve our mechanistic understanding of these reactions, we have used electrospray ionization mass spectrometry for the identification of the ionic intermediates formed upon the treatment of LiCuR2 ⋅LiCN (R=Me, Bu, Ph) with a series of α,β-unsaturated nitriles. Acrylonitrile, the weakest Michael acceptor included, did not afford any detectable intermediates. Fumaronitrile (FN) yielded adducts of the type Lin-1 Cun R2n (FN)n (-) , n=1-3. When subjected to fragmentation in the gas phase, these adducts were not converted into the conjugate addition products, but re-dissociated into the reactants. In contrast, the reaction with 1,1-dicyanoethylene furnished the products of the conjugate addition without any observable intermediates. Tri- and tetracyanoethylene proved to be quite reactive as well. The presence of several cyano groups in these substrates opened up reaction pathways different from simple conjugate additions, however, and led to dimerization and substitution reactions. Moreover, the gas-phase fragmentation behavior of the species formed from these substrates indicated the occurrence of single-electron transfer processes. Additional quantum-chemical calculations provided insight into the structures and stabilities of the observed intermediates and their consecutive reactions. PMID:27461093

  16. Arylpalladium Phosphonate Complexes as Reactive Intermediates in Phosphorus-Carbon Bond Forming Reactions

    SciTech Connect

    Kohler, Mark C.; Grimes, Thomas V.; Wang, Xiaoping; Cundari, Thomas R.; Stockland, Robert A. Jr.

    2009-01-01

    Phosphorus-carbon bond formation from discrete transition metal complexes have been investigated through a combination of synthetic, spectroscopic, crystallographic, and computational methods. Reactive intermediates of the type (diphosphine)Pd(aryl)(P(O)(OEt)(2)) have been prepared, characterized, and studied as possible intermediates in metal-mediated coupling reactions. Several of the reactive intermediates were characterized crystallographicaliy, and a discussion of the solid state structures is presented. In contrast to other carbon-heteroelement bond forming reactions, palladium complexes containing electron-donating substituents on the aromatic fragment exhibited faster rates of reductive elimination. Large bite angle diphosphine ligands induced rapid rates of elimination, while bipyridine and small bite angle diphosphine ligands resulted in much slower rates of elimination. An investigation of the effect of typical impurities on the elimination reaction was carried out. While excess diphosphine, pyridine, and acetonitrile had little effect on the observed rate, the addition of water slowed the phosphorus-carbon bond forming reaction. Coordination of water to the complex was observed spectroscopically and crystallographically. Computational studies were utilized to probe the reaction pathways for P-C bond formation via Pd catalysis.

  17. Contributions of organic peroxides to secondary aerosol formed from reactions of monoterpenes with O3.

    PubMed

    Docherty, Kenneth S; Wu, Wilbur; Lim, Yong Bin; Ziemann, Paul J

    2005-06-01

    The role of organic peroxides in secondary organic aerosol (SOA) formation from reactions of monoterpenes with O3 was investigated in a series of environmental chamber experiments. Reactions were performed with endocyclic (alpha-pinene and delta3-carene) and exocyclic (beta-pinene and sabinene) alkenes in dry and humid air and in the presence of the OH radical scavengers: cyclohexane, 1-propanol, and formaldehyde. A thermal desorption particle beam mass spectrometer was used to probe the identity and volatility of SOA components, and an iodometric-spectrophotometric method was used to quantify organic peroxides. Thermal desorption profiles and mass spectra showed that the most volatile SOA components had vapor pressures similar to pinic acid and that much of the SOA consisted of less volatile species that were probably oligomeric compounds. Peroxide analyses indicated that the SOA was predominantly organic peroxides, providing evidence that the oligomers were mostly peroxyhemiacetals formed by heterogeneous reactions of hydroperoxides and aldehydes. For example, it was estimated that organic peroxides contributed approximately 47 and approximately 85% of the SOA mass formed in the alpha- and beta-pinene reactions, respectively. Reactions performed with different OH radical scavengers indicated that most of the hydroperoxides were formed through the hydroperoxide channel rather than by reactions of stabilized Criegee intermediates. The effect of the OH radical scavenger on the SOA yield was also investigated, and the results were consistent with results of recent experiments and model simulations that support a mechanism based on changes in the [HO2]/[RO2] ratios. These are the first measurements of organic peroxides in monoterpene SOA, and the results have important implications for understanding the mechanisms of SOA formation and the potential effects of atmospheric aerosol particles on the environment and human health.

  18. Externally controlled anisotropy in pattern-forming reaction-diffusion systems.

    PubMed

    Escala, Dario M; Guiu-Souto, Jacobo; Muñuzuri, Alberto P

    2015-06-01

    The effect of centrifugal forces is analyzed in a pattern-forming reaction-diffusion system. Numerical simulations conducted on the appropriate extension of the Oregonator model for the Belousov-Zhabotinsky reaction show a great variety of dynamical behaviors in such a system. In general, the system exhibits an anisotropy that results in new types of patterns or in a global displacement of the previous one. We consider the effect of both constant and periodically modulated centrifugal forces on the different types of patterns that the system may exhibit. A detailed analysis of the patterns and behaviors observed for the different parameter values considered is presented here.

  19. Heat of Combustion of the Product Formed by the Reaction of Acetylene, Ethylene, and Diborane

    NASA Technical Reports Server (NTRS)

    Tannenbaum, Stanley

    1957-01-01

    The net heat of combustion of the product formed by the reaction of diborane with a mixture of acetylene and ethylene was found to be 20,440 +/- 150 Btu per pound for the reaction of liquid fuel to gaseous carbon dioxide, gaseous water, and solid boric oxide. The measurements were made in a Parr oxygen-bomb calorimeter, and the combustion was believed to be 98 percent complete. The estimated net-heat of combustion for complete combustion would therefore be 20,850 +/- 150 Btu per pound.

  20. Investigation of photochemical reaction products of glucose formed during direct UV detection in CE.

    PubMed

    Schmid, Thomas; Himmelsbach, Markus; Buchberger, Wolfgang W

    2016-04-01

    In CE, saccharides are accessible to direct UV detection due to a photochemical reaction in the detection window of the separation capillary resulting in the formation of UV absorbing substances. Employing a CE method that allows long in-capillary irradiation with subsequent UV and MS detection, the present study could identify several reaction products of glucose. Among these were UV absorbing substances so far unknown to be formed during direct UV detection with the chemical formulas C4 H6 O2 , C5 H6 O4 , C5 H8 O3, and C6 H8 O5 . Investigations of the impact of the irradiation time revealed differences between these reaction products suggesting differing reaction mechanisms especially for the smallest products. More detailed information could be obtained by experiments with isotope-labeled substrates performed to determine the parts of glucose that are converted to the particular reaction products. In addition, structural formulas for the reaction products were suggested based on HPLC-MS/MS measurements of off-line irradiated glucose solutions which revealed the existence of functional groups such as carboxylic acid or aldehyde groups.

  1. Light Charged Particles Emission and the Giant Dipole Resonance in Highly Excited Ce Nucleus Formed in Reactions with Different Mass Asymmetries

    NASA Astrophysics Data System (ADS)

    Barlini, S.; Kravchuk, V. L.; Wieland, O.; Bracco, A.; Gramegna, F.; Airoldi, A.; Benzoni, G.; Blasi, N.; Brambilla, S.; Brekiesz, M.; Bruno, M.; Camera, F.; Casini, G.; Chiari, M.; D'Agostino, M.; De Sanctis, J.; Geraci, E.; Kmiecik, M.; Lanchais, A.; Leoni, S.; Maj, A.; Mastinu, P. F.; Million, B.; Moroni, A.; Nannini, A.; Ordine, A.; Sacchi, R.; Vannini, G.

    2006-08-01

    Recent measurements have been performed at the National Laboratoty of Legnaro using mass-symmetric (400, 500 MeV 64Ni + 68Zn) and mass-asymmetric (250 MeV 16O + 116Sn) entrance channel reactions to form 132Ce compound nucleus at different excitation energies (E*=150, 200 and 200 MeV, respectively). The decay of the composite system has been followed studying the γ-rays and Light Charged Particles (LCP) spectra emitted in coincidence with the Evaporation Residues (ER). In this way the emission mechanism of the LCP, depending on the mass-asymmetry at the entrance channel and on the projectile energy, and the results of the Full Width Half-Maximum (FWHM) of the Giant Dipole Resonance as a function of the nuclear temperature have been studied.

  2. A generalized garnet-forming reaction for metaigneous rocks in the Adirondacks

    USGS Publications Warehouse

    McLelland, J.M.; Whitney, P.R.

    1980-01-01

    A generalized reaction is presented to account for garnet formation in a variety of Adirondack metaigneous rocks. This reaction, which is the sum of five partial reactions written in aluminum-fixed frames of reference, is given by: 4(y+1+w)Anorthite+4 k(y+1+2 w)Olivine +4(1-k)(y+1+2 w)Fe-oxide+(8(y+1) -4 k(y+1+2 w))Orthopyroxene = 2(y+1)Garnet +2(y+1+2 w)Clinopyroxene+4 wSpinel where y is a function of plagioclase composition, k refers to the relative amounts of olivine and Fe-oxide participating in the reaction, and w is a measure of silicon mobility. When mass balanced for Mg and Fe, this reaction is found to be consistent with analyzed mineral compositions in a wide range of Adirondack metaigneous rocks. The reaction applies equally well whether the garnets were formed directly from the rectants given above or went through an intermadiate stage involving the formation of spinel, orthopyroxene, and clinopyroxene. The actual reactions which have produced garnet in both undersaturated and quartz-bearing rocks are special cases of the above general reaction. The most important special cases appear to be those in which the reactants include either olivine alone (k=1) or Fe-oxide alone (k=0). Silicon is relatively immobile (w =2) in olivine bearing, magnesium-rich rocks (k???1), and this correlates with the increased intensity in spinel clouding of plagioclase in these rocks. Silicon mobility apparently increases in the more iron-rich rocks, which also tend to contain clear or lightly clouded plagioclase. In all the rocks studied the most common composition of metamorphic plagioclase is close to An33 (i.e., y=1). Plagioclase of lower anorthite content may be too sodic to participate in garnet formation at the P-T conditions involved. ?? 1980 Springer-Verlag.

  3. Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

    NASA Astrophysics Data System (ADS)

    Birdsall, A. W.; Miner, C. R.; Mael, L. E.; Elrod, M. J.

    2014-08-01

    Recently, methacrylic acid epoxide (MAE) has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA): 2-methylglyceric acid (2-MG) and a set of oligomers, nitric acid esters and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR) spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG), and acids (including MAE and 2-MG) in their reactions with MAE were found to be of a similar magnitude, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water); this finding is consistent with previous environmental chamber investigations of the relative humidity-dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.

  4. Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

    NASA Astrophysics Data System (ADS)

    Birdsall, A. W.; Miner, C. R.; Mael, L. E.; Elrod, M. J.

    2014-12-01

    Recently, methacrylic acid epoxide (MAE) has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA): 2-methylglyceric acid (2-MG) and a set of oligomers, nitric acid esters, and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied with experimental methods. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR) spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG), and acids (including MAE and 2-MG) in their reactions with MAE were found to be of similar magnitudes, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water); this finding is consistent with previous environmental chamber investigations of the relative humidity dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.

  5. Turbulent stresses and secondary currents in a tidal-forced channel with significant curvature and asymmetric bed forms

    USGS Publications Warehouse

    Fong, D.A.; Monismith, Stephen G.; Stacey, M.T.; Burau, J.R.

    2009-01-01

    Acoustic Doppler current profilers are deployed to measure both the mean flow and turbulent properties in a channel with significant curvature. Direct measurements of the Reynolds stress show a significant asymmetry over the tidal cycle where stresses are enhanced during the flood tide and less prominent over the ebb tide. This asymmetry is corroborated by logarithmic fits using 10 min averaged velocity data. A smaller yet similar tendency asymmetry in drag coefficient is inferred by fitting the velocity and estimated large-scale pressure gradient to a one-dimensional along-channel momentum balance. This smaller asymmetry is consistent with recent modeling work simulating regional flows in the vicinity of the study site. The asymmetry in drag suggests the importance of previously reported bed forms for this channel and demonstrates spatial and temporarily variations in bed stress. Secondary circulation patterns observed in a relatively straight section of channel appear driven by local curvature rather than being remotely forced by the regions of significant curvature only a few hundred meters from the measurement site. ?? 2009 ASCE.

  6. A non-scale-invariant form for coarse-grained diffusion-reaction equations

    NASA Astrophysics Data System (ADS)

    Ostvar, Sassan; Wood, Brian D.

    2016-09-01

    The process of mixing and reaction is a challenging problem to understand mathematically. Although there have been successes in describing the effective properties of mixing and reaction under a number of regimes, process descriptions for early times have been challenging for cases where the structure of the initial conditions is highly segregated. In this paper, we use the method of volume averaging to develop a rigorous theory for diffusive mixing with reactions from initial to asymptotic times under highly segregated initial conditions in a bounded domain. One key feature that arises in this development is that the functional form of the averaged differential mass balance equations is not, in general, scale invariant. Upon upscaling, an additional source term arises that helps to account for the initial configuration of the reacting chemical species. In this development, we derive the macroscopic parameters (a macroscale source term and an effectiveness factor modifying the reaction rate) defined in the macroscale diffusion-reaction equation and provide example applications for several initial configurations.

  7. Forming compliance dominated memristive switching through interfacial reaction in Ti/TiO2/Au structure

    NASA Astrophysics Data System (ADS)

    Tang, Zhensen; Fang, Liang; Xu, Nuo; Liu, Rulin

    2015-11-01

    The effects of the forming compliance current (CC) on bipolar resistive switching (BRS) characteristics in Au/Ti/TiO2/Au memristive switches were investigated. After forming with a low CC, a typical BRS with an abrupt SET and negative differential resistance RESET behaviors were observed. In comparison, the sample formed with a high CC exhibited an abnormal BRS with stepwise SET and abrupt RESET transitions. The conduction mechanisms at a high resistance state and a low resistance state were analyzed, respectively. The impact of the forming compliance on the interfacial reaction between Ti and TiO2 was discussed. The Ti-induced interfacial layer played an important role of manipulating the oxygen vacancies, thus providing the possibility of affecting the switching behavior. A physical model based on a combination of the bulk and interfacial effects was proposed to explain our observations.

  8. Preparation of asymmetric porous materials

    DOEpatents

    Coker, Eric N.

    2012-08-07

    A method for preparing an asymmetric porous material by depositing a porous material film on a flexible substrate, and applying an anisotropic stress to the porous media on the flexible substrate, where the anisotropic stress results from a stress such as an applied mechanical force, a thermal gradient, and an applied voltage, to form an asymmetric porous material.

  9. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    DOEpatents

    Cortright, Randy D.; Dumesic, James A.

    2013-04-02

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  10. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    DOEpatents

    Cortright, Randy D.; Dumesic, James A.

    2012-04-10

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  11. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    DOEpatents

    Cortright, Randy D.; Dumesic, James A.

    2011-01-18

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  12. Thermodynamic and kinetic considerations for the reaction of semiquinone radicals to form superoxide and hydrogen peroxide

    PubMed Central

    Song, Yang; Buettner, Garry R.

    2010-01-01

    The quinone/semiquinone/hydroquinone triad (Q/SQ•−/H2Q) represents a class of compounds that has great importance in a wide range of biological processes. The half-cell reduction potentials of these redox couples in aqueous solutions at neutral pH, E°′, provide a window to understanding the thermodynamic and kinetic characteristics of this triad and their associated chemistry and biochemistry in vivo. Substituents on the quinone ring can significantly influence the electron density “on the ring” and thus modify E°′ dramatically. E°′ of the quinone governs the reaction of semiquinone with dioxygen to form superoxide. At near-neutral pH the pKa's of the hydroquinone are outstanding indicators of the electron density in the aromatic ring of the members of these triads (electrophilicity) and thus are excellent tools to predict half-cell reduction potentials for both the one-electron and two-electron couples, which in turn allow estimates of rate constants for the reactions of these triads. For example, the higher the pKa's of H2Q, the lower the reduction potentials and the higher the rate constants for the reaction of SQ•− with dioxygen to form superoxide. However, hydroquinone autoxidation is controlled by the concentration of di-ionized hydroquinone; thus, the lower the pKa's the less stable H2Q to autoxidation. Catalysts, e.g., metals and quinone, can accelerate oxidation processes; by removing superoxide and increasing the rate of formation of quinone, superoxide dismutase can accelerate oxidation of hydroquinones and thereby increase the flux of hydrogen peroxide. The principal reactions of quinones are with nucleophiles via Michael addition, for example, with thiols and amines. The rate constants for these addition reactions are also related to E°′. Thus, pKa's of a hydroquinone and E°′ are central to the chemistry of these triads. PMID:20493944

  13. Sequence Analysis of Trimer Isomers Formed by Montmorillonite Catalysis in the Reaction of Binary Monomer Mixtures

    NASA Astrophysics Data System (ADS)

    Ertem, Gözen; Hazen, Robert M.; Dworkin, Jason P.

    2007-10-01

    Oligonucleotides are structurally similar to short RNA strands. Therefore, their formation via non-enzymatic reactions is highly relevant to Gilbert's RNA world scenario (1986) and the origin of life. In laboratory synthesis of oligonucleotides from monomers, it is necessary to remove the water molecules from the reaction medium to shift the equilibrium in favor of oligonucleotide formation, which would have been impossible for reactions that took place in dilute solutions on the early Earth. Model studies designed to address this problem demonstrate that montmorillonite, a phyllosilicate common on Earth and identified on Mars, efficiently catalyzes phosphodiester-bond formation between activated mononucleotides in dilute solutions and produces RNA-like oligomers. The purpose of this study was to examine the sequences and regiospecificity of trimer isomers formed in the reaction of 5'-phosphorimidazolides of adenosine and uridine. Results demonstrated that regiospecificity and sequence specificity observed in the dimer fractions are conserved in their elongation products. With regard to regiospecificity, 61% of the linkages were found to be RNA-like 3',5'-phosphodiester bonds. With regard to sequence specificity, we found that 88% of the linear trimers were hetero-isomers with 61% A-monomer and 39% U-monomer incorporation. These results lend support to Bernal's hypothesis that minerals may have played a significant role in the chemical processes that led to the origin of life by catalyzing the formation of phosphodiester bonds in RNA-like oligomers.

  14. Involvement of ferryl in the reaction between nitrite and the oxy forms of globins.

    PubMed

    Hathazi, Denisa; Mahuţ, Sonia Diana; Scurtu, Florina-Violeta; Bischin, Cristina; Stanciu, Corina; Attia, Amr Ali; Damian, Grigore; Silaghi-Dumitrescu, Radu

    2014-10-01

    The reaction between nitrite and the oxy forms of globins has complex autocatalytic kinetics with several branching steps and evolves through chain reactions mediated by reactive species (including radicals) such as hydrogen peroxide, ferryl and nitrogen dioxide, starting with a lag phase, after which it proceeds onto an autocatalytic phase. Reported here are UV-Vis spectra collected upon stopped-flow mixing of myoglobin with a supraphysiological excess of nitrite. The best fit to the experimental data follows an A → B → C reaction scheme involving the formation of a short-lived intermediate identified as ferryl. This is consistent with a mechanism where nitrite binds to oxy myoglobin to generate an undetectable ferrous-peroxynitrate intermediate, whose decay leads to nitrate and ferryl. The ferryl is then reduced to met by the excess nitrite. DFT calculations reveal an essentially barrierless reaction between nitrite and the oxy heme, with a notable outer-sphere component; the resulting metastable ferrous-peroxynitrate adduct is found to feature a very low barrier towards nitrate liberation, with ferryl as a final product-in good agreement with experiment. PMID:25064750

  15. Asymmetric ion trap

    DOEpatents

    Barlow, Stephan E.; Alexander, Michael L.; Follansbee, James C.

    1997-01-01

    An ion trap having two end cap electrodes disposed asymmetrically about a center of a ring electrode. The inner surface of the end cap electrodes are conformed to an asymmetric pair of equipotential lines of the harmonic formed by the application of voltages to the electrodes. The asymmetry of the end cap electrodes allows ejection of charged species through the closer of the two electrodes which in turn allows for simultaneously detecting anions and cations expelled from the ion trap through the use of two detectors charged with opposite polarity.

  16. Asymmetric ion trap

    DOEpatents

    Barlow, S.E.; Alexander, M.L.; Follansbee, J.C.

    1997-12-02

    An ion trap having two end cap electrodes disposed asymmetrically about a center of a ring electrode is disclosed. The inner surface of the end cap electrodes are conformed to an asymmetric pair of equipotential lines of the harmonic formed by the application of voltages to the electrodes. The asymmetry of the end cap electrodes allows ejection of charged species through the closer of the two electrodes which in turn allows for simultaneously detecting anions and cations expelled from the ion trap through the use of two detectors charged with opposite polarity. 4 figs.

  17. Characteristics of HgS nanoparticles formed in hair by a chemical reaction

    NASA Astrophysics Data System (ADS)

    Patriarche, G.; Walter, P.; Van Elslande, E.; Ayache, J.; Castaing, J.

    2013-01-01

    A chemical reaction, derived from an ancient recipe for hair dyeing, is used to precipitate nanoparticles of mercury sulphide in hair by the simple process of immersion in a water solution of Ca(OH)2 and HgO. After several days, HgS nanoparticles appear throughout the hair and are particularly numerous in the various interfaces. The formation of these nanoparticles has been studied by analytical and atomic resolution electron microscopy. High resolution quantitative analysis allowed the determination of two varieties of HgS precipitate crystal structures formed: a hexagonal cinnabar and a cubic metacinnabar structure. This very simple process of a chemical reaction in hair is a particularly inexpensive way to fabricate semiconductor sulphide nanoparticles with specific properties.

  18. Asymmetrical field emitter

    DOEpatents

    Fleming, James G.; Smith, Bradley K.

    1995-01-01

    Providing a field emitter with an asymmetrical emitter structure having a very sharp tip in close proximity to its gate. One preferred embodiment of the present invention includes an asymmetrical emitter and a gate. The emitter having a tip and a side is coupled to a substrate. The gate is connected to a step in the substrate. The step has a top surface and a side wall that is substantially parallel to the side of the emitter. The tip of the emitter is in close proximity to the gate. The emitter is at an emitter potential, and the gate is at a gate potential such that with the two potentials at appropriate values, electrons are emitted from the emitter. In one embodiment, the gate is separated from the emitter by an oxide layer, and the emitter is etched anisotropically to form its tip and its asymmetrical structure.

  19. Asymmetrical field emitter

    DOEpatents

    Fleming, J.G.; Smith, B.K.

    1995-10-10

    A method is disclosed for providing a field emitter with an asymmetrical emitter structure having a very sharp tip in close proximity to its gate. One preferred embodiment of the present invention includes an asymmetrical emitter and a gate. The emitter having a tip and a side is coupled to a substrate. The gate is connected to a step in the substrate. The step has a top surface and a side wall that is substantially parallel to the side of the emitter. The tip of the emitter is in close proximity to the gate. The emitter is at an emitter potential, and the gate is at a gate potential such that with the two potentials at appropriate values, electrons are emitted from the emitter. In one embodiment, the gate is separated from the emitter by an oxide layer, and the emitter is etched anisotropically to form its tip and its asymmetrical structure. 17 figs.

  20. Cold asymmetrical fermion superfluids

    SciTech Connect

    Caldas, Heron

    2003-12-19

    The recent experimental advances in cold atomic traps have induced a great amount of interest in fields from condensed matter to particle physics, including approaches and prospects from the theoretical point of view. In this work we investigate the general properties and the ground state of an asymmetrical dilute gas of cold fermionic atoms, formed by two particle species having different densities. We have show in a recent paper, that a mixed phase composed of normal and superfluid components is the energetically favored ground state of such a cold fermionic system. Here we extend the analysis and verify that in fact, the mixed phase is the preferred ground state of an asymmetrical superfluid in various situations. We predict that the mixed phase can serve as a way of detecting superfluidity and estimating the magnitude of the gap parameter in asymmetrical fermionic systems.

  1. An experimental and computational study of the ions formed by the reaction of cyclopentanone with O-

    NASA Astrophysics Data System (ADS)

    Hoenigman, Rebecca L.; Kato, Shuji; Borden, Weston Thatcher; Bierbaum, Veronica M.

    2005-03-01

    The structures and reactivities of the ions formed by the reaction of cyclopentanone with O- have been studied using flowing afterglow-selected ion flow tube (FA-SIFT) experiments in conjunction with density functional theory (DFT) calculations. Three C5H6O- isomers were found to be generated - cyclopentanone-2,5-diyl radical anion (4-), 2-carbenacyclopentanone radical anion (5-), and cyclopentanone-2,4-diyl radical anion (6-). The large amount of signal loss observed in this reaction is attributed to formation of 2-cyclopentenone radical anion (10-), in which the electron is predicted to be unbound. DFT calculations predict 4- to be the most stable of the bound C5H6O- ions, and FA-SIFT experiments confirm 4- is the major ion formed in this reaction. Bracketing experiments found the proton affinity (PA) of 4- to be 362 +/- 5 kcal/mol and the electron binding energy (EBE) to be ca. 0.5 eV. Although the PA of this species predicted by DFT calculations (363.2 kcal/mol) is consistent with the experimental value, both DFT and ab initio calculations predict an EBE of ca. 1.6 eV for this radical anion. The apparent conflict between the calculated and experimental EBE is resolved by proposing that, in the gas phase bracketing experiments, the electron transfer process leads adiabatically, not to cyclopentanone-2,5-diyl (4), but, by a retro-Nazarov reaction, to the more stable 1,4-pentadien-3-one (18). DFT calculations show that the difference between the computed and measured EBEs of 4- can be accounted for by the calculated difference between the energies of 18 and 4.

  2. Reaction-Forming Method for Producing Near Net-Shape Refractory Metal Carbides

    SciTech Connect

    Palmisiano, Marc N.; Jakubenas, Kevin J.; Baranwal, Rita

    2004-07-20

    A method for reaction forming refractory metal carbides. The method involves the fabrication of a glassy carbon preform by casting an organic, resin-based liquid mixture into a mold and subsequently heat treating it in two steps, which cures and pyrolizes the resin resulting in a porous carbon preform. By varying the amounts of the constituents in the organic, resin-based liquid mixture, control over the density of the carbon preform is obtained. Control of the density and microstructure of the carbon preform allows for determination of the microstructure and properties of the refractory metal carbide material produced. The glassy carbon preform is placed on a bed of refractory metal or refractory metal--silicon alloy. The pieces are heated above the melting point of the metal or alloy. The molten metal wicks inside the porous carbon preform and reacts, forming the refractory metal carbide or refractory metal carbide plus a minor secondary phase.

  3. Radiation reaction on a classical charged particle: a modified form of the equation of motion.

    PubMed

    Alcaine, Guillermo García; Llanes-Estrada, Felipe J

    2013-09-01

    We present and numerically solve a modified form of the equation of motion for a charged particle under the influence of an external force, taking into account the radiation reaction. This covariant equation is integro-differential, as Dirac-Röhrlich's, but has several technical improvements. First, the equation has the form of Newton's second law, with acceleration isolated on the left hand side and the force depending only on positions and velocities: Thus, the equation is linear in the highest derivative. Second, the total four-force is by construction perpendicular to the four-velocity. Third, if the external force vanishes for all future times, the total force and the acceleration automatically vanish at the present time. We show the advantages of this equation by solving it numerically for several examples of external force. PMID:24125376

  4. Radiation reaction on a classical charged particle: A modified form of the equation of motion

    NASA Astrophysics Data System (ADS)

    Alcaine, Guillermo García; Llanes-Estrada, Felipe J.

    2013-09-01

    We present and numerically solve a modified form of the equation of motion for a charged particle under the influence of an external force, taking into account the radiation reaction. This covariant equation is integro-differential, as Dirac-Röhrlich's, but has several technical improvements. First, the equation has the form of Newton's second law, with acceleration isolated on the left hand side and the force depending only on positions and velocities: Thus, the equation is linear in the highest derivative. Second, the total four-force is by construction perpendicular to the four-velocity. Third, if the external force vanishes for all future times, the total force and the acceleration automatically vanish at the present time. We show the advantages of this equation by solving it numerically for several examples of external force.

  5. Radiation reaction on a classical charged particle: a modified form of the equation of motion.

    PubMed

    Alcaine, Guillermo García; Llanes-Estrada, Felipe J

    2013-09-01

    We present and numerically solve a modified form of the equation of motion for a charged particle under the influence of an external force, taking into account the radiation reaction. This covariant equation is integro-differential, as Dirac-Röhrlich's, but has several technical improvements. First, the equation has the form of Newton's second law, with acceleration isolated on the left hand side and the force depending only on positions and velocities: Thus, the equation is linear in the highest derivative. Second, the total four-force is by construction perpendicular to the four-velocity. Third, if the external force vanishes for all future times, the total force and the acceleration automatically vanish at the present time. We show the advantages of this equation by solving it numerically for several examples of external force.

  6. Interfacial thiol-ene photo-click reactions for forming multilayer hydrogels

    PubMed Central

    Shih, Han; Fraser, Andrew K.; Lin, Chien-Chi

    2014-01-01

    Interfacial visible light-mediated thiol-ene photo-click reactions were developed for preparing step-growth hydrogels with multilayer structures. The effect of a non-cleavage type photoinitiator eosin-Y on visible light-mediated thiol-ene photopolymerization was first characterized using in situ photo-rheometry, gel fraction, and equilibrium swelling ratio. Next, spectrophotometric properties of eosin-Y in the presence of various relevant macromer species were evaluated using UV/Vis spectrometry. It was determined that eosin-Y was able to re-initiate thiol-ene photo-click reaction even after light exposure. Due to its small molecular weight, most eosin-Y molecules readily leached out from the hydrogels. The diffusion of residual eosin-Y from pre-formed hydrogels was exploited for fabricating multilayer step-growth hydrogels. Interfacial hydrogel coating was formed via the same visible light-mediated gelation mechanism without adding fresh initiator. The thickness of the thiol-ene gel coating could be easily controlled by adjusting visible light exposure time, eosin-Y concentration initially loaded in the core gel, or macromer concentration in the coating solution. The major benefits of this interfacial thiol-ene coating system include its simplicity and cytocompatibility. The formation of thiol-ene hydrogels and coatings neither requires nor generates any cytotoxic components. This new gelation chemistry may have great utilities in controlled release of multiple sensitive growth factors and encapsulation of multiple cell types for tissue regeneration. PMID:23384151

  7. Designing a national combined reporting form for adverse drug reactions and medication errors.

    PubMed

    Tanti, A; Serracino-Inglott, A; Borg, J J

    2015-06-09

    The Maltese Medicines Authority was tasked with developing a reporting form that captures high-quality case information on adverse drug reactions (ADRs) and medication errors in order to fulfil its public-health obligations set by the European Union (EU) legislation on pharmacovigilance. This paper describes the process of introducing the first combined ADR/medication error reporting form in the EU for health-care professionals, the analysis of reports generated by it and the promotion of the system. A review of existing ADR forms was carried out and recommendations from the European Medicines Agency and World Health Organization audits integrated. A new, combined ADR/medication error reporting form was developed and pilot tested based on case studies. The Authority's quality system (ISO 9001 certified) was redesigned and a promotion strategy was deployed. The process used in Malta can be useful for countries that need to develop systems relative to ADR/medication error reporting and to improve the quality of data capture within their systems.

  8. Asymmetric photoredox transition-metal catalysis activated by visible light

    NASA Astrophysics Data System (ADS)

    Huo, Haohua; Shen, Xiaodong; Wang, Chuanyong; Zhang, Lilu; Röse, Philipp; Chen, Liang-An; Harms, Klaus; Marsch, Michael; Hilt, Gerhard; Meggers, Eric

    2014-11-01

    Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest. Photoredox catalysis provides the opportunity to generate highly reactive radical ion intermediates with often unusual or unconventional reactivities under surprisingly mild reaction conditions. In such systems, photoactivated sensitizers initiate a single electron transfer from (or to) a closed-shell organic molecule to produce radical cations or radical anions whose reactivities are then exploited for interesting or unusual chemical transformations. However, the high reactivity of photoexcited substrates, intermediate radical ions or radicals, and the low activation barriers for follow-up reactions provide significant hurdles for the development of efficient catalytic photochemical processes that work under stereochemical control and provide chiral molecules in an asymmetric fashion. Here we report a highly efficient asymmetric catalyst that uses visible light for the necessary molecular activation, thereby combining asymmetric catalysis and photocatalysis. We show that a chiral iridium complex can serve as a sensitizer for photoredox catalysis and at the same time provide very effective asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles. This new asymmetric photoredox catalyst, in which the metal centre simultaneously serves as the exclusive source of chirality, the catalytically active Lewis acid centre, and the photoredox centre, offers new opportunities for the `green' synthesis of non-racemic chiral molecules.

  9. Characterization of the selenotrisulfide formed by reaction of selenite with end-capped phytochelatin-2.

    PubMed

    Spain, Stephen M; Rabenstein, Dallas L

    2004-03-01

    The phytochelatins are a family of peptides synthesized by plants in response to exposure to heavy metals and metalloids, including selenium in the form of selenite. The amino acid sequence of the phytochelatin (PC) peptides is (gamma-Glu-Cys)n-Gly, where n typically ranges from 2 to 5. In this paper, the products of the reaction of selenite with an end-capped analogue of PC2, Ac-(gamma-Glu-Cys)2-Gly-NH2, are characterized. Selenite reacts with Ac-(gamma-Glu-Cys)2-Gly-NH2 (Ac-PC2-NH2) to form a compound that contains an intramolecular selenotrisulfide (-SSeS-)-linkage (Se[Ac-PC2-NH2]) and oxidized Ac-PC2-NH2. Both Se[Ac-PC2-NH2] and oxidized Ac-PC2-NH2 were isolated by HPLC and were characterized by MALDI-TOF mass spectrometry, by two-dimensional 1H and 13C NMR and, in the case of Se[Ac-PC2-NH2], by 77Se NMR. Using dihedral angles determined from vicinal 1H-1H coupling constants as constraints for the conformations around the Cys(CalphaH)-Cys(CbetaH) bonds, structures were predicted for the most abundant form of both compounds by Monte Carlo molecular mechanics simulations. PMID:15214417

  10. Hydroxamic Acids in Asymmetric Synthesis

    PubMed Central

    Li, Zhi; Yamamoto, Hisashi

    2012-01-01

    Metal-catalyzed stereoselective reactions are a central theme in organic chemistry research. In these reactions, the stereoselection is achieved predominantly by introducing chiral ligands at the metal catalyst’s center. For decades, researchers have sought better chiral ligands for asymmetric catalysis and have made great progress. Nevertheless, to achieve optimal stereoselectivity and to catalyze new reactions, new chiral ligands are needed. Due to their high metal affinity, hydroxamic acids play major roles across a broad spectrum of fields from biochemistry to metal extraction. Dr. K. Barry Sharpless first revealed their potential as chiral ligands for asymmetric synthesis in 1977: He published the chiral vanadium-hydroxamic-acid-catalyzed, enantioselective epoxidation of allylic alcohols before his discovery of Sharpless Asymmetric Epoxidation, which uses titanium-tartrate complex as the chiral reagent. However, researchers have reported few highly enantioselective reactions using metal-hydroxamic acid as catalysts since then. This Account summarizes our research on metal-catalyzed asymmetric epoxidation using hydroxamic acids as chiral ligands. We designed and synthesized a series of new hydroxamic acids, most notably the C2-symmetric bis-hydroxamic acid (BHA) family. V-BHA-catalyzed epoxidation of allylic and homoallylic alcohols achieved higher activity and stereoselectivity than Sharpless Asymmetric Epoxidation in many cases. Changing the metal species led to a series of unprecedented asymmetric epoxidation reactions, such as (i) single olefins and sulfides with Mo-BHA, (ii) homoallylic and bishomoallylic alcohols with Zr- and Hf-BHA, and (iii) N-alkenyl sulfonamides and N-sulfonyl imines with Hf-BHA. These reactions produce uniquely functionalized chiral epoxides with good yields and enantioselectivities. PMID:23157425

  11. Complete magnesiothermic reduction reaction of vertically aligned mesoporous silica channels to form pure silicon nanoparticles

    NASA Astrophysics Data System (ADS)

    Kim, Kyoung Hwan; Lee, Dong Jin; Cho, Kyeong Min; Kim, Seon Joon; Park, Jung-Ki; Jung, Hee-Tae

    2015-03-01

    Owing to its simplicity and low temperature conditions, magnesiothermic reduction of silica is one of the most powerful methods for producing silicon nanostructures. However, incomplete reduction takes place in this process leaving unconverted silica under the silicon layer. This phenomenon limits the use of this method for the rational design of silicon structures. In this effort, a technique that enables complete magnesiothermic reduction of silica to form silicon has been developed. The procedure involves magnesium promoted reduction of vertically oriented mesoporous silica channels on reduced graphene oxides (rGO) sheets. The mesopores play a significant role in effectively enabling magnesium gas to interact with silica through a large number of reaction sites. Utilizing this approach, highly uniform, ca. 10 nm sized silicon nanoparticles are generated without contamination by unreacted silica. The new method for complete magnesiothermic reduction of mesoporous silica approach provides a foundation for the rational design of silicon structures.

  12. High-temperature oxidation behavior of reaction-formed silicon carbide ceramics

    NASA Technical Reports Server (NTRS)

    Ogbuji, Linus U. J. T.; Singh, M.

    1995-01-01

    The oxidation behavior of reaction-formed silicon carbide (RFSC) ceramics was investigated in the temperature range of 1100 to 1400 C. The oxidation weight change was recorded by TGA; the oxidized materials were examined by light and electron microscopy, and the oxidation product by x-ray diffraction analysis (XRD). The materials exhibited initial weight loss, followed by passive weight gain (with enhanced parabolic rates, k(sub p)), and ending with a negative (logarithmic) deviation from the parabolic law. The weight loss arose from the oxidation of residual carbon, and the enhanced k(sub p) values from internal oxidation and the oxidation of residual silicon, while the logarithmic kinetics is thought to have resulted from crystallization of the oxide. The presence of a small amount of MoSi, in the RFSC material caused a further increase in the oxidation rate. The only solid oxidation product for all temperatures studied was silica.

  13. Microstructural Characterization of Reaction-Formed Silicon Carbide Ceramics. Materials Characterization

    NASA Technical Reports Server (NTRS)

    Singh, M.; Leonhardt, T. A.

    1995-01-01

    Microstructural characterization of two reaction-formed silicon carbide ceramics has been carried out by interference layering, plasma etching, and microscopy. These specimens contained free silicon and niobium disilicide as minor phases with silicon carbide as the major phase. In conventionally prepared samples, the niobium disilicide cannot be distinguished from silicon in optical micrographs. After interference layering, all phases are clearly distinguishable. Back scattered electron (BSE) imaging and energy dispersive spectrometry (EDS) confirmed the results obtained by interference layering. Plasma etching with CF4 plus 4% O2 selectively attacks silicon in these specimens. It is demonstrated that interference layering and plasma etching are very useful techniques in the phase identification and microstructural characterization of multiphase ceramic materials.

  14. Complete magnesiothermic reduction reaction of vertically aligned mesoporous silica channels to form pure silicon nanoparticles

    PubMed Central

    Kim, Kyoung Hwan; Lee, Dong Jin; Cho, Kyeong Min; Kim, Seon Joon; Park, Jung-Ki; Jung, Hee-Tae

    2015-01-01

    Owing to its simplicity and low temperature conditions, magnesiothermic reduction of silica is one of the most powerful methods for producing silicon nanostructures. However, incomplete reduction takes place in this process leaving unconverted silica under the silicon layer. This phenomenon limits the use of this method for the rational design of silicon structures. In this effort, a technique that enables complete magnesiothermic reduction of silica to form silicon has been developed. The procedure involves magnesium promoted reduction of vertically oriented mesoporous silica channels on reduced graphene oxides (rGO) sheets. The mesopores play a significant role in effectively enabling magnesium gas to interact with silica through a large number of reaction sites. Utilizing this approach, highly uniform, ca. 10 nm sized silicon nanoparticles are generated without contamination by unreacted silica. The new method for complete magnesiothermic reduction of mesoporous silica approach provides a foundation for the rational design of silicon structures. PMID:25757800

  15. Catalytic asymmetric synthesis of thiols.

    PubMed

    Monaco, Mattia Riccardo; Prévost, Sébastien; List, Benjamin

    2014-12-10

    The synthesis of enantiopure thiols is of significant interest for industrial and academic applications. However, direct asymmetric approaches to free thiols have previously been unknown. Here we describe a novel organocascade that is catalyzed by a confined chiral phosphoric acid and furnishes O-protected β-hydroxythiols with excellent enantioselectivities. The method relies on an asymmetric thiocarboxylysis of meso-epoxides, followed by an intramolecular trans-esterification reaction. By varying the reaction conditions, the intermediate thioesters can also be obtained chemoselectively and enantioselectively.

  16. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 2: aldol, Mannich addition reactions, deracemization and (S) to (R) interconversion of α-amino acids.

    PubMed

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim

    2013-11-01

    This review provides a comprehensive treatment of literature data dealing with asymmetric synthesis of α-amino-β-hydroxy and α,β-diamino acids via homologation of chiral Ni(II) complexes of glycine Schiff bases using aldol and Mannich-type reactions. These reactions proceed with synthetically useful chemical yields and thermodynamically controlled stereoselectivity and allow direct introduction of two stereogenic centers in a single operation with predictable stereochemical outcome. Furthermore, new application of Ni(II) complexes of α-amino acids Schiff bases for deracemization of racemic α-amino acids and (S) to (R) interconversion providing additional synthetic opportunities for preparation of enantiomerically pure α-amino acids, is also reviewed. Origin of observed diastereo-/enantioselectivity in the aldol, Mannich-type and deracemization reactions, generality and limitations of these methodologies are critically discussed.

  17. Non-stabilized nucleophiles in Cu-catalysed dynamic kinetic asymmetric allylic alkylation

    NASA Astrophysics Data System (ADS)

    You, Hengzhi; Rideau, Emeline; Sidera, Mireia; Fletcher, Stephen P.

    2015-01-01

    The development of new reactions forming asymmetric carbon-carbon bonds has enabled chemists to synthesize a broad range of important carbon-containing molecules, including pharmaceutical agents, fragrances and polymers. Most strategies to obtain enantiomerically enriched molecules rely on either generating new stereogenic centres from prochiral substrates or resolving racemic mixtures of enantiomers. An alternative strategy--dynamic kinetic asymmetric transformation--involves the transformation of a racemic starting material into a single enantiomer product, with greater than 50 per cent maximum yield. The use of stabilized nucleophiles (pKa < 25, where Ka is the acid dissociation constant) in palladium-catalysed asymmetric allylic alkylation reactions has proved to be extremely versatile in these processes. Conversely, the use of non-stabilized nucleophiles in such reactions is difficult and remains a key challenge. Here we report a copper-catalysed dynamic kinetic asymmetric transformation using racemic substrates and alkyl nucleophiles. These nucleophiles have a pKa of >=50, more than 25 orders of magnitude more basic than the nucleophiles that are typically used in such transformations. Organometallic reagents are generated in situ from alkenes by hydrometallation and give highly enantioenriched products under mild reaction conditions. The method is used to synthesize natural products that possess activity against tuberculosis and leprosy, and an inhibitor of para-aminobenzoate biosynthesis. Mechanistic studies indicate that the reaction proceeds through a rapidly isomerizing intermediate. We anticipate that this approach will be a valuable complement to existing asymmetric catalytic methods.

  18. Fundamental study of ammonia-sulfur dioxide reactions to form solid particles. Final report

    SciTech Connect

    Biswas, P.; Bai, H.

    1994-01-18

    The effects of reaction residence time, presence of inert particles and moisture content on the SO{sub 2} removal and the product particle size distributions have been determined. Results indicated that both gas phase and particle phase reach equilibria in a very short time. The presence of inert particles increases the SO{sub 2} removal efficiency slightly, with a greater increase in removal efficiency at higher surface areas. Moisture content is the most important parameter affecting SO{sub 2} removal. Increasing the moisture content from 1.6% to 6.4% by volume results in a 30% increase of the SO{sub 2} removal at a reaction temperature of 51{degree}C. The products at near anhydrous conditions were concluded to be NH{sub 3}SO{sub 2}, (NH{sub 3}){sub 2}SO{sub 2} and (NH{sub 4}){sub 2}S{sub 2}O{sub 5}. While the products at humid conditions could be either the 1:1 sulfites, NH{sub 4}HSO{sub 3} and (NH{sub 4}){sub 2}S{sub 2}O{sub 5}, or the 2:1 sulfites, (NH{sub 4}){sub 2}SO{sub 3} and (NH{sub 4}){sub 2}SO{sub 3} {minus}H{sub 2}O, or a mixture of the 1:1 and 2:1 sulfite. Those sulfite particles could subsequently oxidize to form the more stable sulfate particles. A gas-to-particle formation model has been developed to simulate the NH{sub 3}-SO{sub 2} system in the presence and absence of seed aerosols at trace water conditions. This model accounts for simultaneous nucleation, coagulation, condensation and chemical reaction. The applicability of utilizing ammonia injection to a flue gas system has been discussed in terms of two possible removal schemes. One utilizes ammonia injection alone and the other is in conjunction with the injection of Ca(OH){sub 2} slurry in a spray dryer system. Both schemes have the potential of achieving over 90% SO{sub 2} removal from power plants burning high-sulfur coals.

  19. Kinetics and Mechanism of Deoxygenation Reactions over Proton-Form and Molybdenum-Modified Zeolite Catalysts

    NASA Astrophysics Data System (ADS)

    Bedard, Jeremy William

    The depletion of fossil fuel resources and the environmental consequences of their use have dictated the development of new sources of energy that are both sustainable and economical. Biomass has emerged as a renewable carbon feedstock that can be used to produce chemicals and fuels traditionally obtained from petroleum. The oxygen content of biomass prohibits its use without modification because oxygenated hydrocarbons are non-volatile and have lower energy content. Chemical processes that eliminate oxygen and keep the carbon backbone intact are required for the development of biomass as a viable chemical feedstock. This dissertation reports on the kinetic and mechanistic studies conducted on high and low temperature catalytic processes for deoxygenation of biomass precursors to produce high-value chemicals and fuels. Low temperature, steady state reaction studies of acetic acid and ethanol were used to identify co-adsorbed acetic acid/ethanol dimers as surface intermediates within specific elementary steps involved in the esterification of acetic acid with ethanol on zeolites. A reaction mechanism involving two dominating surface species, an inactive ethanol dimeric species adsorbed on Bronsted sites inhibiting ester formation and a co-adsorbed complex of acetic acid and ethanol on the active site reacting to produce ethyl acetate, is shown to describe the reaction rate as a function of temperature (323 -- 383 K), acetic acid (0.5 -- 6.0 kPa), and ethanol (5.0 -- 13.0 kPa) partial pressure on proton-form BEA, FER, MFI, and MOR zeolites. Measured differences in rates as a function of zeolite structure and the rigorous interpretation of these differences in terms of esterification rate and equilibrium constants is presented to show that the intrinsic rate constant for the activation of the co-adsorbed complex increases in the order FER < MOR < MFI < BEA. High temperature co-processing of acetic acid, formic acid, or carbon dioxide with methane (CH3COOH/CH4 = 0

  20. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach

    PubMed Central

    Chauhan, Pankaj

    2012-01-01

    Summary Ball-milling and pestle and mortar grinding have emerged as powerful methods for the development of environmentally benign chemical transformations. Recently, the use of these mechanochemical techniques in asymmetric organocatalysis has increased. This review highlights the progress in asymmetric organocatalytic reactions assisted by mechanochemical techniques. PMID:23243475

  1. Direct asymmetric dearomatization of 2-naphthols by scandium-catalyzed electrophilic amination.

    PubMed

    Nan, Jiang; Liu, Jingjing; Zheng, Huayu; Zuo, Zhijun; Hou, Lei; Hu, Huaiming; Wang, Yaoyu; Luan, Xinjun

    2015-02-16

    Catalytic asymmetric aminative dearomatization of 1-substituted 2-naphthols was successfully implemented with electrophilic azodicarboxylates under the catalysis of chiral Sc(III)/pybox complexes. This intermolecular reaction represents a hitherto unknown enantioselective C-N bond-forming process through direct dearomatization of phenolic compounds to generate chiral nitrogen-containing quaternary carbon stereocenters.

  2. Catalytic asymmetric bromochlorination of aromatic allylic alcohols promoted by multifunctional Schiff base ligands.

    PubMed

    Huang, Wei-Sheng; Chen, Li; Zheng, Zhan-Jiang; Yang, Ke-Fang; Xu, Zheng; Cui, Yu-Ming; Xu, Li-Wen

    2016-08-16

    It was found that the tridentate O,N,O-type Schiff base ligand bearing suitable substituents was a highly effective promoter in the catalytic asymmetric bromochlorination reaction, in which the corresponding aromatic bromochloroalcohols with vicinal halogen-bearing stereocenters were formed with perfect regioselectivity, with moderate to excellent enantioselectivities (up to 93% ee), and with good yields and chemoselectivities. PMID:27488387

  3. Reaction Kinetics of Primary Rock-forming Minerals under Ambient Conditions

    NASA Astrophysics Data System (ADS)

    Brantley, S. L.

    2003-12-01

    Mineral dissolution kinetics influence such phenomena as development of soil fertility, amelioration of the effects of acid rain, formation of karst, acid mine drainage, transport and sequestration of contaminants, sequestration of carbon dioxide at depth in the earth, ore deposition, and metamorphism. On a global basis, mineral weathering kinetics are also involved in the long-term sink for CO2 in the atmosphere:CaSiO3+CO2=CaCO3+SiO2(1)MgSiO3+CO2=MgCO3+SiO2(2)These reactions (Urey, 1952) describe the processes that balance the volcanic and metamorphic CO2 production to maintain relatively constant levels of atmospheric CO2 over 105-106 yr timescales. In these equations, Ca- and MgSiO3 represent all calcium- and magnesium-containing silicates. Calcium- and magnesium-silicates at the Earth's surface are predominantly plagioclase feldspars, Ca-Mg-pyroxenes, amphiboles, and phyllosilicates, Ca-Mg orthosilicates. Although dissolution of the other main rock-forming mineral class, carbonate minerals, does not draw down CO2 from the atmosphere over geologic timescales, carbonate dissolution is globally important in controlling river and ground water chemistry.Despite the importance of mineral dissolution, field weathering rates are generally observed to be up to five orders of magnitude slower than laboratory dissolution rates (White, 1995), and the reason for this discrepancy remains a puzzle. For example, mean lifetimes of 1 mm spheres of rock-forming minerals calculated from measured rate data following Lasaga (1984) are much smaller than the mean half-life of sedimentary rocks (600 My, Garrels and Mackenzie, 1971). As pointed out by others ( Velbel, 1993a), the order of stability of minerals calculated from measured dissolution kinetics ( Table 1) generally follow weathering trends observed in the field (e.g., Goldich, 1938) with some exceptions. Some have suggested that quantitative prediction of field rates will be near-impossible, although such rate trends may be

  4. Application of micro X-ray diffraction to investigate the reaction products formed by the alkali silica reaction in concrete structures

    SciTech Connect

    Dähn, R.; Arakcheeva, A.; Schaub, Ph.; Pattison, P.; Chapuis, G.; Grolimund, D.; Wieland, E.; Leemann, A.

    2015-12-21

    Alkali–silica reaction (ASR) is one of the most important deterioration mechanisms in concrete leading to substantial damages of structures worldwide. Synchrotron-based micro-X-ray diffraction (micro-XRD) was employed to characterize the mineral phases formed in micro-cracks of concrete aggregates as a consequence of ASR. This particular high spatial resolution technique enables to directly gain structural information on ASR products formed in a 40-year old motorway bridge damaged due to ASR. Micro-X-ray-fluorescence was applied on thin sections to locate the reaction products formed in veins within concrete aggregates. Micro-XRD pattern were collected at selected points of interest along a vein by rotating the sample. Rietveld refinement determined the structure of the ASR product consisting of a new layered framework similar to mountainite and rhodesite. Furthermore, it is conceivable that understanding the structure of the ASR product may help developing new technical treatments inhibiting ASR.

  5. Reactions of the alkoxy radicals formed following OH-addition to alpha-pinene and beta-pinene. C-C bond scission reactions.

    PubMed

    Dibble, T S

    2001-05-01

    The atmospheric degradation pathways of the atmospherically important terpenes alpha-pinene and beta-pinene are studied using density functional theory. We employ the correlation functional of Lee, Yang, and Parr and the three-parameter HF exchange functional of Becke (B3LYP) together with the 6-31G(d) basis set. The C-C bond scission reactions of the beta-hydroxyalkoxy radicals that are formed after OH addition to alpha-pinene and beta-pinene are investigated. Both of the alkoxy radicals formed from the alpha-pinene-OH adduct possess a single favored C-C scission pathway with an extremely low barrier (approximately 3 kcal/mol) leading to the formation of pinonaldehyde. Neither of these pathways produces formaldehyde, and preliminary computational results offer some support for suggestions that 1,5 or 1,6 H-shift (isomerization) reactions of alkoxy radicals contribute to formaldehyde production. In the case of the alkoxy radical formed following OH addition to the methylene group of beta-pinene, there exists two C-C scission reactions with nearly identical barrier heights (approximately 7.5 kcal/mol); one leads to known products (nopinone and formaldehyde) but the ultimate products of the competing reaction are unknown. The single C-C scission pathway of the other alkoxy radical from beta-pinene possesses a very low (approximately 4 kcal/mol) barrier. The kinetically favored C-C scission reactions of all four alkoxy radicals appear to be far faster than expected rates of reaction with O2. The rearrangement of the alpha-pinene-OH adduct, a key step in the proposed mechanism of formation of acetone from alpha-pinene, is determined to possess a barrier of 11.6 kcal/mol. This value is consistent with another computational result and is broadly consistent with the modest acetone yields observed in product yield studies.

  6. Origin of Nanobubbles Electrochemically Formed in a Magnetic Field: Ionic Vacancy Production in Electrode Reaction

    PubMed Central

    Aogaki, Ryoichi; Sugiyama, Atsushi; Miura, Makoto; Oshikiri, Yoshinobu; Miura, Miki; Morimoto, Ryoichi; Takagi, Satoshi; Mogi, Iwao; Yamauchi, Yusuke

    2016-01-01

    As a process complementing conventional electrode reactions, ionic vacancy production in electrode reaction was theoretically examined; whether reaction is anodic or cathodic, based on the momentum conservation by Newton’s second law of motion, electron transfer necessarily leads to the emission of original embryo vacancies, and dielectric polarization endows to them the same electric charge as trans- ferred in the reaction. Then, the emitted embryo vacancies immediately receive the thermal relaxation of solution particles to develop steady-state vacancies. After the vacancy production, nanobubbles are created by the collision of the vacancies in a vertical magnetic field. PMID:27377532

  7. Origin of Nanobubbles Electrochemically Formed in a Magnetic Field: Ionic Vacancy Production in Electrode Reaction.

    PubMed

    Aogaki, Ryoichi; Sugiyama, Atsushi; Miura, Makoto; Oshikiri, Yoshinobu; Miura, Miki; Morimoto, Ryoichi; Takagi, Satoshi; Mogi, Iwao; Yamauchi, Yusuke

    2016-01-01

    As a process complementing conventional electrode reactions, ionic vacancy production in electrode reaction was theoretically examined; whether reaction is anodic or cathodic, based on the momentum conservation by Newton's second law of motion, electron transfer necessarily leads to the emission of original embryo vacancies, and dielectric polarization endows to them the same electric charge as trans- ferred in the reaction. Then, the emitted embryo vacancies immediately receive the thermal relaxation of solution particles to develop steady-state vacancies. After the vacancy production, nanobubbles are created by the collision of the vacancies in a vertical magnetic field. PMID:27377532

  8. Origin of Nanobubbles Electrochemically Formed in a Magnetic Field: Ionic Vacancy Production in Electrode Reaction

    NASA Astrophysics Data System (ADS)

    Aogaki, Ryoichi; Sugiyama, Atsushi; Miura, Makoto; Oshikiri, Yoshinobu; Miura, Miki; Morimoto, Ryoichi; Takagi, Satoshi; Mogi, Iwao; Yamauchi, Yusuke

    2016-07-01

    As a process complementing conventional electrode reactions, ionic vacancy production in electrode reaction was theoretically examined; whether reaction is anodic or cathodic, based on the momentum conservation by Newton’s second law of motion, electron transfer necessarily leads to the emission of original embryo vacancies, and dielectric polarization endows to them the same electric charge as trans- ferred in the reaction. Then, the emitted embryo vacancies immediately receive the thermal relaxation of solution particles to develop steady-state vacancies. After the vacancy production, nanobubbles are created by the collision of the vacancies in a vertical magnetic field.

  9. Origin of Nanobubbles Electrochemically Formed in a Magnetic Field: Ionic Vacancy Production in Electrode Reaction.

    PubMed

    Aogaki, Ryoichi; Sugiyama, Atsushi; Miura, Makoto; Oshikiri, Yoshinobu; Miura, Miki; Morimoto, Ryoichi; Takagi, Satoshi; Mogi, Iwao; Yamauchi, Yusuke

    2016-07-05

    As a process complementing conventional electrode reactions, ionic vacancy production in electrode reaction was theoretically examined; whether reaction is anodic or cathodic, based on the momentum conservation by Newton's second law of motion, electron transfer necessarily leads to the emission of original embryo vacancies, and dielectric polarization endows to them the same electric charge as trans- ferred in the reaction. Then, the emitted embryo vacancies immediately receive the thermal relaxation of solution particles to develop steady-state vacancies. After the vacancy production, nanobubbles are created by the collision of the vacancies in a vertical magnetic field.

  10. A new approach for the asymmetric total synthesis of umbelactone.

    PubMed

    Liu, Huawei; Zhang, Tao; Li, Yulin

    2006-05-01

    The asymmetric total syntheses of (R)-(+)- and (S)-(-)-umbelactone were achieved by using the Sharpless asymmetric epoxidation reaction to generate the stereogenic center and a ring-closing metathesis (RCM) for the formation of the lactone structure. Starting from 3-methyl-2-buten-1-ol, the asymmetric total synthesis was achieved in an efficient 6-step protocol with an overall yield of 16%.

  11. Asymmetric Evolutionary Games

    PubMed Central

    McAvoy, Alex; Hauert, Christoph

    2015-01-01

    Evolutionary game theory is a powerful framework for studying evolution in populations of interacting individuals. A common assumption in evolutionary game theory is that interactions are symmetric, which means that the players are distinguished by only their strategies. In nature, however, the microscopic interactions between players are nearly always asymmetric due to environmental effects, differing baseline characteristics, and other possible sources of heterogeneity. To model these phenomena, we introduce into evolutionary game theory two broad classes of asymmetric interactions: ecological and genotypic. Ecological asymmetry results from variation in the environments of the players, while genotypic asymmetry is a consequence of the players having differing baseline genotypes. We develop a theory of these forms of asymmetry for games in structured populations and use the classical social dilemmas, the Prisoner’s Dilemma and the Snowdrift Game, for illustrations. Interestingly, asymmetric games reveal essential differences between models of genetic evolution based on reproduction and models of cultural evolution based on imitation that are not apparent in symmetric games. PMID:26308326

  12. Does Nature Know Best? Pericyclic Reactions in the Daphniphyllum Alkaloid-Forming Cation Cascade.

    PubMed

    Tantillo, Dean J

    2016-09-16

    Heathcock's classic cyclization/rearrangement cascade for formation of Daphniphyllum alkaloids is subjected to analysis using density functional theory calculations. The results of these calculations are consistent with a two-step pathway involving two pericyclic reactions, a Diels-Alder cycloaddition and an ene reaction. PMID:27559932

  13. Properties of a photonic crystal formed in a solution featuring the Briggs-Rauscher oscillating reaction

    NASA Astrophysics Data System (ADS)

    Usanov, D. A.; Rytik, A. P.

    2016-06-01

    It is shown that a solution featuring the Briggs-Rauscher (BR) oscillating chemical reaction can exhibit the properties of a photonic crystal with alternating bandgap width. Thicknesses and dielectric permittivities of structural elements in the BR reaction solution have been determined by measuring the reflection and transmission spectra of microwave radiation in the range of 5-8 GHz.

  14. Microwave-assisted C-C bond forming cross-coupling reactions: an overview.

    PubMed

    Mehta, Vaibhav P; Van der Eycken, Erik V

    2011-10-01

    Among the fundamental transformations in the field of synthetic organic chemistry, transition-metal-catalyzed reactions provide some of the most attractive methodologies for the formation of C-C and C-heteroatom bonds. As a result, the application of these reactions has increased tremendously during the past decades and cross-coupling reactions became a standard tool for synthetic organic chemists. Furthermore, a tremendous upsurge in the development of new catalysts and ligands, as well as an increased understanding of the mechanisms, has contributed substantially to recent advances in the field. Traditionally, organic reactions are carried out by conductive heating with an external heat source (for example, an oil bath). However, the application of microwave irradiation is a steadily gaining field as an alternative heating mode since its dawn at the end of the last century. This tutorial review focuses on some of the recent developments in the field of cross-coupling reactions assisted by microwave irradiation.

  15. Bifunctional Asymmetric Catalysis

    PubMed Central

    PAULL, DANIEL H.; ABRAHAM, CIBY J.; SCERBA, MICHAEL T.; ALDEN-DANFORTH, ETHAN; LECTKA, THOMAS

    2008-01-01

    CONSPECTUS In the field of catalytic, asymmetric synthesis, there is a growing emphasis on multifunctional systems, in which multiple parts of a catalyst or multiple catalysts work together to promote a specific reaction. These efforts, in part, are result-driven, and they are also part of a movement toward emulating the efficiency and selectivity of nature’s catalysts, enzymes. In this Account, we illustrate the importance of bifunctional catalytic methods, focusing on the cooperative action of Lewis acidic and Lewis basic catalysts by the simultaneous activation of both electrophilic and nucleophilic reaction partners. For our part, we have contributed three separate bifunctional methods that combine achiral Lewis acids with chiral cinchona alkaloid nucleophiles, for example, benzoylquinine (BQ), to catalyze highly enantioselective cycloaddition reactions between ketene enolates and various electrophiles. Each method requires a distinct Lewis acid to coordinate and activate the electrophile, which in turn increases the reaction rates and yields, without any detectable influence on the outstanding enantioselectivities inherent to these reactions. To place our results in perspective, many important contributions to this emerging field are highlighted and our own reports are chronicled. PMID:18402470

  16. The decay of hot nuclei formed in La-induced reactions at E/A=45 MeV

    SciTech Connect

    Libby, B.

    1993-01-01

    The decay of hot nuclei formed in the reactions [sup 139]La + [sup 27]Al, [sup 51]V, [sup nat]Cu, and [sup 139]La were studied by the coincident detection of up to four complex fragments (Z > 3) emitted in these reactions. Fragments were characterized as to their atomic number, energy and in- and out-of-plane angles. The probability of the decay by an event of a given complex fragment multiplicity as a function of excitation energy per nucleon of the source is nearly independent of the system studied. Additionally, there is no large increase in the proportion of multiple fragment events as the excitation energy of the source increases past 5 MeV/nucleon. This is at odds with many prompt multifragmentation models of nuclear decay. The reactions [sup 139]La + [sup 27]Al, [sup 51]V, [sup nat]Cu were also studied by combining a dynamical model calculation that simulates the early stages of nuclear reactions with a statistical model calculation for the latter stages of the reactions. For the reaction [sup 139]La + [sup 27]Al, these calculations reproduced many of the experimental features, but other features were not reproduced. For the reaction [sup 139]La + [sup 51]V, the calculation failed to reproduce somewhat more of the experimental features. The calculation failed to reproduce any of the experimental features of the reaction [sup 139]La + [sup nat]Cu, with the exception of the source velocity distributions.

  17. The decay of hot nuclei formed in La-induced reactions at E/A=45 MeV

    SciTech Connect

    Libby, B.

    1993-05-01

    The decay of hot nuclei formed in the reactions {sup 139}La + {sup 27}Al, {sup 51}V, {sup nat}Cu, and {sup 139}La were studied by the coincident detection of up to four complex fragments (Z > 3) emitted in these reactions. Fragments were characterized as to their atomic number, energy and in- and out-of-plane angles. The probability of the decay by an event of a given complex fragment multiplicity as a function of excitation energy per nucleon of the source is nearly independent of the system studied. Additionally, there is no large increase in the proportion of multiple fragment events as the excitation energy of the source increases past 5 MeV/nucleon. This is at odds with many prompt multifragmentation models of nuclear decay. The reactions {sup 139}La + {sup 27}Al, {sup 51}V, {sup nat}Cu were also studied by combining a dynamical model calculation that simulates the early stages of nuclear reactions with a statistical model calculation for the latter stages of the reactions. For the reaction {sup 139}La + {sup 27}Al, these calculations reproduced many of the experimental features, but other features were not reproduced. For the reaction {sup 139}La + {sup 51}V, the calculation failed to reproduce somewhat more of the experimental features. The calculation failed to reproduce any of the experimental features of the reaction {sup 139}La + {sup nat}Cu, with the exception of the source velocity distributions.

  18. Electron transfer and bond-forming reactions following collisions of I2+ with CO and CS2

    NASA Astrophysics Data System (ADS)

    Fletcher, James D.; Parkes, Michael A.; Price, Stephen D.

    2015-08-01

    Collisions between I2+ and CO have been investigated using time-of-flight mass spectrometry at a range of centre-of-mass collision energies between 0.5 and 3.0 eV. Following I2++CO collisions, we detect I++CO+ from a single-electron transfer reaction and IO++C+ from bond-forming reactivity. Reaction-window calculations, based on Landau-Zener theory, have been used to rationalise the electron transfer reactivity and computational chemistry has been used to explore the [I-CO]2+ potential energy surface to account for the observation of IO+. In addition, collisions between I2+ and CS2 have been investigated over a range of centre-of-mass collision energies between 0.8 and 6.0 eV. Both single- and double-electron transfer reactions are observed in the I2+/CS2 collision system, an observation again rationalised by reaction-window theory. The monocations IS+ and IC+ are also detected following collisions of I2+ with CS2, and these ions are clearly products from a bond-forming reaction. We present a simple model based on the structure of the [I-CS2]2+ collision complex to rationalise the significantly larger yield of IS+ than IC+ in this bond-forming process.

  19. Liquid composition having ammonia borane and decomposing to form hydrogen and liquid reaction product

    DOEpatents

    Davis, Benjamin L; Rekken, Brian D

    2014-04-01

    Liquid compositions of ammonia borane and a suitably chosen amine borane material were prepared and subjected to conditions suitable for their thermal decomposition in a closed system that resulted in hydrogen and a liquid reaction product.

  20. Reaction dynamics of Pt* isotopes formed using stable and radioactive Sn beams

    NASA Astrophysics Data System (ADS)

    Jain, Deepika; Kumar, Raj; Sharma, Manoj K.

    2013-04-01

    The decay of various isotopes of Pt* formed using stable and neutron-rich radioactive beams of Sn is studied by using the dynamical cluster-decay model (DCM). The entrance channel effect in 190Pt* compound nuclei is investigated using different targets and projectiles. For both entrance channels, i.e., 132Sn+58Ni and 126Sn+64Ni, the fragmentation potential and preformation probability of decaying fragments are almost identical at comparable center-of-mass energies (Ec.m.), enabling us to conclude that decay of 190Pt* is independent of its formation effects. In order to check for the persistence of entrance channel independence in the decay of Pt* compound nuclei, various versions of nuclear proximity potentials and different values of level density parameter are employed in the calculations, and the results are sustained. It is also observed that, with inclusion of deformation effects up to quadrupole (β2) within the optimum orientation approach, the structure of potential energy surfaces changes significantly. Besides this, the fission mass distribution of Pt* isotopes is investigated and consequently the barrier modification is estimated to account for the phenomena of fusion hindrance. The 132Sn+58Ni reaction is also studied using four proximity potentials, i.e., Prox 1977, Prox 1988, mod-Prox 1988, and Denisov 2002 within the framework of the ℓ-summed extended-Wong model for addressing the fusion hindrance phenomena. We find that Prox 77 and Prox 88 fit the total fusion cross-section data only at above-barrier energies, whereas Denisov 2002 underestimates the data at all energies due to being least sensitive towards asymmetry and isospin. So a stronger nuclear interaction potential mod-Prox 1988 that accounts for isospin effect and asymmetry of the colliding nuclei is employed, which fits the data with smooth variation of ℓmax(Ec.m.). Our calculations indicate that the isospin and asymmetry of colliding nuclei also play an important role in the fusion

  1. Disassembly of hot nuclear matter formed in Au-induced reactions near the Fermi energy

    SciTech Connect

    Delis, D.N.

    1993-09-01

    Complex fragment emission has been studied in the 60 MeV/A {sup 197}Au + {sup 12}C, {sup 27}Al, {sup 51}V, {sup nat}Cu, and {sup 197}Au reactions. Velocity spectra, angular distributions and cross sections have been constructed for each target from the inclusive data. Coincidence data including 2-, 3-, 4-, and 5-fold events have also been examined. Furthermore neutron multiplicity distributions have been obtained for the above reactions by utilizing a novel neutron calorimetric approach.

  2. A novel asymmetric membrane osmotic pump capsule with in situ formed delivery orifices for controlled release of gliclazide solid dispersion system.

    PubMed

    Yang, Yue; Zhao, Zhinan; Wang, Yongfei; Yang, Lu; Liu, Dandan; Yang, Xinggang; Pan, Weisan

    2016-06-15

    In this study, a novel asymmetric membrane osmotic pump capsule of gliclazide (GLC) solid dispersion was developed to achieve a controlled drug release. The capsule shells were obtained by wet phase inversion process using cellulose acetate as semi-permeable membrane, glycerol and kolliphor P188 as pore formers, then filled with the mixture of GLC solid dispersion and pH modifiers. Differentiate from the conventional formulations, sodium carbonate was chosen as the osmotic agent and effervescent agent simultaneously to control the drug release, instead of the polymer materials. The ternary solid dispersion of GLC, with polyethylene glycol 6000 and kolliphor P188 as carriers, was prepared by solvent-evaporation method, realizing a 2.09-fold increment in solubility and dissolution rate in comparison with unprocessed GLC. Influence of the composition of the coating solution and pH modifiers on the drug release from the asymmetric membrane capsule (AMC) was investigated. The ultimate cumulative release of the optimal formulation reached 91.32% in an approximately zero-order manner. The osmotic pressure test and dye test were conducted to validate the drug release mechanism from the AMC. The in vivo pharmacokinetic study of the AMC indicated a 102.66±10.95% relative bioavailability compared with the commercial tablet, suggesting the bioequivalence between the two formulations. Consequently, the novel controlled delivery system with combination of solid dispersion and AMC system is capable of providing a satisfactory alternative to release the water-insoluble drugs in a controlled manner. PMID:27132166

  3. Reaction specificities of the ε-ionone-forming lycopene cyclase from rice (Oryza sativa) elucidated in vitro.

    PubMed

    Yu, Qiuju; Beyer, Peter

    2012-09-21

    Lycopene cyclases responsible for the formation of ε-ionone rings (LCYe) mark a plant-specific bifurcation of carotenogenesis. We investigated purified rice LCYe (OsLCYe) in a liposome-based biphasic assay system. OsLCYe depends on reduced flavin cofactors stabilizing a transient state formed during the non-redox cyclization reaction. In contrast to OsLCYb, OsLCYe produces predominantly monocyclic products and monocyclic carotene intermediates are not suitable substrates. Determination of the OsLCYe reaction specificities and the combined use of OsLCYb allow the characterization of the reaction sequence leading to heterocyclic carotenoids. It was also found that 5-cis-lycopene, which was thought to be decisive for ε-cyclization, was not involved in the reaction, with OsLCYe acting as an exclusion filter for this naturally occurring isomer.

  4. Metal amides as the simplest acid/base catalysts for stereoselective carbon-carbon bond-forming reactions.

    PubMed

    Yamashita, Yasuhiro; Kobayashi, Shū

    2013-07-15

    In this paper, new possibilities for metal amides are described. Although typical metal amides are recognized as strong stoichiometric bases for deprotonation of inert or less acidic hydrogen atoms, transition-metal amides, namely silver and copper amides, show interesting abilities as one of the simplest acid/base catalysts in stereoselective carbon-carbon bond-forming reactions.

  5. Super-asymmetric fission in the 245Cm(n th, f) reaction at the Lohengrin fission-fragment mass separator

    NASA Astrophysics Data System (ADS)

    Rochman, D.; Tsekhanovich, I.; Gönnenwein, F.; Sokolov, V.; Storrer, F.; Simpson, G.; Serot, O.

    2004-04-01

    Mass, isotopic yields and single-fragment kinetic energy measurements for thermal-neutron induced fission of 245Cm at the Lohengrin fission-product mass separator are described. Using an ionization chamber coupled to the mass separator, we have measured the mass and isotopic yields from fragment mass A=67 up to A=77 over three yield decades. This considerably extends the data set previously known for the light peak. A full set of data is now available for this actinide in the super-asymmetric mass region. The results of mass and isotopic yields are compared with those of other compound nuclei to highlight the shell effect at mass 70 for the 246Cm ★ compound-nucleus system. Also, the present results are compared to the data from the European library JEF2 and the evaluation from Wahl's Zp model.

  6. Defect-free ultrahigh flux asymmetric membranes

    DOEpatents

    Pinnau, Ingo; Koros, William J.

    1990-01-01

    Defect-free, ultrahigh flux integrally-skinned asymmetric membranes having extremely thin surface layers (<0.2 .mu.m) comprised of glassy polymers are disclosed. The membranes are formed by casting an appropriate drope followed by forced convective evaporation of solvent to obtain a dry phase separated asymmetrical structure. The structure is then washed in a precipitation liquid and dried.

  7. Heat of Combustion of the Product Formed by the Reaction of Acetylene and Diborane (LFPL-CZ-3)

    NASA Technical Reports Server (NTRS)

    Allen, Harrison, Jr.; Tannenbaum, Stanley

    1957-01-01

    The heat of combustion of the product formed by the reaction acetylene and diborane was found to be 20,100 +/- 100 Btu per pound for the reaction of liquid fuel to gaseous carbon dioxide, gaseous water, and solid boric oxide. The measurements were made in a Parr oxygen-bomb calorimeter, and chemical analyses both of the sample and of the combustion products indicated combustion in the bomb calorimeter to have been 97 percent complete. The estimated net heat of combustion for complete combustion would therefore be 20,700 +/- 100 Btu per pound.

  8. Heat of Combustion of the Product Formed by the Reaction of Diborane with 1,3-Butadiene

    NASA Technical Reports Server (NTRS)

    Tannenbaum, Stanley; Allen, Harrison, Jr.

    1953-01-01

    The net heat of combustion of the product formed by the reaction of diborane with 1,3-butadiene was found to be 18,700+/-150 Btu per pound for the reaction of liquid fuel to gaseous carbon dioxide, gaseous water, and solid boric oxide. The measurements were made in a Parr oxygen-bomb calorimeter, and the combustion was believed to be 98 percent complete. The estimated net heat of combustion for complete combustion would therefore be 19,075+/-150 Btu per pound. Since this value is approximately the same as the heat of combustion of butadiene, it seems certain that the material is partially oxidized.

  9. IDENTIFICATION OF CASO4 FORMED BY REACTION OF CAO AND SO2

    EPA Science Inventory

    The injection of calcium-based sorbents into coal-fired boilers for reaction with, and reduction in the levels of, sulfur dioxide (SO2) in the flue gas has undergone considerable research and development. Significant effort has also been made in developing models for the overall ...

  10. In Pursuit of an Ideal C-C Bond-Forming Reaction

    PubMed Central

    RajanBabu, T. V.

    2009-01-01

    Attempts to introduce the highly versatile vinyl group into other organic molecules in a chemo-, regio- and stereoselective fashion via catalytic activation of ethylene provided challenging opportunities to explore new ligand and salt effects in homogeneous catalysis. This review provides a personal account of the development of enantioselective reactions involving ethylene. PMID:19606231

  11. l-Isoleucine in a Choline Chloride/Ethylene Glycol Deep Eutectic Solvent: A Reusable Reaction Kit for the Asymmetric Cross-Aldol Carboligation.

    PubMed

    Fanjul-Mosteirín, Noé; Concellón, Carmen; Del Amo, Vicente

    2016-09-01

    l-Isoleucine is able to catalyze the cross-aldol reaction between cyclohexanone and aromatic aldehydes in a deep eutectic solvent consisting in choline chloride and ethylene glycol, rendering products with high diatereo- and enantioselectivity. This protocol is straightforward and green: the organocatalyst and the reaction medium can be recycled up to five times, allowing the preparation of different substrates with a single load of solvent and catalyst.

  12. l-Isoleucine in a Choline Chloride/Ethylene Glycol Deep Eutectic Solvent: A Reusable Reaction Kit for the Asymmetric Cross-Aldol Carboligation.

    PubMed

    Fanjul-Mosteirín, Noé; Concellón, Carmen; Del Amo, Vicente

    2016-09-01

    l-Isoleucine is able to catalyze the cross-aldol reaction between cyclohexanone and aromatic aldehydes in a deep eutectic solvent consisting in choline chloride and ethylene glycol, rendering products with high diatereo- and enantioselectivity. This protocol is straightforward and green: the organocatalyst and the reaction medium can be recycled up to five times, allowing the preparation of different substrates with a single load of solvent and catalyst. PMID:27526718

  13. Asymmetric Ashes

    NASA Astrophysics Data System (ADS)

    2006-11-01

    that oscillate in certain directions. Reflection or scattering of light favours certain orientations of the electric and magnetic fields over others. This is why polarising sunglasses can filter out the glint of sunlight reflected off a pond. When light scatters through the expanding debris of a supernova, it retains information about the orientation of the scattering layers. If the supernova is spherically symmetric, all orientations will be present equally and will average out, so there will be no net polarisation. If, however, the gas shell is not round, a slight net polarisation will be imprinted on the light. This is what broad-band polarimetry can accomplish. If additional spectral information is available ('spectro-polarimetry'), one can determine whether the asymmetry is in the continuum light or in some spectral lines. In the case of the Type Ia supernovae, the astronomers found that the continuum polarisation is very small so that the overall shape of the explosion is crudely spherical. But the much larger polarization in strongly blue-shifted spectral lines evidences the presence, in the outer regions, of fast moving clumps with peculiar chemical composition. "Our study reveals that explosions of Type Ia supernovae are really three-dimensional phenomena," says Dietrich Baade. "The outer regions of the blast cloud is asymmetric, with different materials found in 'clumps', while the inner regions are smooth." "This study was possible because polarimetry could unfold its full strength thanks to the light-collecting power of the Very Large Telescope and the very precise calibration of the FORS instrument," he adds. The research team first spotted this asymmetry in 2003, as part of the same observational campaign (ESO PR 23/03 and ESO PR Photo 26/05). The new, more extensive results show that the degree of polarisation and, hence, the asphericity, correlates with the intrinsic brightness of the explosion. The brighter the supernova, the smoother, or less clumpy

  14. Synthesis gas reactions over catalysts formed by oxidation of thorium-containing intermetallic compounds

    SciTech Connect

    Imamura, H.; Wallace, W.E.

    1980-09-01

    Intermetallic compounds containing 1:1, 1:2, 1:5, and 7:3 thorium-nickel ratios were prepared, powdered, and treated with oxygen at room temperature or 350/sup 0/C. The resulting catalysts contained mainly thorium dioxide and metallic nickel, and the nickel dispersions, as measured by CO adsorption, were 1.1-6.0%. The catalysts were active for the reaction of 3:1 hydrogen/carbon monoxide in proportion to the amount of oxygen uptake during pretreatment, and were highly selective for methane formation. Turnover numbers of up to 10.6 were obtained at 205/sup 0/C. The methanation reaction over 3.9 and 25Vertical Bar3< nickel on thoria support prepared by the conventional impregnation method gave similar conversions at 490/sup 0/-510/sup 0/C as the oxidized intermetallic compounds did at approx. 200/sup 0/C.

  15. Collision dynamics of O(3P) + DMMP using a specific reaction parameters potential form.

    PubMed

    Conforti, Patrick F; Braunstein, Matthew; Stearns, Jaime A; Dodd, James A

    2012-03-15

    Starting from previous benchmark CBS-QB3 electronic structure calculations (Conforti, P. F.; Braunstein, M.; Dodd, J. A. J. Phys. Chem. A 2009, 113, 13752), we develop two global potential energy surfaces for O((3)P) + DMMP collisions, using the specific reaction parameters approach. Each surface is simultaneously fit along the three major reaction pathways: hydrogen abstraction, hydrogen elimination, and methyl elimination. We then use these surfaces in classical dynamics simulations and compute reactive cross sections from 4 to 10 km s(-1) collision velocity. We examine the energy disposal and angular distributions of the reactive and nonreactive products. We find that for reactive collisions, an unusually large amount of the initial collision energy is transformed into internal energy. We analyze the nonreactive and reactive product internal energy distributions, many of which fit Boltzmann temperatures up to ~2000 K.

  16. Analysis of the Pressure and Temperature Dependence of the Complex-Forming Bimolecular Reaction CH3OCH3 + Fe(.).

    PubMed

    Ard, Shaun G; Johnson, Ryan S; Martinez, Oscar; Shuman, Nicholas S; Guo, Hua; Troe, Jürgen; Viggiano, Albert

    2016-07-14

    The kinetics of the reaction CH3OCH3 + Fe(+) has been studied between 250 and 600 K in the buffer gas He at pressures between 0.4 and 1.6 Torr. Total rate constants and branching ratios for the formation of Fe(+)O(CH3)2 adducts and of Fe(+)OCH2 + CH4 products were determined. Quantum-chemical calculations provided the parameters required for an analysis in terms of statistical unimolecular rate theory. The analysis employed a recently developed simplified representation of the rates of complex-forming bimolecular reactions, separating association and chemical activation contributions. Satisfactory agreement between experimental results and kinetic modeling was obtained that allows for an extrapolation of the data over wide ranges of conditions. Possible reaction pathways with or without spin-inversion are discussed in relation to the kinetic modeling results.

  17. Analysis of the Pressure and Temperature Dependence of the Complex-Forming Bimolecular Reaction CH3OCH3 + Fe(.).

    PubMed

    Ard, Shaun G; Johnson, Ryan S; Martinez, Oscar; Shuman, Nicholas S; Guo, Hua; Troe, Jürgen; Viggiano, Albert

    2016-07-14

    The kinetics of the reaction CH3OCH3 + Fe(+) has been studied between 250 and 600 K in the buffer gas He at pressures between 0.4 and 1.6 Torr. Total rate constants and branching ratios for the formation of Fe(+)O(CH3)2 adducts and of Fe(+)OCH2 + CH4 products were determined. Quantum-chemical calculations provided the parameters required for an analysis in terms of statistical unimolecular rate theory. The analysis employed a recently developed simplified representation of the rates of complex-forming bimolecular reactions, separating association and chemical activation contributions. Satisfactory agreement between experimental results and kinetic modeling was obtained that allows for an extrapolation of the data over wide ranges of conditions. Possible reaction pathways with or without spin-inversion are discussed in relation to the kinetic modeling results. PMID:27228310

  18. Fission fragment mass distributions in reactions forming the {sup 213}Fr compound nucleus

    SciTech Connect

    Appannababu, S.; Mukherjee, S.; Deshmukh, N. N.; Rath, P. K.; Singh, N. L.; Nayak, B. K.; Thomas, R. G.; Choudhury, R. K.; Sugathan, P.; Jhingan, A.; Negi, D.; Prasad, E.

    2011-03-15

    The fission fragment mass angle correlations and mass ratio distributions have been investigated for the two systems {sup 16}O+{sup 197}Au and {sup 27}Al+{sup 186}W, leading to the same compound nucleus {sup 213}Fr around the Coulomb barrier energies. Systematic analysis of the variance of the mass distributions as a function of temperature and angular momentum suggests true compound nuclear fission for both the reactions, indicating the absence of nonequilibrium fission processes.

  19. Joining of Silicon Carbide-Based Ceramics by Reaction Forming Method

    NASA Technical Reports Server (NTRS)

    Singh, M.; Kiser, J. D.

    1997-01-01

    Recently, there has been a surge of interest in the development and testing of silicon-based ceramics and composite components for a number of aerospace and ground based systems. The designs often require fabrication of complex shaped parts which can be quite expensive. One attractive way of achieving this goal is to build up complex shapes by joining together geometrically simple shapes. However, the joints should have good mechanical strength and environmental stability comparable to the bulk materials. These joints should also be able to maintain their structural integrity at high temperatures. In addition, the joining technique should be practical, reliable, and affordable. Thus, joining has been recognized as one of the enabling technologies for the successful utilization of silicon carbide based ceramic components in high temperature applications. Overviews of various joining techniques, i.e., mechanical fastening, adhesive bonding, welding, brazing, and soldering have been provided in recent publications. The majority of the techniques used today are based on the joining of monolithic ceramics with metals either by diffusion bonding, metal brazing, brazing with oxides and oxynitrides, or diffusion welding. These techniques need either very high temperatures for processing or hot pressing (high pressures). The joints produced by these techniques have different thermal expansion coefficients than the ceramic materials, which creates a stress concentration in the joint area. The use temperatures for these joints are around 700 C. Ceramic joint interlayers have been developed as a means of obtaining high temperature joints. These joint interlayers have been produced via pre-ceramic polymers, in-situ displacement reactions, and reaction bonding techniques. Joints produced by the pre-ceramic polymer approach exhibit a large amounts of porosity and poor mechanical properties. On the other hand, hot pressing or high pressures are needed for in-situ displacement

  20. A mechanistic rationale for the 9-amino(9-deoxy)epi cinchona alkaloids catalyzed asymmetric reactions via iminium ion activation of enones.

    PubMed

    Moran, Antonio; Hamilton, Alex; Bo, Carles; Melchiorre, Paolo

    2013-06-19

    The 9-amino(9-deoxy)epi cinchona alkaloids have expanded the synthetic potential of asymmetric aminocatalysis, enabling the highly stereoselective functionalization of a variety of sterically hindered carbonyl compounds. However, there is a lack of basic understanding of the mechanisms of cinchona-based primary aminocatalysis. Herein, we describe how a combination of experimental and theoretical mechanistic studies has revealed the origin of the stereoselectivity of the Friedel-Crafts alkylation of indoles with α,β-unsaturated ketones catalyzed by 9-amino(9-deoxy)epi quinine. An essential role for the achiral acid cocatalyst is uncovered: upon condensation of the cinchona catalyst with the enone, the resulting covalent imine intermediate and the acid interact to build-up a well-structured ion-pair supramolecular catalytic assembly, which is stabilized by multiple attractive noncovalent interactions. All the components of the assembly cooperatively participate in the stereocontrolling event, with the anion of the achiral acid being the structural element responsible for the π-facial discrimination of the iminium ion intermediate.

  1. Carbon-sulfur bond-forming reaction catalysed by the radical SAM enzyme HydE

    NASA Astrophysics Data System (ADS)

    Rohac, Roman; Amara, Patricia; Benjdia, Alhosna; Martin, Lydie; Ruffié, Pauline; Favier, Adrien; Berteau, Olivier; Mouesca, Jean-Marie; Fontecilla-Camps, Juan C.; Nicolet, Yvain

    2016-05-01

    Carbon-sulfur bond formation at aliphatic positions is a challenging reaction that is performed efficiently by radical S-adenosyl-L-methionine (SAM) enzymes. Here we report that 1,3-thiazolidines can act as ligands and substrates for the radical SAM enzyme HydE, which is involved in the assembly of the active site of [FeFe]-hydrogenase. Using X-ray crystallography, in vitro assays and NMR spectroscopy we identified a radical-based reaction mechanism that is best described as the formation of a C-centred radical that concomitantly attacks the sulfur atom of a thioether. To the best of our knowledge, this is the first example of a radical SAM enzyme that reacts directly on a sulfur atom instead of abstracting a hydrogen atom. Using theoretical calculations based on our high-resolution structures we followed the evolution of the electronic structure from SAM through to the formation of S-adenosyl-L-cysteine. Our results suggest that, at least in this case, the widely proposed and highly reactive 5‧-deoxyadenosyl radical species that triggers the reaction in radical SAM enzymes is not an isolable intermediate.

  2. Asymmetrical hypersensitivity to bovine collagen.

    PubMed

    Somerville, P; Wray, R C

    1993-05-01

    We report a unique patient with true asymmetrical hypersensitivity to bovine collagen. Hypersensitivity is the development of an inflammatory response at a treatment site after a negative skin test. She developed an inflammatory response in only one of two simultaneously injected sites. About 1.5% of patients with a negative skin test have a hypersensitivity reaction consisting of firmness, erythema, and swelling. The signs and symptoms generally resolve spontaneously in a few months.

  3. Decay analysis of compound nuclei with masses A ≈30 - 200 formed in reactions involving loosely bound projectiles

    NASA Astrophysics Data System (ADS)

    Kaur, Mandeep; Singh, BirBikram; Sharma, Manoj K.; Gupta, Raj K.

    2015-08-01

    The dynamics of compound nuclei formed in the reactions using loosely bound projectiles are analyzed within the framework of the dynamical cluster-decay model (DCM) of Gupta and Collaborators. We have considered the reactions with neutron-rich and neutron-deficient projectiles, respectively, as 7Li , 9Be , and 7Be , on various targets at three different Elab energies, forming compound nuclei in the mass region A ˜30 - 200. For these reactions, the contributions of light-particle (LP, A ≤4 ) cross sections σLP, energetically favored intermediate-mass-fragment (IMF, 5 ≤A2≤20 ) cross sections σIMF, as well as the fusion-fission ff cross sections σff constitute the σfus(=σLP+σIMF+σff ), i.e., the contributions of the emitted LPs, IMFs, and ff fragments are added for all the angular momenta up to the ℓmax value for the respective reactions. Interestingly, we find that the empirically fitted neck-length parameter Δ Remp , the only parameter of the DCM, is uniquely fixed to address σfus for all the reactions having the same loosely bound projectile at a chosen incident laboratory energy. It may be noted that, in DCM, the dynamical collective mass motion of preformed LPs, IMFs, and ff fragments or clusters, through the modified interaction potential barrier, are treated on parallel footing. The modification of the barrier is due to nonzero Δ Remp , and the values of corresponding modified interaction-barrier heights Δ VBemp for such reactions are almost of the same order, specifically at the respective ℓmax value.

  4. Aryl esters of the aci form of methanetrisulfonyl fluoride and their reactions

    SciTech Connect

    Yagupol'skii, Yu.L.; Savina, T.I.

    1986-03-10

    The aryl esters of the aci form of methanetrisulfonyl fluoride are formed during the thermal decomposition of arenediazoniotris(fluorosulfonyl)methanides, which are produced by the action of methanetrisulfonyl fluoride on arenediazonium chlorides. The ylide fluorine atom is substituted by NR/sub 2/ and POh groups with silicon-containing reagents and by a phenyl group with phenyllithium. The obtained ylides add cesium fluoride and silver fluorides at the C=S bond in diglyme.

  5. Transition-metal catalyzed oxidative cross-coupling reactions to form C-C bonds involving organometallic reagents as nucleophiles.

    PubMed

    Shi, Wei; Liu, Chao; Lei, Aiwen

    2011-05-01

    Transition-metal-catalyzed coupling reactions have become a versatile tool for chemical bond formation. From the variation of the coupling partners, coupling reactions can be classified into three models: traditional coupling, reductive coupling and oxidative coupling. The oxidative coupling, which is different from the traditional coupling, occurs between two nucleophiles. This critical review focuses on transition-metal-catalyzed oxidative coupling reactions involving organometallic reagents as nucleophiles. Since the scope of the oxidative coupling is highly diversified, this paper only reviews the oxidative coupling reactions concerning C-C bond formation, including the coupling between organometal reagents and hydrocarbons as well as coupling between two organometal reagents. Since terminal alkynes are normally activated by metal salts and in situ form the alkynyl metal reagents in coupling reactions, they are directly considered as organometal reagents in this review. Intramolecular oxidative couplings and oxidative cyclizations are not included in this critical review. Moreover, there are many examples of oxidative coupling leading to the formation of functional materials, such as the oxidative polymerization of thiophenes. Since several reviews in these areas have been published they are not included in this review either (99 references).

  6. Characterization of iron dinitrosyl species formed in the reaction of nitric oxide with a biological Rieske center.

    PubMed

    Tinberg, Christine E; Tonzetich, Zachary J; Wang, Hongxin; Do, Loi H; Yoda, Yoshitaka; Cramer, Stephen P; Lippard, Stephen J

    2010-12-29

    Reactions of nitric oxide with cysteine-ligated iron-sulfur cluster proteins typically result in disassembly of the iron-sulfur core and formation of dinitrosyl iron complexes (DNICs). Here we report the first evidence that DNICs also form in the reaction of NO with Rieske-type [2Fe-2S] clusters. Upon treatment of a Rieske protein, component C of toluene/o-xylene monooxygenase from Pseudomonas sp. OX1, with an excess of NO(g) or NO-generators S-nitroso-N-acetyl-D,L-pencillamine and diethylamine NONOate, the absorbance bands of the [2Fe-2S] cluster are extinguished and replaced by a new feature that slowly grows in at 367 nm. Analysis of the reaction products by electron paramagnetic resonance, Mössbauer, and nuclear resonance vibrational spectroscopy reveals that the primary product of the reaction is a thiolate-bridged diiron tetranitrosyl species, [Fe(2)(μ-SCys)(2)(NO)(4)], having a Roussin's red ester (RRE) formula, and that mononuclear DNICs account for only a minor fraction of nitrosylated iron. Reduction of this RRE reaction product with sodium dithionite produces the one-electron-reduced RRE, having absorptions at 640 and 960 nm. These results demonstrate that NO reacts readily with a Rieske center in a protein and suggest that dinuclear RRE species, not mononuclear DNICs, may be the primary iron dinitrosyl species responsible for the pathological and physiological effects of nitric oxide in such systems in biology.

  7. Synthesis and Characterization of New Binuclear Co(0) Complexes with Diphosphinoamine Ligands. A Potential Approach for Asymmetric Pauson-Khand Reactions.

    PubMed

    Gimbert, Yves; Robert, Frédéric; Durif, André; Averbuch, Marie-Thérèse; Kann, Nina; Greene, Andrew E.

    1999-05-14

    The synthesis of P-N-P bidentate ligands and the evaluation, based on IR and X-ray data, of their pi-acceptor properties in the complexes derived from phenylacetylene-dicobalt hexacarbonyl have been carried out. In addition, the reactivity of these complexes in the Pauson-Khand reaction has been examined.

  8. Asymmetric organocatalytic decarboxylative Mannich reaction using β-keto acids: A new protocol for the synthesis of chiral β-amino ketones

    PubMed Central

    Jiang, Chunhui; Zhong, Fangrui

    2012-01-01

    Summary The first decarboxylative Mannich reaction employing β-keto acids, catalyzed by cinchonine-derived bifunctional thiourea catalyst has been described. The desired β-amino ketones were obtained in excellent yields and with moderate to good enantioselectivities. PMID:23019459

  9. Zn-Mediated Reduction of Oxalyl Chloride Forming CO and Its Application in Carbonylation Reactions.

    PubMed

    Markovič, Martin; Lopatka, Pavol; Koóš, Peter; Gracza, Tibor

    2015-11-20

    An efficient protocol for the generation of carbon monoxide by Zn-mediated reduction of oxalyl chloride has been developed. Oxalyl chloride was applied as an extremely effective substitute for toxic gaseous CO in the palladium-catalyzed alkoxy-/amino-/hydrogen-/hydroxycarbonylation processes providing industrially interesting esters, amides, aldehydes, and carboxylic acids in good to excellent yields. This new procedure can be applied to various carbonylation reactions in the presence of a transition metal catalyst under mild conditions and with a stoichiometric amount of CO source. PMID:26555577

  10. Transmetalation from B to Rh in the course of the catalytic asymmetric 1,4-addition reaction of phenylboronic acid to enones: a computational comparison of diphosphane and diene ligands.

    PubMed

    Li, You-Gui; He, Gang; Qin, Hua-Li; Kantchev, Eric Assen B

    2015-02-14

    Transmetalation is a key elementary reaction of many important catalytic reactions. Among these, 1,4-addition of arylboronic acids to organic acceptors such as α,β-unsaturated ketones has emerged as one of the most important methods for asymmetric C-C bond formation. A key intermediate for the B-to-Rh transfer arising from quaternization on a boronic acid by a Rh-bound hydroxide (the active catalyst) has been proposed. Herein, DFT calculations (IEFPCM/PBE0/DGDZVP level of theory) establish the viability of this proposal, and characterize the associated pathways. The delivery of phenylboronic acid in the orientation suited for the B-to-Rh transfer from the very beginning is energetically preferable, and occurs with expulsion of Rh-coordinated water molecules. For the bulkier binap ligand, the barriers are higher (particularly for the phenylboronic acid activation step) due to a less favourable entropy term to the free energy, in accordance with the experimentally observed slower transmetalation rate. PMID:25422851

  11. Transmetalation from B to Rh in the course of the catalytic asymmetric 1,4-addition reaction of phenylboronic acid to enones: a computational comparison of diphosphane and diene ligands.

    PubMed

    Li, You-Gui; He, Gang; Qin, Hua-Li; Kantchev, Eric Assen B

    2015-02-14

    Transmetalation is a key elementary reaction of many important catalytic reactions. Among these, 1,4-addition of arylboronic acids to organic acceptors such as α,β-unsaturated ketones has emerged as one of the most important methods for asymmetric C-C bond formation. A key intermediate for the B-to-Rh transfer arising from quaternization on a boronic acid by a Rh-bound hydroxide (the active catalyst) has been proposed. Herein, DFT calculations (IEFPCM/PBE0/DGDZVP level of theory) establish the viability of this proposal, and characterize the associated pathways. The delivery of phenylboronic acid in the orientation suited for the B-to-Rh transfer from the very beginning is energetically preferable, and occurs with expulsion of Rh-coordinated water molecules. For the bulkier binap ligand, the barriers are higher (particularly for the phenylboronic acid activation step) due to a less favourable entropy term to the free energy, in accordance with the experimentally observed slower transmetalation rate.

  12. Functional properties of nisin-carbohydrate conjugates formed by radiation induced Maillard reaction

    NASA Astrophysics Data System (ADS)

    Muppalla, Shobita R.; Sonavale, Rahul; Chawla, Surinder P.; Sharma, Arun

    2012-12-01

    Nisin-carbohydrate conjugates were prepared by irradiating nisin either with glucose or dextran. Increase in browning and formation of intermediate products was observed with a concomitant decrease in free amino and reducing sugar groups indicating occurrence of the Maillard reaction catalyzed by irradiation. Nisin-carbohydrate conjugates showed a broad spectrum antibacterial activity against Gram negative bacteria (Escherichia coli, Pseudomonas fluorescence) as well as Gram positive bacteria (Staphylococcus aureus, Bacillus cereus). Results of antioxidant assays, including that of DPPH radical-scavenging activity and reducing power, showed that the nisin-dextran conjugates possessed better antioxidant potential than nisin-glucose conjugate. These results suggested that it was possible to enhance the functional properties of nisin by preparing radiation induced conjugates suitable for application in food industry.

  13. Synthesis of Diverse Heterocyclic Scaffolds via Tandem Additions to Imine Derivatives and Ring-Forming Reactions

    PubMed Central

    Sunderhaus, James D.; Dockendorff, Chris; Martin, Stephen F.

    2009-01-01

    A novel strategy has been developed for the efficient syntheses of diverse arrays of heterocyclic compounds. The key elements of the approach comprise a Mannich-type, multicomponent coupling reaction in which functionalized amines, aromatic aldehydes, acylating agents, and π- and organometallic nucleophiles are combined to generate intermediates that are then further transformed into diverse heterocyclic scaffolds via a variety of cyclization manifolds. Significantly, many of these scaffolds bear functionality that may be exploited by further manipulation to create diverse collections of compounds having substructures found in biologically active natural products and clinically useful drugs. The practical utility of this strategy was exemplified by its application to the first, and extraordinarily concise synthesis of the isopavine alkaloid roelactamine. PMID:20625454

  14. Stochastic Modeling of the Reaction Response of Reactive Intermetallic-Forming Materials

    NASA Astrophysics Data System (ADS)

    Specht, Paul E.; Thadhani, Naresh N.; Baer, Mel R.

    2011-06-01

    Microstructure at the meso-scale greatly affects the shock compression response of composites, due to the development of multiple wave interactions, that lead to complex loading scenarios. This microstructure-dependent response is inherently stochastic and lends itself to a probabilistic description. To understand this stochastic nature, three-dimensional simulations on a real, heterogeneous microstructure of a Ni and Al powder compact were performed in CTH, a Eulerian, finite volume hydrocode. These simulation results provide relationships between the mechanical and thermodynamic state of the composite under dynamic loading, which can be used for developing a probabilistic model for the bulk reaction response. Research funded by ONR/MURI grant No. N00014-07-1-0740.

  15. Synthesis, Identification, and Structure Elucidation of Adducts Formed by Reactions of Hydroxycinnamic Acids with Glutathione or Cysteinylglycine.

    PubMed

    Ferreira-Lima, Nayla; Vallverdú-Queralt, Anna; Meudec, Emmanuelle; Mazauric, Jean-Paul; Sommerer, Nicolas; Bordignon-Luiz, Marilde T; Cheynier, Véronique; Le Guernevé, Christine

    2016-09-23

    Grape polyphenols, especially hydroxycinnamic acids such as caftaric and caffeic acid, are prone to enzymatic oxidation reactions during the winemaking process, forming o-quinones and leading to color darkening. Glutathione is capable of trapping these o-quinones and thus limiting juice browning. In this study, the addition of glutathione or cysteinylglycine onto caftaric or caffeic acid o-quinones formed by polyphenoloxidase-catalyzed reactions was investigated by UPLC-DAD-ESIMS and NMR data analyses. Complete identification of adducts has been achieved via NMR data. The results confirmed that the favored reaction is the substitution of the sulfanyl group of cysteine at C-2 of the aromatic ring. Several minor isomers, namely, the cis-isomer of the 2-S adduct and trans-isomers of the 5-S and 6-S adducts, and the 2,5-di-S-glutathionyl adducts were also identified and quantified by qNMR. With the exception of 2-(S-glutathionyl)- and 2,5-di(S-glutathionyl)-trans-caftaric acid, these products had never been formally identified. In particular, the 5-S and 6-S derivatives are reported here for the first time. The first formal identification of 2-S cis-derivatives is also provided. Moreover, NMR and UPLC-DAD-ESIMS analysis showed that signature UV and MS spectra can serve as markers of the conformation and substitution position in the aromatic ring for each of the isomers.

  16. Synthesis, Identification, and Structure Elucidation of Adducts Formed by Reactions of Hydroxycinnamic Acids with Glutathione or Cysteinylglycine.

    PubMed

    Ferreira-Lima, Nayla; Vallverdú-Queralt, Anna; Meudec, Emmanuelle; Mazauric, Jean-Paul; Sommerer, Nicolas; Bordignon-Luiz, Marilde T; Cheynier, Véronique; Le Guernevé, Christine

    2016-09-23

    Grape polyphenols, especially hydroxycinnamic acids such as caftaric and caffeic acid, are prone to enzymatic oxidation reactions during the winemaking process, forming o-quinones and leading to color darkening. Glutathione is capable of trapping these o-quinones and thus limiting juice browning. In this study, the addition of glutathione or cysteinylglycine onto caftaric or caffeic acid o-quinones formed by polyphenoloxidase-catalyzed reactions was investigated by UPLC-DAD-ESIMS and NMR data analyses. Complete identification of adducts has been achieved via NMR data. The results confirmed that the favored reaction is the substitution of the sulfanyl group of cysteine at C-2 of the aromatic ring. Several minor isomers, namely, the cis-isomer of the 2-S adduct and trans-isomers of the 5-S and 6-S adducts, and the 2,5-di-S-glutathionyl adducts were also identified and quantified by qNMR. With the exception of 2-(S-glutathionyl)- and 2,5-di(S-glutathionyl)-trans-caftaric acid, these products had never been formally identified. In particular, the 5-S and 6-S derivatives are reported here for the first time. The first formal identification of 2-S cis-derivatives is also provided. Moreover, NMR and UPLC-DAD-ESIMS analysis showed that signature UV and MS spectra can serve as markers of the conformation and substitution position in the aromatic ring for each of the isomers. PMID:27616743

  17. Exact model reduction with delays: closed-form distributions and extensions to fully bi-directional monomolecular reactions

    PubMed Central

    Leier, Andre; Barrio, Manuel; Marquez-Lago, Tatiana T.

    2014-01-01

    In order to systematically understand the qualitative and quantitative behaviour of chemical reaction networks, scientists must derive and analyse associated mathematical models. However, biochemical systems are often very large, with reactions occurring at multiple time scales, as evidenced by signalling pathways and gene expression kinetics. Owing to the associated computational costs, it is then many times impractical, if not impossible, to solve or simulate these systems with an appropriate level of detail. By consequence, there is a growing interest in developing techniques for the simplification or reduction of complex biochemical systems. Here, we extend our recently presented methodology on exact reduction of linear chains of reactions with delay distributions in two ways. First, we report that it is now possible to deal with fully bi-directional monomolecular systems, including degradations, synthesis and generalized bypass reactions. Second, we provide all derivations of associated delays in analytical, closed form. Both advances have a major impact on further reducing computational costs, while still retaining full accuracy. Thus, we expect our new methodology to respond to current simulation needs in pharmaceutical, chemical and biological research. PMID:24694895

  18. Organocatalytic enantioselective Michael-Michael-Michael-aldol condensation reactions: control of five stereocenters in a quadruple-cascade asymmetric synthesis of highly functionalized hexahydrophenanthrenes.

    PubMed

    Raja, Arun; Hong, Bor-Cherng; Lee, Gene-Hsiang

    2014-11-01

    A cascade organocatalysis has been developed for the enantioselective synthesis of a highly functionalized hexahydrophenanthrene-2-carbaldehyde containing five contiguous stereogenic centers with high diastereoselectivity and high enantioselectivity (>99% ee). The one-pot method comprises a cascade of organocatalytic Michael-Michael-Michael-aldol reactions of 2-methyl-1,5-dinitro-3-((E)-2-nitrovinyl)benzene and α,β-unsaturated aldehydes (e.g., cinnamaldehyde). The structure and absolute configuration of a product were confirmed by X-ray analysis of an appropriate derivative.

  19. Colloid formation during waste form reaction: implications for nuclear waste disposal

    USGS Publications Warehouse

    Bates, J. K.; Bradley, J.; Teetsov, A.; Bradley, C. R.; ten Brink, Marilyn Buchholtz

    1992-01-01

    Insoluble plutonium- and americium-bearing colloidal particles formed during simulated weathering of a high-level nuclear waste glass. Nearly 100 percent of the total plutonium and americium in test ground water was concentrated in these submicrometer particles. These results indicate that models of actinide mobility and repository integrity, which assume complete solubility of actinides in ground water, underestimate the potential for radionuclide release into the environment. A colloid-trapping mechanism may be necessary for a waste repository to meet long-term performance specifications.

  20. Theoretical investigations toward the tandem reactions of N-aziridinyl imine compounds forming triquinanes via trimethylenemethane diyls: mechanisms and stereoselectivity.

    PubMed

    Qiao, Yan; Han, Ke-Li

    2014-02-28

    In this paper, we have investigated the tandem reaction mechanism for the N-aziridinyl imine compounds forming triquinanes via trimethylenemethane (TMM) diyls in detail. Based on the calculated results, the reaction is initiated by the cleavage of the N-aziridinyl in the substrate, followed by an intramolecular 1,3-dipolar (3 + 2) cycloaddition preferentially leading to a linearly-fused tetrahydrocyclopentapyrazole intermediate. Next, the intermediate loses N2 to form the singlet TMM diyl M3S, which can then undergo another concerted (3 + 2) cycloaddition to generate the linearly-fused cis–trans or cis–syn triquinane products. In addition, M3S can also undergo intersystem crossing to the triplet TMM diyl M3T, and the six possible reaction pathways associated with M3T have also been identified. The calculated results reveal that the cis–trans fused pathway associated with M3S is energetically preferred with the highest free energy barrier of 25.0 kcal mol(−1). In comparison, the cyclization of M3T requires much higher activation free energies (ΔG(≠) = 34.4–57.8 kcal mol(−1)). At the experimental temperature 110 °C, only the linearly-fused cis–trans and cis–syn pathways associated with M3T (ΔG(≠) = 34.4 and 35.5 kcal mol(−1) respectively) are possible. The calculated results also indicate that for both M3S and M3T, the linearly-fused cis–trans triquinane should be the main product, which is consistent with the experimental observation. At last, conformational and NBO analyses on key transition states identified the cis–trans stereocontrol factors. Further calculations indicate that the methyl substituent on the allene group of the reactant substrate improves the stereoselectivity of the reaction but does not affect the rate-determining step.

  1. A G-Rich Sequence within the c-kit Oncogene Promoter Forms a Parallel G-Quadruplex Having Asymmetric G-Tetrad Dynamics

    PubMed Central

    Hsu, Shang-Te Danny; Varnai, Peter; Bugaut, Anthony; Reszka, Anthony P.; Neidle, Stephen; Balasubramanian, Shankar

    2011-01-01

    Guanine-rich DNA sequences with the ability to form quadruplex structures are enriched in the promoter regions of protein-coding genes, particularly those of proto-oncogenes. G-quadruplexes are structurally polymorphic and their folding topologies can depend on the sample conditions. We report here on a structural study using solution state NMR spectroscopy of a second G-quadruplex-forming motif (c-kit2) that has been recently identified in the promoter region of the c-kit oncogene. In the presence of potassium ions, c-kit2 exists as an ensemble of structures that share the same parallel-stranded propeller-type conformations. Subtle differences in structural dynamics have been identified using hydrogen–deuterium exchange experiments by NMR spectroscopy, suggesting the coexistence of at least two structurally similar but dynamically distinct substates, which undergo slow interconversion on the NMR timescale. PMID:19705869

  2. A G-rich sequence within the c-kit oncogene promoter forms a parallel G-quadruplex having asymmetric G-tetrad dynamics.

    PubMed

    Hsu, Shang-Te Danny; Varnai, Peter; Bugaut, Anthony; Reszka, Anthony P; Neidle, Stephen; Balasubramanian, Shankar

    2009-09-23

    Guanine-rich DNA sequences with the ability to form quadruplex structures are enriched in the promoter regions of protein-coding genes, particularly those of proto-oncogenes. G-quadruplexes are structurally polymorphic and their folding topologies can depend on the sample conditions. We report here on a structural study using solution state NMR spectroscopy of a second G-quadruplex-forming motif (c-kit2) that has been recently identified in the promoter region of the c-kit oncogene. In the presence of potassium ions, c-kit2 exists as an ensemble of structures that share the same parallel-stranded propeller-type conformations. Subtle differences in structural dynamics have been identified using hydrogen-deuterium exchange experiments by NMR spectroscopy, suggesting the coexistence of at least two structurally similar but dynamically distinct substates, which undergo slow interconversion on the NMR timescale. PMID:19705869

  3. Thioredoxin A Active-Site Mutants Form Mixed Disulfide Dimers That Resemble Enzyme–Substrate Reaction Intermediates

    PubMed Central

    Kouwen, Thijs R.H.M.; Andréll, Juni; Schrijver, Rianne; Dubois, Jean-Yves F.; Maher, Megan J.; Iwata, So; Carpenter, Elisabeth P.; van Dijl, Jan Maarten

    2008-01-01

    Thioredoxin functions in nearly all organisms as the major thiol–disulfide oxidoreductase within the cytosol. Its prime purpose is to maintain cysteine-containing proteins in the reduced state by converting intramolecular disulfide bonds into dithiols in a disulfide exchange reaction. Thioredoxin has been reported to contribute to a wide variety of physiological functions by interacting with specific sets of substrates in different cell types. To investigate the function of the essential thioredoxin A (TrxA) in the low-GC Gram-positive bacterium Bacillus subtilis, we purified wild-type TrxA and three mutant TrxA proteins that lack either one or both of the two cysteine residues in the CxxC active site. The pure proteins were used for substrate-binding studies known as “mixed disulfide fishing” in which covalent disulfide-bonded reaction intermediates can be visualized. An unprecedented finding is that both active-site cysteine residues can form mixed disulfides with substrate proteins when the other active-site cysteine is absent, but only the N-terminal active-site cysteine forms stable interactions. A second novelty is that both single-cysteine mutant TrxA proteins form stable homodimers due to thiol oxidation of the remaining active-site cysteine residue. To investigate whether these dimers resemble mixed enzyme–substrate disulfides, the structure of the most abundant dimer, C32S, was characterized by X-ray crystallography. This yielded a high-resolution (1.5Å) X-ray crystallographic structure of a thioredoxin homodimer from a low-GC Gram-positive bacterium. The C32S TrxA dimer can be regarded as a mixed disulfide reaction intermediate of thioredoxin, which reveals the diversity of thioredoxin/substrate-binding modes. PMID:18455736

  4. Yields of beta-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates formed from OH radical-initiated reactions of 2-methyl-1-alkenes.

    PubMed

    Matsunaga, Aiko; Ziemann, Paul J

    2010-04-13

    Yields of beta-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates, in particles formed from OH radical-initiated reactions of C(9)-C(15) 2-methyl-1-alkenes in the presence of NO(x) were measured by using a thermal desorption particle beam mass spectrometer coupled to a high-performance liquid chromatograph with a UV-visible (UV-vis) detector. Yields of beta-hydroxynitrates and dihydroxynitrates increased with carbon number primarily due to enhanced gas-to-particle partitioning before reaching plateaus at approximately C(14)-C(15), where the compounds were essentially entirely in the particle phase. Plateau yields of beta-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates were 0.183 +/- 0.005, 0.045 +/- 0.005, and 0.034 +/- 0.005, and, after normalization for OH radical addition to the C = C double bond, were 0.225 +/- 0.007, 0.055 +/- 0.006, and 0.042 +/- 0.006. The fractions of 1-hydroxy and 2-hydroxy beta-hydroxynitrate isomers were 0.90/0.10. Yields measured here and in our previous study of reactions of linear internal alkenes and linear 1-alkenes indicate that, for these alkene classes, the relative branching ratios for forming tertiary, secondary, and primary beta-hydroxyalkyl radicals by OH radical addition to the C=C double bond are 4.3/1.9/1.0, and the branching ratios for forming beta-hydroxynitrates from reactions of tertiary, secondary, and primary beta-hydroxyperoxy radicals with NO are 0.25, 0.15, and 0.12. The effects of H(2)O vapor and NH(3) on yields were also explored.

  5. Room temperature gas-solid reaction of titanium on glass surfaces forming a very low resistivity layer

    NASA Astrophysics Data System (ADS)

    Solís, Hugo; Clark, Neville; Azofeifa, Daniel; Avendano, E.

    2016-09-01

    Titanium films were deposited on quartz, glass, polyamide and PET substrates in a high vacuum system at room temperature and their electrical resistance monitored in vacuo as a function of thickness. These measurements indicate that a low electrical resistance layer is formed in a gas-solid reaction during the condensation of the initial layers of Ti on glass and quartz substrates. Layers begin to show relative low electrical resistance at around 21 nm for glass and 9nm for quartz. Samples deposited on polyamide and PET do not show this low resistance feature.

  6. Hyaluronic Acid Hydrogels Formed in Situ by Transglutaminase-Catalyzed Reaction.

    PubMed

    Ranga, Adrian; Lutolf, Matthias P; Hilborn, Jöns; Ossipov, Dmitri A

    2016-05-01

    Enzymatically cross-linked hydrogels can be formed in situ and permit highly versatile and selective tethering of bioactive molecules, thereby allowing for a wealth of applications in cell biology and tissue engineering. While a number of studies have reported the bioconjugation of extracellular matrix (ECM) proteins and peptides into such matrices, the site-specific incorporation of biologically highly relevant polysaccharides such as hyaluronic acid (HA) has thus far not been reported, limiting our ability to reconstruct this key feature of the in vivo ECM. Here we demonstrate a novel strategy for transglutaminase-mediated covalent linking of HA moieties to a synthetic poly(ethylene glycol) (PEG) macromer resulting in the formation of hybrid HA-PEG hydrogels. We characterize the ensuing matrix properties and demonstrate how these cytocompatible gels can serve to modulate the cellular phenotype of human mammary cancer epithelial cells as well as mouse myoblasts. The use of HA as a novel building block in the increasingly varied library of synthetic PEG-based artificial ECMs should have applications as a structural as well as a signaling component and offers significant potential as an injectable matrix for regenerative medicine. PMID:27014785

  7. Mechanistic Insights into Homogeneous and Heterogeneous Asymmetric Iron Catalysis

    NASA Astrophysics Data System (ADS)

    Sonnenberg, Jessica

    Our group has been focused on replacing toxic and expensive precious metal catalysts with iron for the synthesis of enantiopure compounds for industrial applications. During an investigation into the mechanism of asymmetric transfer hydrogenation with our first generation iron-(P-N-N-P) catalysts we found substantial evidence for zero-valent iron nanoparticles coated in chiral ligand acting as the active site. Extensive experimental and computational experiments were undertaken which included NMR, DFT, reaction profile analysis, substoichiometric poisoning, electron microscope imaging, XPS and multiphasic analysis, all of which supported the fact that NPs were the active species in catalysis. Reversibility of this asymmetric reaction on the nanoparticle surface was then probed using oxidative kinetic resolution of racemic alcohols, yielding modest enantiopurity and high turnover frequencies (TOF) for a range of aromatic alcohols. Efficient dehydrogenation of ammonia-borane for hydrogen evolution and the formation of B-N oligomers was also shown using the NP system, yielding highly active systems, with a maximum TOF of 3.66 H2/s-1 . We have also begun to focus on the development of iron catalysts for asymmetric direct hydrogenation of ketones using hydrogen gas. New chiral iron-(P-N-P) catalysts were developed and shown to be quite active and selective for a wide range of substrates. Mechanistic investigations primarily using NMR and DFT indicated that a highly active trans-dihydride species was being formed during catalyst activation. Lastly, a new library of chiral P-N-P and P-NH-P ligands were developed, as well as their corresponding iron complexes, some of which show promise for the development of future generations of active asymmetric direct hydrogenation catalysts.

  8. Characterization of three deoxynivalenol sulfonates formed by reaction of deoxynivalenol with sulfur reagents.

    PubMed

    Schwartz, Heidi Elisabeth; Hametner, Christian; Slavik, Veronika; Greitbauer, Oliver; Bichl, Gerlinde; Kunz-Vekiru, Elisavet; Schatzmayr, Dian; Berthiller, Franz

    2013-09-18

    Reduction of the Fusarium mycotoxin deoxynivalenol (DON) in animal feed by treatment with sodium bisulfite and sodium metabisulfite has been successfully demonstrated in several studies. All of them reported formation of one DON sulfonate of strongly reduced toxicity compared to DON. The starting point of the present work was investigation of different sulfur reagents for reduction of DON. In the course of these experiments, three different DON sulfonates termed DON sulfonate 1 (1), DON sulfonate 2 (2), and DON sulfonate 3 (3) were identified and structurally elucidated by UHPLC-HRMS/MS as well as NMR spectroscopy. Compound 1 is characterized by loss of the epoxide group, and 2 by formation of a hemiketal. Compound 3 is an equilibrating mixture of two isomers, a ketone and a hemiketal. The MS/MS pattern can be used to differentiate the three DON sulfonates, despite their same mass and molecular formula. Investigation of parameters influencing formation and stability of DON sulfonates revealed that rapid formation of 1 and 2 occurs at alkaline pH, whereas at acidic pH, slow formation of 3 takes place, irrespective of the sulfur reagent used. Whereas 1 and 2 are stable across a broad pH range, 3 decomposes to DON, 1, and 2 at alkaline pH. In addition, both 2 and 3 are unstable in solid form. The formation, characterization, and stability of three novel DON sulfonates with respect to results from previous studies are discussed, providing insights of relevance for detoxification of DON-containing animal feed.

  9. Virus-based Photo-Responsive Nanowires Formed By Linking Site-Directed Mutagenesis and Chemical Reaction

    NASA Astrophysics Data System (ADS)

    Murugesan, Murali; Abbineni, Gopal; Nimmo, Susan L.; Cao, Binrui; Mao, Chuanbin

    2013-05-01

    Owing to the genetic flexibility and error-free bulk production, bio-nanostructures such as filamentous phage showed great potential in materials synthesis, however, their photo-responsive behaviour is neither explored nor unveiled. Here we show M13 phage genetically engineered with tyrosine residues precisely fused to the major coat protein is converted into a photo-responsive organic nanowire by a site-specific chemical reaction with an aromatic amine to form an azo dye structure on the surface. The resulting azo-M13-phage nanowire exhibits reversible photo-responsive properties due to the photo-switchable cis-trans isomerisation of the azo unit formed on the phage. This result shows that site-specific display of a peptide on bio-nanostructures through site-directed genetic mutagenesis can be translated into site-directed chemical reaction for developing advanced materials. The photo-responsive properties of the azo-M13-phage nanowires may open the door for the development of light controllable smart devices for use in non-linear optics, holography data storage, molecular antenna, and actuators.

  10. Virus-based photo-responsive nanowires formed by linking site-directed mutagenesis and chemical reaction.

    PubMed

    Murugesan, Murali; Abbineni, Gopal; Nimmo, Susan L; Cao, Binrui; Mao, Chuanbin

    2013-01-01

    Owing to the genetic flexibility and error-free bulk production, bio-nanostructures such as filamentous phage showed great potential in materials synthesis, however, their photo-responsive behaviour is neither explored nor unveiled. Here we show M13 phage genetically engineered with tyrosine residues precisely fused to the major coat protein is converted into a photo-responsive organic nanowire by a site-specific chemical reaction with an aromatic amine to form an azo dye structure on the surface. The resulting azo-M13-phage nanowire exhibits reversible photo-responsive properties due to the photo-switchable cis-trans isomerisation of the azo unit formed on the phage. This result shows that site-specific display of a peptide on bio-nanostructures through site-directed genetic mutagenesis can be translated into site-directed chemical reaction for developing advanced materials. The photo-responsive properties of the azo-M13-phage nanowires may open the door for the development of light controllable smart devices for use in non-linear optics, holography data storage, molecular antenna, and actuators. PMID:23673356

  11. Virus-based Photo-Responsive Nanowires Formed By Linking Site-Directed Mutagenesis and Chemical Reaction

    PubMed Central

    Murugesan, Murali; Abbineni, Gopal; Nimmo, Susan L.; Cao, Binrui; Mao, Chuanbin

    2013-01-01

    Owing to the genetic flexibility and error-free bulk production, bio-nanostructures such as filamentous phage showed great potential in materials synthesis, however, their photo-responsive behaviour is neither explored nor unveiled. Here we show M13 phage genetically engineered with tyrosine residues precisely fused to the major coat protein is converted into a photo-responsive organic nanowire by a site-specific chemical reaction with an aromatic amine to form an azo dye structure on the surface. The resulting azo-M13-phage nanowire exhibits reversible photo-responsive properties due to the photo-switchable cis-trans isomerisation of the azo unit formed on the phage. This result shows that site-specific display of a peptide on bio-nanostructures through site-directed genetic mutagenesis can be translated into site-directed chemical reaction for developing advanced materials. The photo-responsive properties of the azo-M13-phage nanowires may open the door for the development of light controllable smart devices for use in non-linear optics, holography data storage, molecular antenna, and actuators. PMID:23673356

  12. A Petal-type Chiral NADH Model: Design, Synthesis and its Asymmetric Reduction

    PubMed Central

    Bai, Cui-Bing; Wang, Nai-Xing; Wang, Yan-Jing; Xing, Yalan; Zhang, Wei; Lan, Xing-Wang

    2015-01-01

    A new type of NADH model compound has been synthesized by an efficient and convenient method. This model compound exhibits high reactivity and enantioselectivity in asymmetric reduction reactions. The results show that chiral NADH model S could be effectively combined with Mg2+ to form ternary complexes. This novel C3 symmetrical NADH model is capable of fluorescence emission at 460 nm when excited at 377 nm. PMID:26648413

  13. Bond forming reactions of carbyne and nitrene complexes. Final technical report for DE-FG02-96ER14608

    SciTech Connect

    Templeton, J.L.

    2002-09-01

    An isolobal relationship among terminal carbyne, nitrene and oxo ligands provided the basis for our efforts to explore new synthetic routes to such complexes and to probe bond forming reactions of these ligands. The specific goals of this project were to explore reactions of carbyne and nitrene ligands, and a summary of our results follows. Manipulation of metal-ligand pi bonds to control reactivity patterns provided the conceptual basis for this work. New transformations and coupling reactions of the CR and NR moieties bound to metal centers have been explored and transformations of carbyne or nitrene ligands have been achieved. Perhaps the most exciting results have come in the area of the simplest ligand: the CH carbyne unit. Treatment of [Tp'(CO){sub 2}W{triple_bond}C-PPh{sub 3}] [PF{sub 6}] Tp' = hydridotris(3,5-dimethylpyrazolylborate) with Na[HBEt{sub 3}] forms the methylidyne complex Tp' (CO){sub 2}W{triple_bond}C-H via formyl and carbene intermediates. Protonation of the Tp'(CO){sub 2}W{triple_bond}C-H methylidyne complex yields the cationic agostic methylidene complex, [Tp'(CO){sub 2}W=CH{sub 2}][BF{sub 4}]. The methylidyne complex with a pK{sub a} of 28.7 can be deprotonated to provide the anionic terminal carbide Tp' (CO){sub 2}W{triple_bond}C-Li; a resonance at 556 ppm in the {sup 13}C NMR spectrum has been assigned to the carbide carbon. Addition of excess Na[HBEt{sub 3}] to Tp'(CO){sub 2}W{triple_bond}C-H generates the anionic methylidene complex [Na] [Tp'(CO){sub 2}W{triple_bond}CH{sub 2}].

  14. Moderate Hypoxia Exhibits Increased Endothelial Progenitor Vessel-forming Ability However Gestational Diabetes Caused to Impede Compensatory Defense Reaction

    PubMed Central

    Dincer, U. Deniz

    2016-01-01

    Endothelium represents a defense barrier and responds and integrates neuro humoral stimulus which describes as a compensatory mechanism. Endothelium formed with endothelial cells (ECs) and their progenitors. Endothelial progenitor cells (EPCs) represent minor subpopulation of mononuclear cells in the blood. During acute hypoxia, larger amount of EPCs mobilize into the peripheral blood and they directly contribute revascularization process. One of the subtypes of EPC is termed endothelial colony forming cells (ECFCs) which they possess de novo vessel-forming ability. The present study aims to investigate the role of hypoxia in EPCs functional and vessel-forming ability. Furthermore, it was investigated whether fetal exposure to a diabetic intrauterine environment influence EPCs adaptation ability. Human umbilical cord blood (HUCB) derived ECFCs were selected in all experimental procedures obtained from normal and gestational diabetes mellitus (GDM) subjects via in vitro cell culture methods. Early passage (<5) HUCB ECFCs obtain from GDM (n; 5) and control (n; 5) subjects were cultured with plates pre-coated with collagen in vitro 72 h hypoxic as well as normoxic condition. Endothelial, angiogenic and hypoxia associated gene specific primers designed to perform Real-time PCR. Senescenes assay conducted onto HUCB ECFCs to investigate their functional clonogenic ability. To quantify their vessel forming ability matrigel assay was applied. These data demonstrates that moderate hypoxia results increased vessel-forming ability and VEGFA expression in HUCB ECFCs obtained from control subjects. However, GDM caused to impede compensatory defense reaction against hypoxia which observed in control subjects. Thus, it illuminates beneficial information related future therapeutic modalities. PMID:27426097

  15. Design and Synthesis of Chiral Zn2+ Complexes Mimicking Natural Aldolases for Catalytic C–C Bond Forming Reactions in Aqueous Solution

    PubMed Central

    Itoh, Susumu; Sonoike, Shotaro; Kitamura, Masanori; Aoki, Shin

    2014-01-01

    Extending carbon frameworks via a series of C–C bond forming reactions is essential for the synthesis of natural products, pharmaceutically active compounds, active agrochemical ingredients, and a variety of functional materials. The application of stereoselective C–C bond forming reactions to the one-pot synthesis of biorelevant compounds is now emerging as a challenging and powerful strategy for improving the efficiency of a chemical reaction, in which some of the reactants are subjected to successive chemical reactions in just one reactor. However, organic reactions are generally conducted in organic solvents, as many organic molecules, reagents, and intermediates are not stable or soluble in water. In contrast, enzymatic reactions in living systems proceed in aqueous solvents, as most of enzymes generally function only within a narrow range of temperature and pH and are not so stable in less polar organic environments, which makes it difficult to conduct chemoenzymatic reactions in organic solvents. In this review, we describe the design and synthesis of chiral metal complexes with Zn2+ ions as a catalytic factor that mimic aldolases in stereoselective C–C bond forming reactions, especially for enantioselective aldol reactions. Their application to chemoenzymatic reactions in aqueous solution is also presented. PMID:24481060

  16. Asymmetric catalytic synthesis of the proposed structure of trocheliophorolide B.

    PubMed

    Trost, Barry M; Quintard, Adrien

    2012-09-01

    A concise catalytic asymmetric synthesis of the proposed structure of trocheliophorolide B is reported. The synthetic sequence notably features an asymmetric acetaldehyde alkynylation, a Ru-catalyzed alder-ene reaction, and a Zn-ProPhenol ynone aldol condensation. Comparison with the reported data suggests a misassignment of the natural product structure.

  17. RESEARCH REPORT: Eliciting students' understandings of chemical reactions using two forms of essay questions during a learning cycle

    NASA Astrophysics Data System (ADS)

    Cavallo, Ann M. L.

    2003-05-01

    We examined ninth-grade students' explanations of chemical reactions using two forms of an open-ended essay question during a learning cycle. One form provided students with key terms to be used as 'anchors' upon which to base their essay, whereas the second form did not. The essays were administered at three points: pre-learning cycle, post-concept application, and after additional concept application activities. Students' explanations were qualitatively examined and grouped according to common patterns representing their understandings or misunderstandings. Findings indicated that more misunderstandings were elicited by the use of key terms as compared to the non-use of key terms in the pre-test. Misunderstandings in the key term essay responses generally involved the misuse of these terms and their association with the concept. Findings also indicated significant positive shifts in students' understanding over the learning cycle. No perceptible increase in understanding occurred after additional application activities. Differences in gender were observed, with females showing equal or greater understanding compared to males, contradicting reports that males typically outperform females in the physical sciences and supporting the need to reconstruct assessment techniques to better reveal the conceptual understandings of all students.

  18. Recent Advances in Substrate-Controlled Asymmetric Induction Derived from Chiral Pool α-Amino Acids for Natural Product Synthesis.

    PubMed

    Paek, Seung-Mann; Jeong, Myeonggyo; Jo, Jeyun; Heo, Yu Mi; Han, Young Taek; Yun, Hwayoung

    2016-07-21

    Chiral pool α-amino acids have been used as powerful tools for the total synthesis of structurally diverse natural products. Some common naturally occurring α-amino acids are readily available in both enantiomerically pure forms. The applications of the chiral pool in asymmetric synthesis can be categorized prudently as chiral sources, devices, and inducers. This review specifically examines recent advances in substrate-controlled asymmetric reactions induced by the chirality of α-amino acid templates in natural product synthesis research and related areas.

  19. Reaction phase-forming and mechanical properties of Fe[sub 3]Al produced from elemental powders

    SciTech Connect

    Zhuang, L.Z.; Buekenhout, L. . Lab. for Materials Science); Duszczyk, J. )

    1994-04-01

    The Fe[sub 3]Al-based intermetallics can be produced by several conventional processing routes. However, there are applications where the powder metallurgy (P/M) process offers a better or the only route for producing these materials. A refined microstructure of the P/M products is beneficial for improving mechanical properties of the Fe[sub 3]Al-based intermetallics. Conventional P/M processing routes utilize mostly the prealloyed powders and consolidation is conducted by sintering, hot isostatic pressing (HIP) or hot extrusion. These methods involve generally processing steps and are, therefore, rather expensive. Reactive sintering, as an alternative fabrication method, is one of the novel and attractive processes. It is a method to obtain dense intermetallic compounds and intermetallic matrix composites from elemental powders using a self-sustaining reaction. This process, also known as combustion process, offers advantages over conventional processing methods including the use of less expensive, readily available, and easily compacted elemental powder, lower processing temperatures and shorter processing times, in short, low cost and energy savings. On the other hand, the reaction process of elemental iron-aluminium mixtures has a particular problem, i.e., a high porosity of the products due to extensive swelling. In order to achieve near-full density, the reactive sintering process should be assisted by an external pressure. In this case, reactive sintering is conducted in a HIP unit or a hot press. One should also appreciate that reactive hipping may provide near-net shape components which is important for reducing the cost because most of the intermetallics are hard-to-fabricate materials. This study describes the preparation of a binary Fe[sub 3]Al intermetallic compound by in-situ reaction phase-forming/consolidation from elemental powders, its mechanical properties, and a comparison of these properties with those of conventionally processed materials.

  20. Catalysis and Multi-Component Reactions

    NASA Astrophysics Data System (ADS)

    Shibasaki, Masakatsu; Yus, Miguel; Bremner, Stacy; Comer, Eamon; Shore, Gjergji; Morin, Sylvie; Organ, Michael G.; van der Eycken, Erik; Merkul, Eugen; Dorsch, Dieter; Müller, Thomas J. J.; Ryabukhin, Sergey V.; Ostapchuk, Eugeniy N.; Plaskon, Andrey S.; Volochnyuk, Dmitriy M.; Shivanyuk, Alexander N.; Tolmachev, Andrey A.; Sheibani, Hassan; Babaie, Maryam; Behzadi, Soheila; Dabiri, Minoo; Bahramnejad, Mahboobeh; Bashiribod, Sahareh; Hekmatshoar, Rahim; Sadjadi, Sodeh; Khorasani, Mohammad; Polyakov, Anatoliy I.; Eryomina, Vera A.; Medvedeva, Lidiya A.; Tihonova, Nadezhda I.; Listratova, Anna V.; Voskressensky, Leonid G.; Merkul, Eugen; Dorsch, Dieter; Müller, Thomas J. J.; Sheibani, Hassan; Esfandiarpoor, Zeinab; Behzadi, Soheila; Titova, Julia A.; Fedorova, Olga V.; Ovchinnikova, Irina G.; Valova, Marina S.; Koryakova, Olga V.; Rusinov, Gennady L.; Charushin, Valery N.; Hekmatshoar, Rahim; Sadjadi, Sodeh

    We have been studying the development of new asymmetric two-center catalysis using rare earth alkoxides and bifunctional sugar and related ligands. In The Fourth International Conference on Multi-Component Reactions and Related Chemistry (MCR 2009), new catalytic asymmetric reactions using catalysts 1 and 2 and catalytic asymmetric syntheses of ranirestat 3 and tamiflu 4 will be presented.

  1. Nucleoside adducts are formed by cooperative reaction of acetaldehyde and alcohols: possible mechanism for the role of ethanol in carcinogenesis.

    PubMed

    Fraenkel-Conrat, H; Singer, B

    1988-06-01

    The exocyclic amino groups of ribonucleosides and deoxyribonucleosides react rapidly at ambient temperature with acetaldehyde and alcohols to yield mixed acetals [--NH--CH(CH3)OR]. Nucleotides and nucleoside di- and triphosphates also react. Depending on the nucleoside used and on the relative amounts of aldehyde, alcohol, and water, preparative reactions reach equilibrium with yields up to 75% in a few hours. The structures have been confirmed by fast atom bombardment MS and proton NMR. Half-lives at 37 degrees C have been determined, and maximum stability is in the pH range of 7.5-9.5. In the absence of alcohol, acetaldehyde-nucleoside adducts could be isolated at 4 degrees C, but these were too unstable to characterize except for their UV spectra, also at 4 degrees C. Ethanol is often present in human blood and tissues, and acetaldehyde is its initial metabolic product, as well as being formed by many other metabolic processes. Both chemicals have separately been implicated in carcinogenic and other cytopathologic processes, but no cooperative mechanism has been proposed. The reactions reported here are of biological concern because they also occur in dilute aqueous solution. These findings supply a mechanism by which ethanol can be covalently bound to nucleic acids under physiological conditions.

  2. Reactivity of Cations and Zwitterions Formed in Photochemical and Acid-Catalyzed Reactions from m-Hydroxycycloalkyl-Substituted Phenol Derivatives.

    PubMed

    Cindro, Nikola; Antol, Ivana; Mlinarić-Majerski, Kata; Halasz, Ivan; Wan, Peter; Basarić, Nikola

    2015-12-18

    Three m-substituted phenol derivatives, each with a labile benzylic alcohol group and bearing either protoadamantyl 4, homoadamantyl 5, or a cyclohexyl group 6, were synthesized and their thermal acid-catalyzed and photochemical solvolytic reactivity studied, using preparative irradiations, fluorescence measurements, nanosecond laser flash photolysis, and quantum chemical calculations. The choice of m-hydroxy-substitution was driven by the potential for these phenolic systems to generate m-quinone methides on photolysis, which could ultimately drive the excited-state pathway, as opposed to forming simple benzylic carbocations in the corresponding thermal route. Indeed, thermal acid-catalyzed reactions gave the corresponding cations, which undergo rearrangement and elimination from 4, only elimination from 5, and substitution and elimination from 6. On the other hand, upon photoexcitation of 4-6 to S1 in a polar protic solvent, proton dissociation from the phenol, coupled with elimination of the benzylic OH (as hydroxide ion) gave zwitterions (formal m-quinone methides). The zwitterions exhibit reactivity different from the corresponding cations due to a difference in charge distribution, as shown by DFT calculations. Thus, protoadamantyl zwitterion has a less nonclassical character than the corresponding cation, so it does not undergo 1,2-shift of the carbon atom, as observed in the acid-catalyzed reaction. PMID:26595342

  3. Theoretical considerations for Reaction-Formed Silicon Carbide (RFSC) formation by molten silicon infiltration into slurry-derived preforms

    NASA Technical Reports Server (NTRS)

    Behrendt, D. R.; Singh, M.

    1993-01-01

    For reaction-formed silicon carbide (RFSC) ceramics produced by silicon melt infiltration of porous carbon preforms, equations are developed to relate the amount of residual silicon to the initial carbon density. Also, for a slurry derived preform containing both carbon and silicon powder, equations are derived which relate the amount of residual silicon in the RFSC to the relative density of the carbon in the preform and to the amount of silicon powder added to the slurry. For a porous carbon preform that does not have enough porosity to prevent choking-off of the silicon infiltration, these results show that complete silicon infiltration can occur by adding silicon powder to the slurry mixture used to produce these preforms.

  4. Synthesis of asymmetric tetracarboxylic acids and corresponding dianhydrides

    NASA Technical Reports Server (NTRS)

    Chuang, Chun-Hua (Inventor)

    2008-01-01

    This invention relates to processes for preparing asymmetrical biphenyl tetracarboxylic acids and the corresponding asymmetrical dianhydrides, namely 2,3,3',4'-biphenyl dianhydride (a-BPDA), 2,3,3',4'-benzophenone dianhydride (a-BTDA) and 3,4'-methylenediphthalic anhydride (-MDPA). By cross-coupling reactions of reactive metal substituted o-xylenes or by cross-coupling o-xylene derivatives in the presence of catalysts, this invention specifically produces asymmetrical biphenyl intermediates that are subsequently oxidized or hydrolyzed and oxidized to provide asymmetric biphenyl tetracarboxylic acids in comparatively high yields. These asymmetrical biphenyl tetracarboxylic acids are subsequently converted to the corresponding asymmetrical dianhydrides without contamination by symmetrical biphenyl dianhydrides.

  5. Chiral Brønsted Acids for Asymmetric Organocatalysis

    NASA Astrophysics Data System (ADS)

    Kampen, Daniela; Reisinger, Corinna M.; List, Benjamin

    Chiral Brønsted acid catalysis is an emerging area of organocatalysis. Since the pioneering studies of the groups of Akiyama and Terada in 2004 on the use of chiral BINOL phosphates as powerful Brønsted acid catalysts in asymmetric Mannich-type reactions, numerous catalytic asymmetric transformations involving imine activation have been realized by means of this catalyst class, including among others Friedel-Crafts, Pictet-Spengler, Strecker, cycloaddition reactions, transfer hydrogenations, and reductive aminations. More recently, chiral BINOL phosphates found application in multicomponent and cascade reactions as for example in an asymmetric version of the Biginelli reaction. With the introduction of chiral BINOL-derived N-triflyl phosphoramides in 2006, asymmetric Brønsted acid catalysis is no longer restricted to reactive substrates. Also certain carbonyl compounds can be activated through these stronger Brønsted acid catalysts. In dealing with sensitive substrate classes, chiral dicarboxylic acids proved of particular value.

  6. N-Methylphthalimide-substituted benzimidazolium salts and PEPPSI Pd-NHC complexes: synthesis, characterization and catalytic activity in carbon-carbon bond-forming reactions.

    PubMed

    Akkoç, Senem; Gök, Yetkin; İlhan, İlhan Özer; Kayser, Veysel

    2016-01-01

    A series of novel benzimidazolium salts (1-4) and their pyridine enhanced precatalyst preparation stabilization and initiation (PEPPSI) themed palladium N-heterocyclic carbene complexes [PdCl2(NHC)(Py)] (5-8), where NHC = 1-(N-methylphthalimide)-3-alkylbenzimidazolin-2-ylidene and Py = 3-chloropyridine, were synthesized and characterized by means of (1)H and (13)C{(1)H} NMR, UV-vis (for 5-8), ESI-FTICR-MS (for 2, 4, 6-8) and FTIR spectroscopic methods and elemental analysis. The synthesized compounds were tested in Suzuki-Miyaura cross-coupling (for 1-8) and arylation (for 5-8) reactions. As catalysts, they demonstrated a highly efficient route for the formation of asymmetric biaryl compounds even though they were used in very low loading. For example, all compounds displayed good catalytic activity for the C-C bond formation of 4-tert-butylphenylboronic acid with 4-chlorotoluene. PMID:26877810

  7. Chlorine in solid fuels fired in pulverized fuel boilers sources, forms, reactions, and consequences: a literature review

    SciTech Connect

    David A. Tillman; Dao Duong; Bruce Miller

    2009-07-15

    Chlorine is a significant source of corrosion and deposition, both from coal and from biomass, and in PF boilers. This investigation was designed to highlight the potential for corrosion risks associated with once-through units and advanced cycles. The research took the form of a detailed literature investigation to evaluate chlorine in solid fuels: coals of various ranks and origins, biomass fuels of a variety of types, petroleum cokes, and blends of the above. The investigation focused upon an extensive literature review of documents dating back to 1991. The focus is strictly corrosion and deposition. To address the deposition and corrosion issues, this review evaluates the following considerations: concentrations of chlorine in available solid fuels including various coals and biomass fuels, forms of chlorine in those fuels, and reactions - including reactivities - of chlorine in such fuels. The assessment includes consideration of alkali metals and alkali earth elements as they react with, and to, the chlorine and other elements (e.g., sulfur) in the fuel and in the gaseous products of combustion. The assessment also includes other factors of combustion: for example, combustion conditions including excess O{sub 2} and combustion temperatures. It also considers analyses conducted at all levels: theoretical calculations, bench scale laboratory data and experiments, pilot plant experiments, and full scale plant experience. Case studies and plant surveys form a significant consideration in this review. The result of this investigation focuses upon the concentrations of chlorine acceptable in coals burned exclusively, in coals burned with biomass, and in biomass cofired with coal. Values are posited based upon type of fuel and combustion technology. Values are also posited based upon both first principles and field experience. 86 refs., 8 figs., 7 tabs.

  8. Kinetic resolution of acids in acylation reactions in the presence of chiral tertiary amines

    SciTech Connect

    Potapov, V.M.; Dem'yanovich, V.M.; Khlebnikov, V.A.

    1988-07-10

    Asymmetric synthesis has now become an important method for the production of optically active compounds, and its most attractive form is asymmetric catalysis. This work was devoted to an investigation into asymmetric catalysis with chiral tertiary amines in acylation reactions. During the acylation of alcohols and amines by the action of racemic 2-phenylpropionic and 2-methyl-3-phenylpropionic acids in the presence of S-nicotine the initial acids are resolved kinetically. The (R)-2-phenylpropionic acid obtained in this way had an optical purity of 0.5-1.5%.

  9. Antioxidative, Antibacterial, and Food Functional Properties of the Half-Fin Anchovy Hydrolysates-Glucose Conjugates Formed via Maillard Reaction.

    PubMed

    Song, Ru; Yang, Peiyu; Wei, Rongbian; Ruan, Guanqiang

    2016-01-01

    The antioxidative, antibacterial, and food functional properties of the half-fin anchovy hydrolysates (HAHp)-glucose conjugates formed by Maillard reaction (MR) were investigated, respectively. Results of sugar and amino acid contents loss rates, browning index, and molecular weight distribution indicated that the initial pH of HAHp played an important role in the process of MR between HAHp and glucose. HAHp-glucose Maillard reaction products (HAHp-G MRPs) demonstrated enhanced antioxidative activities of reducing power and scavenging DPPH radicals compared to control groups. HAHp-G MRPs produced from the condition of pH 9.6 displayed the strongest reducing power. The excellent scavenging activity on DPPH radicals was found for HAHp(5.6)-G MRPs which was produced at pH 5.6. Additionally, HAHp(5.6)-G MRPs showed variable antibacterial activities against Escherichia coli, Pseudomonas fluorescens, Proteus vulgaris, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus subtilis, Bacillus megaterium, and Sarcina lutea, with the MIC values ranging from 8.3 to 16.7 μg/mL. Result of scanning electron microscopy (SEM) on E. coli suggested that HAHp(5.6)-G MRPs exhibited antibacterial activity by destroying the cell integrity through membrane permeabilization. Moreover, HAHp(5.6)-G MRPs had excellent foaming ability and stability at alkaline conditions of pH 8.0, and showed emulsion properties at acidic pH 4.0. These results suggested that specific HAHp-G MRPs should be promising functional ingredients used in foods. PMID:27331806

  10. Homogeneous asymmetric catalysis in fragrance chemistry.

    PubMed

    Ciappa, Alessandra; Bovo, Sara; Bertoldini, Matteo; Scrivanti, Alberto; Matteoli, Ugo

    2008-06-01

    Opposite enantiomers of a chiral fragrance may exhibit different olfactory activities making a synthesis in high enantiomeric purity commercially and scientifically interesting. Accordingly, the asymmetric synthesis of four chiral odorants, Fixolide, Phenoxanol, Citralis, and Citralis Nitrile, has been investigated with the aim to develop practically feasible processes. In the devised synthetic schemes, the key step that leads to the formation of the stereogenic center is the homogeneous asymmetric hydrogenation of a prochiral olefin. By an appropriate choice of the catalyst and the reaction conditions, Phenoxanol, Citralis, and Citralis Nitrile were obtained in high enantiomeric purity, and odor profiles of the single enantiomers were determined.

  11. Asymmetric catalysis with short-chain peptides.

    PubMed

    Lewandowski, Bartosz; Wennemers, Helma

    2014-10-01

    Within this review article we describe recent developments in asymmetric catalysis with peptides. Numerous peptides have been established in the past two decades that catalyze a wide variety of transformations with high stereoselectivities and yields, as well as broad substrate scope. We highlight here catalytically active peptides, which have addressed challenges that had thus far remained elusive in asymmetric catalysis: enantioselective synthesis of atropoisomers and quaternary stereogenic centers, regioselective transformations of polyfunctional substrates, chemoselective transformations, catalysis in-flow and reactions in aqueous environments.

  12. Comparison of the morphology of alkali–silica gel formed in limestones in concrete affected by the so-called alkali–carbonate reaction (ACR) and alkali–silica reaction (ASR)

    SciTech Connect

    Grattan-Bellew, P.E.; Chan, Gordon

    2013-05-15

    The morphology of alkali–silica gel formed in dolomitic limestone affected by the so-called alkali–carbonate reaction (ACR) is compared to that formed in a siliceous limestone affected by alkali–silica reaction (ASR). The particle of dolomitic limestone was extracted from the experimental sidewalk in Kingston, Ontario, Canada that was badly cracked due to ACR. The siliceous limestone particle was extracted from a core taken from a highway structure in Quebec, affected by ASR. Both cores exhibited marked reaction rims around limestone particles. The aggregate particles were polished and given a light gold coating in preparation for examination in a scanning electron microscope. The gel in the ACR aggregate formed stringers between the calcite crystals in the matrix of the rock, whereas gel in ASR concrete formed a thick layer on top of the calcite crystals, that are of the same size as in the ACR aggregate.

  13. ProPhenol-Catalyzed Asymmetric Additions by Spontaneously Assembled Dinuclear Main Group Metal Complexes

    PubMed Central

    2016-01-01

    Conspectus The development of catalytic enantioselective transformations has been the focus of many research groups over the past half century and is of paramount importance to the pharmaceutical and agrochemical industries. Since the award of the Nobel Prize in 2001, the field of enantioselective transition metal catalysis has soared to new heights, with the development of more efficient catalysts and new catalytic transformations at increasing frequency. Furthermore, catalytic reactions that allow higher levels of redox- and step-economy are being developed. Thus, alternatives to asymmetric alkene dihydroxylation and the enantioselective reduction of α,β-unsaturated ketones can invoke more strategic C–C bond forming reactions, such as asymmetric aldol reactions of an aldehyde with α-hydroxyketone donors or enantioselective alkynylation of an aldehyde, respectively. To facilitate catalytic enantioselective addition reactions, including the aforementioned aldol and alkynylation reactions, our lab has developed the ProPhenol ligand. In this Account, we describe the development and application of the ProPhenol ligand for asymmetric additions of both carbon- and heteroatom-based nucleophiles to various electrophiles. The ProPhenol ligand spontaneously forms chiral dinuclear metal complexes when treated with an alkyl metal reagent, such as Et2Zn or Bu2Mg. The resulting complex contains both a Lewis acidic site to activate an electrophile and a Brønsted basic site to deprotonate a pronucleophile. Initially, our research focused on the use of Zn-ProPhenol complexes to facilitate the direct aldol reaction. Fine tuning of the reaction through ligand modification and the use of additives enabled the direct aldol reaction to proceed in high yields and stereoselectivities with a broad range of donor substrates, including acetophenones, methyl ynones, methyl vinyl ketone, acetone, α-hydroxy carbonyl compounds, and glycine Schiff bases. Additionally, an analogous

  14. "N"-Heterocyclic Carbene-Catalyzed Reaction of Chalcone and Cinnamaldehyde to Give 1,3,4-Triphenylcyclopentene Using Organocatalysis to Form a Homoenolate Equivalent

    ERIC Educational Resources Information Center

    Snider, Barry B.

    2015-01-01

    In this experiment, students carry out a modern organocatalytic reaction using IMes·HCl and NaOH to catalyze the formation of 1,3,4-triphenylcyclopentene from cinnamaldehyde and chalcone in water. Deprotonation of IMes·HCl with NaOH forms the "N"-heterocyclic carbene IMes that reacts with cinnamaldehyde to form a homoenolate equivalent…

  15. SiC (SCS-6) Fiber Reinforced-Reaction Formed SiC Matrix Composites: Microstructure and Interfacial Properties

    NASA Technical Reports Server (NTRS)

    Singh, M.; Dickerson, R. M.; Olmstead, Forrest A.; Eldridge, J. I.

    1997-01-01

    Microstructural and interfacial characterization of unidirectional SiC (SCS-6) fiber reinforced-reaction formed SiC (RFSC) composites has been carried out. Silicon-1.7 at.% molybdenum alloy was used as the melt infiltrant, instead of pure silicon, to reduce the activity of silicon in the melt as well as to reduce the amount of free silicon in the matrix. Electron microprobe analysis was used to evaluate the microstructure and phase distribution in these composites. The matrix is SiC with a bi-modal grain-size distribution and small amounts of MoSi2, silicon, and carbon. Fiber push-outs tests on these composites showed that a desirably low interfacial shear strength was achieved. The average debond shear stress at room temperature varied with specimen thickness from 29 to 64 MPa, with higher values observed for thinner specimens. Initial frictional sliding stresses showed little thickness dependence with values generally close to 30 MPa. Push-out test results showed very little change when the test temperature was increased to 800 C from room temperature, indicating an absence of significant residual stresses in the composite.

  16. Development of a polymerase chain reaction (PCR) test for the detection of virulent forms of Vibrio parahaemolyticus.

    PubMed

    Kadhim, H M; Miah, A; Munn, C B; Gilpin, M L

    2012-04-01

    Vibrio parahaemolyticus is a marine bacterium and some strains cause gastroenteritis in humans. Clinical isolates are thought to possess virulence factors that are absent from the majority of environmental isolates. Use of randomly amplified polymorphic DNA (RAPD)-PCR produced a unique 600 bp amplicon (band Y) in the majority of clinical isolates and rarely in environmental isolates tested. The DNA from band Y was cloned and sequenced and found to code for an outer membrane protein (OMP). Two polymerase chain reaction (PCR) primers were designed to specifically amplify a 200 bp unique sequence from presumptive virulent strains (PCR-OMP). The virulence of 23 clinical and 32 environmental isolates was assessed in cytotoxicity tests by treatment of Caco-2 cells with extracellular products (ECPs). All but two of the clinical isolates (91%) were positive for the 200 bp PCR-OMP and their ECPs produced a significantly higher (p < 0.05) lactate dehydrogenase (LDH) release (mean 72.88%) than the ECPs of environmental isolates (mean 15.3%) with the exception of one environmental isolate that produced the 200 bp amplicon. A positive 200 bp PCR-OMP is strongly correlated with virulence, as determined by the cytotoxicity assay, and identified virulent forms better than current PCR tests for tdh, trh or T3SS2.

  17. Bimolecular recombination reactions: K-adiabatic and K-active forms of the bimolecular master equations and analytic solutions

    NASA Astrophysics Data System (ADS)

    Ghaderi, Nima

    2016-03-01

    Expressions for a K-adiabatic master equation for a bimolecular recombination rate constant krec are derived for a bimolecular reaction forming a complex with a single well or complexes with multiple well, where K is the component of the total angular momentum along the axis of least moment of inertia of the recombination product. The K-active master equation is also considered. The exact analytic solutions, i.e., the K-adiabatic and K-active steady-state population distribution function of reactive complexes, g(EJK) and g(EJ), respectively, are derived for the K-adiabatic and K-active master equation cases using properties of inhomogeneous integral equations (Fredholm type). The solutions accommodate arbitrary intermolecular energy transfer models, e.g., the single exponential, double exponential, Gaussian, step-ladder, and near-singularity models. At the high pressure limit, the krec for both the K-adiabatic and K-active master equations reduce, respectively, to the K-adiabatic and K-active bimolecular Rice-Ramsperger-Kassel-Marcus theory (high pressure limit expressions). Ozone and its formation from O + O2 are known to exhibit an adiabatic K. The ratio of the K-adiabatic to the K-active recombination rate constants for ozone formation at the high pressure limit is calculated to be ˜0.9 at 300 K. Results on the temperature and pressure dependence of the recombination rate constants and populations of O3 will be presented elsewhere.

  18. Bimolecular recombination reactions: K-adiabatic and K-active forms of the bimolecular master equations and analytic solutions.

    PubMed

    Ghaderi, Nima

    2016-03-28

    Expressions for a K-adiabatic master equation for a bimolecular recombination rate constant krec are derived for a bimolecular reaction forming a complex with a single well or complexes with multiple well, where K is the component of the total angular momentum along the axis of least moment of inertia of the recombination product. The K-active master equation is also considered. The exact analytic solutions, i.e., the K-adiabatic and K-active steady-state population distribution function of reactive complexes, g(EJK) and g(EJ), respectively, are derived for the K-adiabatic and K-active master equation cases using properties of inhomogeneous integral equations (Fredholm type). The solutions accommodate arbitrary intermolecular energy transfer models, e.g., the single exponential, double exponential, Gaussian, step-ladder, and near-singularity models. At the high pressure limit, the krec for both the K-adiabatic and K-active master equations reduce, respectively, to the K-adiabatic and K-active bimolecular Rice-Ramsperger-Kassel-Marcus theory (high pressure limit expressions). Ozone and its formation from O + O2 are known to exhibit an adiabatic K. The ratio of the K-adiabatic to the K-active recombination rate constants for ozone formation at the high pressure limit is calculated to be ∼0.9 at 300 K. Results on the temperature and pressure dependence of the recombination rate constants and populations of O3 will be presented elsewhere. PMID:27036434

  19. Microbial transformations 59: first kilogram scale asymmetric microbial Baeyer-Villiger oxidation with optimized productivity using a resin-based in situ SFPR strategy.

    PubMed

    Hilker, Iris; Wohlgemuth, Roland; Alphand, Véronique; Furstoss, Roland

    2005-12-20

    This study is demonstrating the scale up of asymmetric microbial Baeyer-Villiger oxidation of racemic bicyclo[3.2.0]hept-2-en-6-one (1) to the kilogram scale using a 50 L bioreactor. The process has been optimized with respect to bottlenecks identified in downscaled experiments. A high productivity was obtained combining a resin-based in situ substrate feeding and product removal methodology (in situ SFPR), a glycerol feed control, and an improved oxygenation device (using a sintered-metal sparger). As expected both regioisomeric lactones [(-)-(1S,5R)-2 and (-)-(1R,5S)-3] were obtained in nearly enantiopure form (ee > 98%) and good yield. This represents the first example of such an asymmetric Baeyer-Villiger biooxidation reaction ever operated at that scale. This novel resin-based in situ SFPR technology therefore clearly opens the way to further (industrial) upscaling of this highly valuable (asymmetric) reaction.

  20. Asymmetric Membrane Osmotic Capsules for Terbutaline Sulphate

    PubMed Central

    Gobade, N. G.; Koland, Marina; Harish, K. H.

    2012-01-01

    The aim of the present study was to design an asymmetric membrane capsule, an osmotic pump-based drug delivery system of ethyl cellulose for controlled release of terbutaline sulphate. asymmetric membrane capsules contains pore-forming water soluble additive, sorbitol in different concentrations in the capsule shell membrane, which after coming in contact with water, dissolves, resulting in an in situ formation of a microporous structure. The terbutaline sulphate is a β-adrenoreceptor agonist widely used in the treatment of asthma. The oral dosage regimen of terbutaline sulphate is 5 mg twice or thrice daily, the plasma half-life is approximate 3-4 h and it produces GI irritation with extensive first pass metabolism. Hence, terbutaline sulphate was chosen as a model drug with an aim to develop controlled release system. Different formulations of ethyl cellulose were prepared by phase inversion technique using different concentrations of sorbitol as pore forming agent. It was found that the thickness of the prepared asymmetric membrane capsules was increased with increase in concentration of ethyl cellulose and pore forming agent, i.e. sorbitol. The dye release study in water and 10% sodium chloride solution indicates that, the asymmetric membrane capsules follow osmotic principle to release content. The pores formed due to sorbitol were confirmed by microscopic observation of transverse section of capsule membrane. Data of in vitro release study of terbutaline sulphate from asymmetric membrane capsules indicated that, the capsules prepared with 10% and 12.5% of ethyl cellulose and 25% of sorbitol released as much as 97.44% and 76.27% in 12 h, respectively with zero order release rate. Hence asymmetric membrane capsule of 10% ethyl cellulose and 25% of sorbitol is considered as optimum for controlled oral delivery of terbutaline sulphate. PMID:23204625

  1. Asymmetric membrane osmotic capsules for terbutaline sulphate.

    PubMed

    Gobade, N G; Koland, Marina; Harish, K H

    2012-01-01

    The aim of the present study was to design an asymmetric membrane capsule, an osmotic pump-based drug delivery system of ethyl cellulose for controlled release of terbutaline sulphate. asymmetric membrane capsules contains pore-forming water soluble additive, sorbitol in different concentrations in the capsule shell membrane, which after coming in contact with water, dissolves, resulting in an in situ formation of a microporous structure. The terbutaline sulphate is a β-adrenoreceptor agonist widely used in the treatment of asthma. The oral dosage regimen of terbutaline sulphate is 5 mg twice or thrice daily, the plasma half-life is approximate 3-4 h and it produces GI irritation with extensive first pass metabolism. Hence, terbutaline sulphate was chosen as a model drug with an aim to develop controlled release system. Different formulations of ethyl cellulose were prepared by phase inversion technique using different concentrations of sorbitol as pore forming agent. It was found that the thickness of the prepared asymmetric membrane capsules was increased with increase in concentration of ethyl cellulose and pore forming agent, i.e. sorbitol. The dye release study in water and 10% sodium chloride solution indicates that, the asymmetric membrane capsules follow osmotic principle to release content. The pores formed due to sorbitol were confirmed by microscopic observation of transverse section of capsule membrane. Data of in vitro release study of terbutaline sulphate from asymmetric membrane capsules indicated that, the capsules prepared with 10% and 12.5% of ethyl cellulose and 25% of sorbitol released as much as 97.44% and 76.27% in 12 h, respectively with zero order release rate. Hence asymmetric membrane capsule of 10% ethyl cellulose and 25% of sorbitol is considered as optimum for controlled oral delivery of terbutaline sulphate. PMID:23204625

  2. Bismuth(III) trifluoromethanesulfonate catalyzed ring opening reaction of mono epoxy oleochemicals to form keto and diketo derivatives

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Using a catalytic system, methyl oleate is transformed into long chain keto and diketo derivatives via an epoxide route. Methyl 9(10)-oxooctadecanoate and methyl 9,10-dioxooctadecanoate were made by a ring opening reaction of epoxidized methyl oleate using bismuth triflate catalyst. Lower reaction t...

  3. Mach bands change asymmetrically during solar eclipses.

    PubMed

    Ross, John; Diamond, Mark R; Badcock, David R

    2003-01-01

    Observations made during two partial eclipses of the Sun show that the Mach bands on shadows cast by the Sun disappear and reappear asymmetrically as an eclipse progresses. These changes can be explained as due to changes in the shape of the penumbras of shadows as the visible portion of the Sun forms crescents of different orientation. PMID:12892435

  4. Mach bands change asymmetrically during solar eclipses.

    PubMed

    Ross, John; Diamond, Mark R; Badcock, David R

    2003-01-01

    Observations made during two partial eclipses of the Sun show that the Mach bands on shadows cast by the Sun disappear and reappear asymmetrically as an eclipse progresses. These changes can be explained as due to changes in the shape of the penumbras of shadows as the visible portion of the Sun forms crescents of different orientation.

  5. Asymmetric total synthesis of halicholactone.

    PubMed

    Baba, Y; Saha, G; Nakao, S; Iwata, C; Tanaka, T; Ibuka, T; Ohishi, H; Takemoto, Y

    2001-01-12

    The asymmetric total synthesis of the marine metabolite, halicholactone 1, is described. The bisallylic triol 6 with three chiral centers at C8, C12, and C15 was constructed by [2,3]-sigmatropic rearrangement of the sulfoxide 18, which was prepared stereoselectively using the chirality of (diene)Fe(CO)3 complexes. Introduction of the trans-substituted cyclopropane subunit into 21 was successfully achieved using the modified regio- and stereoselective Simmons-Smith reaction. The use of RCM (ring-closing metathesis) methodology (4-->35) was pivotal for the formation of a nine-membered unsaturated lactone fragment of halicholactone 1. As this approach is flexible and stereoselective, other oxylipins could be synthesized by the protocol described herein.

  6. Asymmetric total synthesis of vindoline.

    PubMed

    Kato, Daisuke; Sasaki, Yoshikazu; Boger, Dale L

    2010-03-24

    A concise asymmetric total synthesis of (-)-vindoline (1) is detailed based on a tandem intramolecular [4+2]/[3+2] cycloaddition cascade of a 1,3,4-oxadiazole inspired by the natural product structure, in which the tether linking the initiating dienophile and oxadiazole bears a chiral substituent that controls the facial selectivity of the initiating Diels-Alder reaction and sets absolute stereochemistry of the remaining six stereocenters in the cascade cycloadduct. This key reaction introduces three rings and four C-C bonds central to the pentacyclic ring system setting all six stereocenters and introducing essentially all the functionality found in the natural product in a single step. Implementation of the approach also required the development of a unique ring expansion reaction to provide a six-membered ring suitably functionalized for introduction of the Delta (6, 7)-double bond found in the core structure of vindoline and defined our use of a protected hydroxymethyl group as the substituent used to control the stereochemical course of the cycloaddition cascade.

  7. Asymmetric Redox-Annulation of Cyclic Amines

    PubMed Central

    2015-01-01

    Cyclic amines such as 1,2,3,4-tetrahydroisoquinoline undergo regiodivergent annulation reactions with 4-nitrobutyraldehydes. These redox-neutral transformations enable the asymmetric synthesis of highly substituted polycyclic ring systems in just two steps from commercial materials. The utility of this process is illustrated in a rapid synthesis of (−)-protoemetinol. Computational studies provide mechanistic insights and implicate the elimination of acetic acid from an ammonium nitronate intermediate as the rate-determining step. PMID:26348653

  8. Asymmetric soft-error resistant memory

    NASA Technical Reports Server (NTRS)

    Buehler, Martin G. (Inventor); Perlman, Marvin (Inventor)

    1991-01-01

    A memory system is provided, of the type that includes an error-correcting circuit that detects and corrects, that more efficiently utilizes the capacity of a memory formed of groups of binary cells whose states can be inadvertently switched by ionizing radiation. Each memory cell has an asymmetric geometry, so that ionizing radiation causes a significantly greater probability of errors in one state than in the opposite state (e.g., an erroneous switch from '1' to '0' is far more likely than a switch from '0' to'1'. An asymmetric error correcting coding circuit can be used with the asymmetric memory cells, which requires fewer bits than an efficient symmetric error correcting code.

  9. Aqueous-Medium Carbon-Carbon Bond-Forming Radical Reactions Catalyzed by Excited Rhodamine B as a Metal-Free Organic Dye under Visible Light Irradiation.

    PubMed

    Yoshioka, Eito; Kohtani, Shigeru; Jichu, Takahisa; Fukazawa, Takuya; Nagai, Toyokazu; Kawashima, Akira; Takemoto, Yoshiji; Miyabe, Hideto

    2016-08-19

    The utility of rhodamine B as a water-soluble organic photocatalyst was studied in the cascade radical addition-cyclization-trapping reactions under visible light irradiation. In the presence of (i-Pr)2NEt, the electron transfer from the excited rhodamine B to perfluoroalkyl iodides proceeded smoothly to promote the carbon-carbon bond-forming radical reactions in aqueous media. When i-C3F7I was employed as a radical precursor, the aqueous-medium radical reactions proceeded even in the absence of (i-Pr)2NEt. In these reactions, the direct electron transfer from the excited singlet state of rhodamine B would take place. Furthermore, the cleavage of the C-I bond in less reactive i-PrI could be achieved by the reductive electron transfer from the excited rhodamine B, which was confirmed by the fluorescence quenching of rhodamine B with the addition of i-PrI.

  10. Post-column reaction for simultaneous analysis of chromatic and leuco forms of malachite green and crystal violet by high-performance liquid chromatography with photometric detection

    USGS Publications Warehouse

    Allen, J.L.; Meinertz, J.R.

    1991-01-01

    The chromatic and leuco forms of malachite green and crystal violet were readily separated and detected by a sensitive and selective high-performance liquid chromatographic procedure. The chromatic and leuco forms of the dyes were separated within 11 min on a C18 column with a mobile phase of 0.05 M sodium acetate and 0.05 M acetic acid in water (19%) and methanol (81%). A reaction chamber, containing 10% PbO2 in Celite 545, was placed between the column and the spectrophotometric detector to oxidize the leuco forms of the dyes to their chromatic forms. Chromatic and leuco malachite green were quantified by their absorbance at 618 nm; and chromatic and leuco Crystal Violet by their absorbance at 588 nm. Detection limits for chromatic and leuco forms of both dyes ranged from 0.12 to 0.28 ng. A linear range of 1 to 100 ng was established for both forms of the dyes.

  11. Development of an analytical technique for the detection of alteration minerals formed in bentonite by reaction with alkaline solutions

    NASA Astrophysics Data System (ADS)

    Sakamoto, H.; Shibata, M.; Owada, H.; Kaneko, M.; Kuno, Y.; Asano, H.

    A multibarrier system consisting of cement-based backfill, structures and support materials, and a bentonite-based buffer material has been studied for the TRU waste disposal concept being developed in Japan, the aim being to restrict the migration of radionuclides. Concern regarding bentonite-based materials in this disposal environment relates to long-term alteration under hyper-alkaline conditions due to the presence of cementitious materials. In tests simulating the interaction between bentonite and cement, formation of secondary minerals due to alteration reactions under the conditions expected for geological disposal of TRU waste (equilibrated water with cement at low liquid/solid ratio) has not been observed, although alteration was observed under extremely hyper-alkaline conditions with high temperatures. This was considered to be due to the fact that analysis of C-S-H gel formed at the interface as a secondary mineral was difficult using XRD, because of its low crystallinity and low content. This paper describes an analytical technique for the characterization of C-S-H gel using a heavy liquid separation method which separates C-S-H gel from Kunigel V1 bentonite (bentonite produced in Japan) based on the difference in specific gravity between the crystalline minerals constituting Kunigel V1 and the secondary C-S-H gel. For development of C-S-H gel separation methods, simulated alteration samples were prepared by mixing 990 mg of unaltered Kunigel V1 and 10 mg of C-S-H gel synthesized using pure chemicals at a ratio of Ca/Si = 1.2. The simulated alteration samples were dispersed in bromoform-methanol mixtures with specific gravities ranging from 2.00 to 2.57 g/cm 3 and subjected to centrifuge separation to recover the light density fraction. Subsequent XRD analysis to identify the minerals was complemented by dissolution in 0.6 N hydrochloric acid to measure the Ca and Si contents. The primary peak (2 θ = 29.4°, Cu Kα) and secondary peaks (2 θ = 32.1

  12. Quantum state-resolved differential cross sections for complex-forming chemical reactions: Asymmetry is the rule, symmetry the exception

    SciTech Connect

    Larrégaray, Pascal Bonnet, Laurent

    2015-10-14

    We argue that statistical theories are generally unable to accurately predict state-resolved differential cross sections for triatomic bimolecular reactions studied in beam experiments, even in the idealized limit where the dynamics are fully chaotic. The basic reason is that quenching of interferences between partial waves is less efficient than intuitively expected, especially around the poles.

  13. Multipartite asymmetric quantum cloning

    SciTech Connect

    Iblisdir, S.; Gisin, N.; Acin, A.; Cerf, N.J.; Filip, R.; Fiurasek, J.

    2005-10-15

    We investigate the optimal distribution of quantum information over multipartite systems in asymmetric settings. We introduce cloning transformations that take N identical replicas of a pure state in any dimension as input and yield a collection of clones with nonidentical fidelities. As an example, if the clones are partitioned into a set of M{sub A} clones with fidelity F{sup A} and another set of M{sub B} clones with fidelity F{sup B}, the trade-off between these fidelities is analyzed, and particular cases of optimal N{yields}M{sub A}+M{sub B} cloning machines are exhibited. We also present an optimal 1{yields}1+1+1 cloning machine, which is an example of a tripartite fully asymmetric cloner. Finally, it is shown how these cloning machines can be optically realized.

  14. Asymmetric dipolar ring

    DOEpatents

    Prosandeev, Sergey A.; Ponomareva, Inna V.; Kornev, Igor A.; Bellaiche, Laurent M.

    2010-11-16

    A device having a dipolar ring surrounding an interior region that is disposed asymmetrically on the ring. The dipolar ring generates a toroidal moment switchable between at least two stable states by a homogeneous field applied to the dipolar ring in the plane of the ring. The ring may be made of ferroelectric or magnetic material. In the former case, the homogeneous field is an electric field and in the latter case, the homogeneous field is a magnetic field.

  15. Asymmetric information and economics

    NASA Astrophysics Data System (ADS)

    Frieden, B. Roy; Hawkins, Raymond J.

    2010-01-01

    We present an expression of the economic concept of asymmetric information with which it is possible to derive the dynamical laws of an economy. To illustrate the utility of this approach we show how the assumption of optimal information flow leads to a general class of investment strategies including the well-known Q theory of Tobin. Novel consequences of this formalism include a natural definition of market efficiency and an uncertainty principle relating capital stock and investment flow.

  16. Asymmetrical Capacitors for Propulsion

    NASA Technical Reports Server (NTRS)

    Canning, Francis X.; Melcher, Cory; Winet, Edwin

    2004-01-01

    Asymmetrical Capacitor Thrusters have been proposed as a source of propulsion. For over eighty years, it has been known that a thrust results when a high voltage is placed across an asymmetrical capacitor, when that voltage causes a leakage current to flow. However, there is surprisingly little experimental or theoretical data explaining this effect. This paper reports on the results of tests of several Asymmetrical Capacitor Thrusters (ACTs). The thrust they produce has been measured for various voltages, polarities, and ground configurations and their radiation in the VHF range has been recorded. These tests were performed at atmospheric pressure and at various reduced pressures. A simple model for the thrust was developed. The model assumed the thrust was due to electrostatic forces on the leakage current flowing across the capacitor. It was further assumed that this current involves charged ions which undergo multiple collisions with air. These collisions transfer momentum. All of the measured data was consistent with this model. Many configurations were tested, and the results suggest general design principles for ACTs to be used for a variety of purposes.

  17. Oscillating asymmetric dark matter

    SciTech Connect

    Tulin, Sean; Yu, Hai-Bo; Zurek, Kathryn M. E-mail: haiboyu@umich.edu

    2012-05-01

    We study the dynamics of dark matter (DM) particle-antiparticle oscillations within the context of asymmetric DM. Oscillations arise due to small DM number-violating Majorana-type mass terms, and can lead to recoupling of annihilation after freeze-out and washout of the DM density. Asymmetric DM oscillations 'interpolate' between symmetric and asymmetric DM freeze-out scenarios, and allow for a larger DM model-building parameter space. We derive the density matrix equations for DM oscillations and freeze-out from first principles using nonequilibrium field theory, and our results are qualitatively different than in previous studies. DM dynamics exhibits particle-vs-antiparticle 'flavor' effects, depending on the interaction type, analogous to neutrino oscillations in a medium. 'Flavor-sensitive' DM interactions include scattering or annihilation through a new vector boson, while 'flavor-blind' interactions include scattering or s-channel annihilation through a new scalar boson. In particular, we find that flavor-sensitive annihilation does not recouple when coherent oscillations begin, and that flavor-blind scattering does not lead to decoherence.

  18. Utility of oxidation-reduction reaction for the determination of ranitidine hydrochloride in pure form, in dosage forms and in the presence of its oxidative degradates

    NASA Astrophysics Data System (ADS)

    Amin, A. S.; Ahmed, I. S.; Dessouki, H. A.; Gouda, E. A.

    2003-03-01

    Three simple, accurate and sensitive colorimetric methods (A, B and C) for the determination of ranitidine HCl (RHCl) in bulk sample, in dosage forms and in the presence of its oxidative degradates are described. The first method A is based on the oxidation of the drug by N-bromosuccinimide (NBS) and determination of the unreacted NBS by measurement of the decrease in absorbance of amaranth dye (AM) at a suitable λmax=520 nm. The methods B and C involve the addition of excess Ce 4+ and determination of the unreacted oxidant by decrease the red color of chromotrope 2R (C2R) at a suitable λmax=528 nm for method B or decrease the orange pink color of rhodamine 6G (Rh6G) at a suitable λmax=526 nm for method C. Regression analysis of Beer-Lambert plots showed good correlation in the concentration ranges 0.2-3.6, 0.1-2.8 and 0.1-2.6 μg ml -1 for methods A, B and C, respectively. The apparent molar absorptivity. Sandell sensitivity, detection and quantitation limits were calculated. For more accurate results, Ringbom optimum concentration ranges were 0.3-3.4, 0.2-2.6 and 0.2-2.4 μg ml -1 for methods A, B and C, respectively. Analyzing pure and dosage forms containing RHCl tested the validity of the proposed methods. The relative standard deviations were ≤1.38 with recoveries 98.9-101.0%.

  19. Asymmetric catalysis: An enabling science

    PubMed Central

    Trost, Barry M.

    2004-01-01

    Chirality of organic molecules plays an enormous role in areas ranging from medicine to material science, yet the synthesis of such entities in one enantiomeric form is one of the most difficult challenges. The advances being made stem from the convergence of a broader understanding of theory and how structure begets function, the developments in the interface between organic and inorganic chemistry and, most notably, the organic chemistry of the transition metals, and the continuing advancements in the tools to help define structure, especially in solution. General themes for designing catalysts to effect asymmetric induction are helping to make this strategy more useful, in general, with the resultant effect of a marked enhancement of synthetic efficiency. PMID:14990801

  20. Branching Ratios and Vibrational Distributions in Water-Forming Reactions of OH and OD Radicals with Methylamines.

    PubMed

    Butkovskaya, N I; Setser, D W

    2016-09-01

    Reactions of OH and OD radicals with (CH3)3N, (CH3)2NH, and CH3NH2 were studied by Fourier transform infrared emission spectroscopy (FTIR) of the water product molecules from a fast-flow reactor at 298 K. The rate constants (4.4 ± 0.5) × 10(-11), (5.2 ± 0.8) × 10(-11), and (2.0 ± 0.4) × 10(-11) cm(3) molecule(-1) s(-1) were determined for OD + (CH3)3N, (CH3)2NH, and CH3NH2, respectively, by comparing the HOD emission intensities to the HOD intensity from the OD reaction with H2S. Abstraction from the nitrogen site competes with abstraction from the methyl group, as obtained from an analysis of the HOD and D2O emission intensities from the OD reactions with the deuterated reactants, (CD3)2NH and CD3NH2. After adjustment for the hydrogen-deuterium kinetic isotope effect, the product branching fractions of the hydrogen abstraction from the nitrogen for di- and monomethylamine were found to be 0.34 ± 0.04 and 0.26 ± 0.05, respectively. Vibrational distributions of the H2O, HOD, and D2O molecules are typical for direct hydrogen atom abstraction from polar molecules, even though activation energies are negative because of the formation of pre-transition-state complexes. Comparison is made to the reactions of hydroxyl radicals with ammonia and with other compounds with primary C-H bonds to discuss specific features of disposal of energy to water product. PMID:27504785

  1. DNA–Based Asymmetric Catalysis: Role of Ionic Solvents and Glymes

    PubMed Central

    Zhao, Hua; Shen, Kai

    2014-01-01

    Recently, DNA has been evaluated as a chiral scaffold for metal complexes to construct so called ‘DNA-based hybrid catalysts’, a robust and inexpensive alternative to enzymes. The unique chiral structure of DNA allows the hybrid catalysts to catalyze various asymmetric synthesis reactions. However, most current studies used aqueous buffers as solvents for these asymmetric reactions, where substrates/products are typically suspended in the solutions. The mass transfer limitation usually requires a long reaction time. To overcome this hurdle and to advance DNA-based asymmetric catalysis, we evaluated a series of ionic liquids (ILs), inorganic salts, deep eutectic solvents (DES), glymes, glycols, acetonitrile and methanol as co-solvents/additives for the DNA-based asymmetric Michael addition. In general, these additives induce indistinguishable changes to the DNA B-form duplex conformation as suggested by circular dichroism (CD) spectroscopy, but impose a significant influence on the catalytic efficiency of the DNA-based hybrid catalyst. Conventional organic solvents (e.g. acetonitrile and methanol) led to poor product yields and/or low enantioselectivities. Most ILs and inorganic salts cause the deactivation of the hybrid catalyst except 0.2 M [BMIM][CF3COO] (95.4% ee and 93% yield) and 0.2 M [BMIM]Cl (93.7% ee and 89% yield). Several other additives have also been found to improve the catalytic efficiency of the DNA-based hybrid catalyst (control reaction without additive gives >99% ee and 87% yield): 0.4 M glycerol (>99% ee and 96% yield at 5 °C or 96.2% ee and 83% yield at room temperature), 0.2 M choline chloride/glycerol (1:2) (92.4% ee and 90% yield at 5 °C or 94.0% ee and 88% yield at room temperature), and 0.5 M dipropylene glycol dimethyl ether (>99% ee and 87% yield at room temperature). The use of some co-solvents/additives allows the Michael addition to be performed at a higher temperature (e.g. room temperature vs 5 °C) and a shorter reaction time

  2. DNA-Based Asymmetric Catalysis: Role of Ionic Solvents and Glymes.

    PubMed

    Zhao, Hua; Shen, Kai

    2014-01-01

    Recently, DNA has been evaluated as a chiral scaffold for metal complexes to construct so called 'DNA-based hybrid catalysts', a robust and inexpensive alternative to enzymes. The unique chiral structure of DNA allows the hybrid catalysts to catalyze various asymmetric synthesis reactions. However, most current studies used aqueous buffers as solvents for these asymmetric reactions, where substrates/products are typically suspended in the solutions. The mass transfer limitation usually requires a long reaction time. To overcome this hurdle and to advance DNA-based asymmetric catalysis, we evaluated a series of ionic liquids (ILs), inorganic salts, deep eutectic solvents (DES), glymes, glycols, acetonitrile and methanol as co-solvents/additives for the DNA-based asymmetric Michael addition. In general, these additives induce indistinguishable changes to the DNA B-form duplex conformation as suggested by circular dichroism (CD) spectroscopy, but impose a significant influence on the catalytic efficiency of the DNA-based hybrid catalyst. Conventional organic solvents (e.g. acetonitrile and methanol) led to poor product yields and/or low enantioselectivities. Most ILs and inorganic salts cause the deactivation of the hybrid catalyst except 0.2 M [BMIM][CF3COO] (95.4% ee and 93% yield) and 0.2 M [BMIM]Cl (93.7% ee and 89% yield). Several other additives have also been found to improve the catalytic efficiency of the DNA-based hybrid catalyst (control reaction without additive gives >99% ee and 87% yield): 0.4 M glycerol (>99% ee and 96% yield at 5 °C or 96.2% ee and 83% yield at room temperature), 0.2 M choline chloride/glycerol (1:2) (92.4% ee and 90% yield at 5 °C or 94.0% ee and 88% yield at room temperature), and 0.5 M dipropylene glycol dimethyl ether (>99% ee and 87% yield at room temperature). The use of some co-solvents/additives allows the Michael addition to be performed at a higher temperature (e.g. room temperature vs 5 °C) and a shorter reaction time (24

  3. Processes forming Gas, Tar, and Coke in Cellulose Gasification from Gas-Phase Reactions of Levoglucosan as Intermediate.

    PubMed

    Fukutome, Asuka; Kawamoto, Haruo; Saka, Shiro

    2015-07-01

    The gas-phase pyrolysis of levoglucosan (LG), the major intermediate species during cellulose gasification, was studied experimentally over the temperature range of 400-900 °C. Gaseous LG did not produce any dehydration products, which include coke, furans, and aromatic substances, although these are characteristic products of the pyrolysis of molten LG. Alternatively, at >500 °C, gaseous LG produced only fragmentation products, such as noncondensable gases and condensable C1 -C3 fragments, as intermediates during noncondensable gas formation. Therefore, it was determined that secondary reactions of gaseous LG can result in the clean (tar- and coke-free) gasification of cellulose. Cooling of the remaining LG in the gas phase caused coke formation by the transition of the LG to the molten state. The molecular mechanisms that govern the gas- and molten-phase reactions of LG are discussed in terms of the acid catalyst effect of intermolecular hydrogen bonding to promote the molten-phase dehydration reactions. PMID:26099988

  4. Processes forming Gas, Tar, and Coke in Cellulose Gasification from Gas-Phase Reactions of Levoglucosan as Intermediate.

    PubMed

    Fukutome, Asuka; Kawamoto, Haruo; Saka, Shiro

    2015-07-01

    The gas-phase pyrolysis of levoglucosan (LG), the major intermediate species during cellulose gasification, was studied experimentally over the temperature range of 400-900 °C. Gaseous LG did not produce any dehydration products, which include coke, furans, and aromatic substances, although these are characteristic products of the pyrolysis of molten LG. Alternatively, at >500 °C, gaseous LG produced only fragmentation products, such as noncondensable gases and condensable C1 -C3 fragments, as intermediates during noncondensable gas formation. Therefore, it was determined that secondary reactions of gaseous LG can result in the clean (tar- and coke-free) gasification of cellulose. Cooling of the remaining LG in the gas phase caused coke formation by the transition of the LG to the molten state. The molecular mechanisms that govern the gas- and molten-phase reactions of LG are discussed in terms of the acid catalyst effect of intermolecular hydrogen bonding to promote the molten-phase dehydration reactions.

  5. Garnet-forming reactions in felsic orthogneiss: Implications for densification and strengthening of the lower continental crust

    NASA Astrophysics Data System (ADS)

    Williams, M. L.; Dumond, G.; Mahan, K.; Regan, S.; Holland, M.

    2014-11-01

    Growth of garnet and pyroxene in orthogneiss from the Athabasca granulite terrane (AGT), northern Saskatchewan, provides a model for progressive densification and strengthening of the lower continental crust with implications for the recycling and long-term evolution of continental crust. Two distinct assemblages and textures are preserved in granitic and granodioritic gneiss. Low-strain orthogneiss displays igneous textures and assemblages of Opx+Kfs+Pl+Mag+Qz (± Bt, Hbl, Ilm). High-strain, dynamically recrystallized tectonites have additional garnet, clinopyroxene, and a more Na-rich plagioclase, along with relict orthopyroxene. The reaction (Opx+Ca-rich Pl=Grt+Cpx+Na-rich Pl+Qz) is informally called the “Mary reaction” after documented occurrences in the Mary granitoid batholith. The reaction represents the transition from medium-pressure to high-pressure granulite (Green and Ringwood, 1967), but reaction progress was achieved in these deep crustal rocks along an isobaric cooling path at ca. 1 GPa (35-40 km-depth). Ambient P-T conditions were well within the product (low-T-side) stability field. The abundance of the product assemblage (Grt+Cpx+Na-rich Pl) increases with deformation. Metastable igneous assemblages are widely preserved in low-strain samples. With increasing strain, garnet occurs within recrystallized mantles of plagioclase porphyroclasts, and clinopyroxene occurs in the deformed tails of orthopyroxene crystals. Deformation is interpreted to aid in the breakdown of plagioclase and/or the nucleation of garnet and clinopyroxene. Garnet and pyroxene modes have been observed to exceed 10 vol% in the AGT, but larger amounts are possible because Ca-rich plagioclase and orthopyroxene remnants are widely preserved. Densities increase from ca. 2.6 to ca. 3.0 g/cm and modeled P-wave velocities approach 7.0 km/s in felsic rocks. Densities in mafic rocks approach 3.4 cm. The reaction occurred at least twice in the AGT, 2.6 and 1.9 Ga, and may have

  6. Growth behavior of LiMn2O4 particles formed by solid-state reactions in air and water vapor

    NASA Astrophysics Data System (ADS)

    Kozawa, Takahiro; Yanagisawa, Kazumichi; Murakami, Takeshi; Naito, Makio

    2016-11-01

    Morphology control of particles formed during conventional solid-state reactions without any additives is a challenging task. Here, we propose a new strategy to control the morphology of LiMn2O4 particles based on water vapor-induced growth of particles during solid-state reactions. We have investigated the synthesis and microstructural evolution of LiMn2O4 particles in air and water vapor atmospheres as model reactions; LiMn2O4 is used as a low-cost cathode material for lithium-ion batteries. By using spherical MnCO3 precursor impregnated with LiOH, LiMn2O4 spheres with a hollow structure were obtained in air, while angulated particles with micrometer sizes were formed in water vapor. The pore structure of the particles synthesized in water vapor was found to be affected at temperatures below 700 °C. We also show that the solid-state reaction in water vapor is a simple and valuable method for the large-scale production of particles, where the shape, size, and microstructure can be controlled.

  7. Trimeric forms of the photosystem I reaction center complex pre-exist in the membranes of the cyanobacterium Spirulina platensis.

    PubMed

    Shubin, V V; Tsuprun, V L; Bezsmertnaya, I N; Karapetyan, N V

    1993-11-01

    Oligomeric and monomeric forms of chlorophyll-protein complexes of photosystem I (PSI) have been isolated from the mesophilic cyanobacterium Spirulina [(1992) FEBS Lett. 309, 340-342]. Electron microscopic analysis of the complexes showed that the oligomeric form is a trimer of the shape and dimensions similar to those of the trimer from thermophilic cyanobacteria. The chlorophyl ratio in the isolated trimer and monomer was found to be 7:3. The trimeric form of PSI complex in contrast to the monomeric one contains the chlorophyll emitting at 760 nm (77K), which is also found in Spirulina membranes and therefore could be used as an intrinsic probe for the trimeric complex. The 77K circular dichroism spectrum of the trimeric form is much more similar to that of Spirulina membranes than the spectrum of the monomer. Thus, the trimeric PSI complexes exist and dominate in the Spirulina membranes. PMID:8224233

  8. Chemistry of the catalytic conversion of phthalate into its cis-dihydrodiol during the reaction of oxygen with the reduced form of phthalate dioxygenase.

    PubMed

    Tarasev, Michael; Ballou, David P

    2005-04-26

    The phthalate dioxygenase system, a Rieske non-heme iron dioxygenase, catalyzes the dihydroxylation of phthalate to form the 4,5-dihydro-cis-dihydrodiol of phthalate (DHD). It has two components: phthalate dioxygenase (PDO), a multimer with one Rieske-type [2Fe-2S] and one mononuclear Fe(II) center per monomer, and a reductase (PDR) that contains flavin mononucleotide (FMN) and a plant-type ferredoxin [2Fe-2S] center. This work shows that product formation in steady-state reactions is tightly coupled to electron delivery, with 1 dihydrodiol (DHD) of phthalate formed for every 2 electrons delivered from NADH. However, in reactions of reduced PDO with O(2), only about 0.5 DHD is formed per Rieske center that becomes oxidized. Although the product forms rapidly, its release from PDO is slow in these reactions with oxygen that do not include reductase and NADH. EPR data show that, at the completion of the oxidation, iron in the mononuclear center remains in the ferrous state. In contrast, naphthalene dioxygenase (NDO) [Wolfe, M. D., Parales, J. V., Gibson, D. T., and Lipscomb, J. D. (2001) J. Biol. Chem. 276, 1945-1953] and benzoate dioxygenase (BZDO) [Wolfe, M. D., Altier, D. J., Stubna, A., Popescu, C. V., Munck, E., and Lipscomb, J. D. (2002) Biochemistry, 41, 9611-9626], related Rieske non-heme iron dioxygenases, form 1 DHD per Rieske center oxidized, and the mononuclear center iron ends up ferric. Thus, both electrons from reduced NDO and BZDO monomers are used to form the product, whereas only the reduced Rieske centers in PDO become oxidized during production of DHD. This emphasizes the importance of PDO subunit interaction in catalysis. Electron redistribution was practically unaffected by the presence of oxidized PDR. A scheme is presented that emphasizes some of the differences in the mechanisms involved in substrate hydroxylation employed by PDO and either NDO or BZDO. PMID:15835907

  9. Forming metal-intermetallic or metal-ceramic composites by self-propagating high-temperature reactions

    DOEpatents

    Rawers, James C.; Alman, David E.; Petty, Jr., Arthur V.

    1996-01-01

    Industrial applications of composites often require that the final product have a complex shape. In this invention intermetallic or ceramic phases are formed from sheets of unreacted elemental metals. The process described in this invention allows the final product shape be formed prior to the formation of the composite. This saves energy and allows formation of shaped articles of metal-intermetallic composites composed of brittle materials that cannot be deformed without breaking.

  10. Project for measuring the neutron electromagnetic form factor in the reaction e{sup +}e{sup -} {yields} nn-bar at the VEPP-2000 collider

    SciTech Connect

    Golubev, V. B.; Serednyakov, S. I.; Skovpen, K. Yu. Usov, Yu. V.

    2009-04-15

    A project aimed at measuring the neutron electromagnetic form factor in the reaction e{sup +}e{sup -} {yields} nn-bar with the SND detector at the VEPP-2000 e{sup +}e{sup -} collider is presented. The results obtained for the time resolution of the NaI(Tl) counter using flash-ADC are reported along with estimates of the efficiency of separation of neutron-antineutron events.

  11. Gas-phase reactivity of peptide thiyl (RS•), perthiyl (RSS•), and sulfinyl (RSO•) radical ions formed from atmospheric pressure ion/radical reactions.

    PubMed

    Tan, Lei; Xia, Yu

    2013-04-01

    In this study, we demonstrated the formation of gas-phase peptide perthiyl (RSS•) and thiyl (RS•) radical ions besides sulfinyl radical (RSO•) ions from atmospheric pressure (AP) ion/radical reactions of peptides containing inter-chain disulfide bonds. The identity of perthiyl radical was verified from characteristic 65 Da (•SSH) loss in collision-induced dissociation (CID). This signature loss was further used to assess the purity of peptide perthiyl radical ions formed from AP ion/radical reactions. Ion/molecule reactions combined with CID were carried out to confirm the formation of thiyl radical. Transmission mode ion/molecule reactions in collision cell (q2) were developed as a fast means to estimate the population of peptide thiyl radical ions. The reactivity of peptide thiyl, perthiyl, and sulfinyl radical ions was evaluated based on ion/molecule reactions toward organic disulfides, allyl iodide, organic thiol, and oxygen, which followed in order of thiyl (RS•) > perthiyl (RSS•) > sulfinyl (RSO•). The gas-phase reactivity of these three types of sulfur-based radicals is consistent with literature reports from solution studies.

  12. Asymmetric AgPd-AuNR heterostructure with enhanced photothermal performance and SERS activity

    NASA Astrophysics Data System (ADS)

    Zhang, Han; Liu, Zeke; Kang, Xiaolin; Guo, Jun; Ma, Wanli; Cheng, Si

    2016-01-01

    Most as-reported nanostructures through galvanic replacement reactions are still symmetric hollow structures, until now. Asymmetric structures fabricated through a galvanic replacement reaction have been rarely reported. However, asymmetric heterostructures can generally lead to new intriguing properties through asymmetric synergistic coupling. Here, we report a simple synthesis of an asymmetric one-ended AgPd bimetal on Au nanorods (AuNR) by combining a galvanic replacement reaction with an Ostwald ripening process. The morphological evolution from a nanodumbbell to a dandelion structure is thoroughly investigated. The unique asymmetric AgPd-AuNR heterostructures possess the required plasmonic performance and avoid strong damping caused by the poor plasmonic metal Pd, resulting in a superior photothermal heating performance and enhanced SERS sensitivity for in situ monitoring of a catalytic reaction compared with the symmetric counterparts.Most as-reported nanostructures through galvanic replacement reactions are still symmetric hollow structures, until now. Asymmetric structures fabricated through a galvanic replacement reaction have been rarely reported. However, asymmetric heterostructures can generally lead to new intriguing properties through asymmetric synergistic coupling. Here, we report a simple synthesis of an asymmetric one-ended AgPd bimetal on Au nanorods (AuNR) by combining a galvanic replacement reaction with an Ostwald ripening process. The morphological evolution from a nanodumbbell to a dandelion structure is thoroughly investigated. The unique asymmetric AgPd-AuNR heterostructures possess the required plasmonic performance and avoid strong damping caused by the poor plasmonic metal Pd, resulting in a superior photothermal heating performance and enhanced SERS sensitivity for in situ monitoring of a catalytic reaction compared with the symmetric counterparts. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07333b

  13. Microfluidic fabrication of asymmetric giant lipid vesicles

    PubMed Central

    Hu, Peichi C.; Li, Su; Malmstadt, Noah

    2011-01-01

    We have developed a microfluidic technology for the fabrication of compositionally asymmetric giant unilamellar vesicles (GUVs). The vesicles are assembled in two independent steps. In each step, a lipid monolayer is formed at a water-oil interface. The first monolayer is formed inside of a microfluidic device with a multiphase droplet flow configuration consisting of a continuous oil stream in which water droplets are formed. These droplets are dispensed into a vessel containing a layer of oil over a layer of water. The second lipid monolayer is formed by transferring the droplets through this second oil-water interface by centrifugation. By dissolving different lipid compositions in the different oil phases, the composition of each leaflet of the resulting lipid bilayer can be controlled. We have demonstrated membrane asymmetry by showing differential fluorescence quenching of labeled lipids in each leaflet and by demonstrating that asymmetric GUVs will bind an avidin-coated surface only when biotinylated lipids are targeted to the outer leaflet. In addition, we have demonstrated the successful asymmetric targeting of phosphatidylserine lipids to each leaflet, producing membranes with a biomimetic and physiologically relevant compositional asymmetry. PMID:21449588

  14. Identification of secondary phases formed during unsaturated reaction of UO{sub 2} with EJ-13 water

    SciTech Connect

    Bates, J.K.; Tani, B.S.; Veleckis, E.

    1989-11-01

    A set of experiments, wherein UO{sub 2} has been contacted by dripping water, has been conducted over a period of 182.5 weeks. The experiments are being conducted to develop procedures to study spent fuel reaction under unsaturated conditions that are expected to exist over the lifetime of the proposed Yucca Mountain repository site. One half of the experiments have been terminated, while one half are ongoing. Analyses of solutions that have dripped from the reacted UO{sub 2} have been performed for all experiments, while the reacted UO{sub 2} surfaces have been examined for the terminated experiments. A pulse of uranium release from the UO{sub 2} solid, combined with the formation of schoepite on the surface of the UO{sub 2}, was observed between 39 and 96 weeks of reaction. Thereafter, the uranium release decreased and a second set of secondary phases was observed. The latter phases incorporated cations from the EJ-13 water and included boltwoodite, uranophane, sklodowskite, compreignacite, and schoepite. The experiments are continuing to monitor whether additional changes in solution chemistry or secondary phase formation occurs. 6 refs., 2 figs., 2 tabs.

  15. Asymmetric quantum convolutional codes

    NASA Astrophysics Data System (ADS)

    La Guardia, Giuliano G.

    2016-01-01

    In this paper, we construct the first families of asymmetric quantum convolutional codes (AQCCs). These new AQCCs are constructed by means of the CSS-type construction applied to suitable families of classical convolutional codes, which are also constructed here. The new codes have non-catastrophic generator matrices, and they have great asymmetry. Since our constructions are performed algebraically, i.e. we develop general algebraic methods and properties to perform the constructions, it is possible to derive several families of such codes and not only codes with specific parameters. Additionally, several different types of such codes are obtained.

  16. Spectroscopic investigations of humic-like acids formed via polycondensation reactions between glycine, catechol and glucose in the presence of natural zeolites

    NASA Astrophysics Data System (ADS)

    Fukuchi, Shigeki; Miura, Akitaka; Okabe, Ryo; Fukushima, Masami; Sasaki, Masahide; Sato, Tsutomu

    2010-10-01

    Polycondensation reactions between low-molecular-weight compounds, such as amino acids, sugars and phenols, are crucially important processes in the formation of humic substances, and clay minerals have the ability to catalyze these reactions. In the present study, catechol (CT), glycine (Gly) and glucose (Gl) were used as representative phenols, amino acids and sugars, respectively, and the effects of the catalytic activities of natural zeolites on polycondensation reactions between these compounds were investigated. The extent of polycondensation was evaluated by measuring the specific absorbance at 600 nm ( E600) as an index of the degree of darkening. After a 3-week incubation period, the E600 values for solutions that contained zeolite samples were 4-10 times greater than those measured in the absence of zeolite, suggesting that the zeolite had, in fact, catalyzed the polycondensation reaction. The humic-like acids (HLAs) produced in the reactions were isolated, and their elemental composition and molecular weights determined. When formed in the presence of a zeolite, the nitrogen contents and molecular weights for the HLAs were significantly higher, compared to the HLA sample formed in the absence of zeolite. In addition, solid-state CP-MAS 13C NMR spectra and carboxylic group analyses of the HLA samples indicated that the concentration of carbonyl carbon species for quinones and ketones produced in the presence of zeolite were higher than the corresponding values for samples produced in the absence of a zeolite. Carbonyl carbons in quinones and ketones indicate the nucleophilic characteristics of the samples. Therefore, a nitrogen atom in Gly, which serves as nucleophile, is incorporated into quinones and ketones in CT and Gl. The differences in the catalytic activities of the zeolite samples can be attributed to differences in their transition metal content (Fe, Mn and Ti), which function as Lewis acids.

  17. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    DOE PAGESBeta

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-12-23

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenatedmore » molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV–visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

  18. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    DOE PAGESBeta

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-08-19

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (·OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified,more » including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than ·OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

  19. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    SciTech Connect

    Yu, Lu; Smith, Jeremy; Laskin, Alexander; Anastasio, Cort N.; Laskin, Julia; Zhang, Qi

    2014-01-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (•OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), desorption electrospray ionization mass spectrometry (DESIMS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O/C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than •OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O/C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  20. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-08-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants - the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (\\centerdot OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than \\centerdot OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  1. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-12-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants - the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  2. Asymmetric inclusion process.

    PubMed

    Reuveni, Shlomi; Eliazar, Iddo; Yechiali, Uri

    2011-10-01

    We introduce and explore the asymmetric inclusion process (ASIP), an exactly solvable bosonic counterpart of the fermionic asymmetric exclusion process (ASEP). In both processes, random events cause particles to propagate unidirectionally along a one-dimensional lattice of n sites. In the ASEP, particles are subject to exclusion interactions, whereas in the ASIP, particles are subject to inclusion interactions that coalesce them into inseparable clusters. We study the dynamics of the ASIP, derive evolution equations for the mean and probability generating function (PGF) of the sites' occupancy vector, obtain explicit results for the above mean at steady state, and describe an iterative scheme for the computation of the PGF at steady state. We further obtain explicit results for the load distribution in steady state, with the load being the total number of particles present in all lattice sites. Finally, we address the problem of load optimization, and solve it under various criteria. The ASIP model establishes bridges between statistical physics and queueing theory as it represents a tandem array of queueing systems with (unlimited) batch service, and a tandem array of growth-collapse processes. PMID:22181081

  3. Asymmetric squares as standing waves in rayleigh-Benard convection

    PubMed

    Das; Ghosal; Kumar

    2000-09-01

    Possibility of thermal convection in the form of asymmetric squares in a thin layer of Boussinesq fluids of large lateral extension confined between stress-free and conducting flat boundaries is investigated numerically using a seven mode Lorenz-like model. For fluids with moderate and high Prandtl numbers (4asymmetric squares appear as standing waves at the onset of secondary instability. Asymmetric squares, two-dimensional rolls, and again asymmetric squares with their corners shifted by half a wavelength form a stable limit cycle. The oscillatory bifurcation is supercritical. PMID:11088876

  4. Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

    PubMed Central

    Van Wyngarden, A. L.; Pérez-Montaño, S.; Bui, J. V. H.; Li, E. S. W.; Nelson, T. E.; Ha, K. T.; Leong, L.; Iraci, L. T.

    2016-01-01

    Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40–80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance–Fourier transform infrared (ATR-FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and

  5. Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

    NASA Astrophysics Data System (ADS)

    Van Wyngarden, A. L.; Pérez-Montaño, S.; Bui, J. V. H.; Li, E. S. W.; Nelson, T. E.; Ha, K. T.; Leong, L.; Iraci, L. T.

    2014-11-01

    Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, Attenuated Total Reflectance-Fourier Transform Infrared and 1H Nuclear Magnetic Resonance spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene, which was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence for products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and methylglyoxal

  6. Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

    NASA Astrophysics Data System (ADS)

    Van Wyngarden, A. L.; Pérez-Montaño, S.; Bui, J. V. H.; Li, E. S. W.; Nelson, T. E.; Ha, K. T.; Leong, L.; Iraci, L. T.

    2015-04-01

    Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt%) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and

  7. Effect of the Keto Group on Yields and Composition of Organic Aerosol Formed from OH Radical-Initiated Reactions of Ketones in the Presence of NOx.

    PubMed

    Algrim, Lucas B; Ziemann, Paul J

    2016-09-01

    Yields of secondary organic aerosol (SOA) were measured for OH radical-initiated reactions of the 2- through 6-dodecanone positional isomers and also n-dodecane and n-tetradecane in the presence of NOx. Yields decreased in the order n-tetradecane > dodecanone isomer average > n-dodecane, and the dodecanone isomer yields decreased as the keto group moved toward the center of the molecule, with 6-dodecanone being an exception. Trends in the yields can be explained by the effect of carbon number and keto group presence and position on product vapor pressures, and by the isomer-specific effects of the keto group on branching ratios for keto alkoxy radical isomerization, decomposition, and reaction with O2. Most importantly, results indicate that isomerization of keto alkoxy radicals via 1,5- and 1,6-H shifts are significantly hindered by the presence of a keto group whereas decomposition is enhanced. Analysis of particle composition indicates that the SOA products are similar for all isomers, and that compared to those formed from the corresponding reactions of alkanes the presence of a pre-existing keto group opens up additional heterogeneous/multiphase reaction pathways that can lead to the formation of new products. The results demonstrate that the presence of a keto group alters gas and particle phase chemistry and provide new insights into the potential effects of molecular structure on the products of the atmospheric oxidation of volatile organic compounds and subsequent formation of SOA.

  8. Effect of the Keto Group on Yields and Composition of Organic Aerosol Formed from OH Radical-Initiated Reactions of Ketones in the Presence of NOx.

    PubMed

    Algrim, Lucas B; Ziemann, Paul J

    2016-09-01

    Yields of secondary organic aerosol (SOA) were measured for OH radical-initiated reactions of the 2- through 6-dodecanone positional isomers and also n-dodecane and n-tetradecane in the presence of NOx. Yields decreased in the order n-tetradecane > dodecanone isomer average > n-dodecane, and the dodecanone isomer yields decreased as the keto group moved toward the center of the molecule, with 6-dodecanone being an exception. Trends in the yields can be explained by the effect of carbon number and keto group presence and position on product vapor pressures, and by the isomer-specific effects of the keto group on branching ratios for keto alkoxy radical isomerization, decomposition, and reaction with O2. Most importantly, results indicate that isomerization of keto alkoxy radicals via 1,5- and 1,6-H shifts are significantly hindered by the presence of a keto group whereas decomposition is enhanced. Analysis of particle composition indicates that the SOA products are similar for all isomers, and that compared to those formed from the corresponding reactions of alkanes the presence of a pre-existing keto group opens up additional heterogeneous/multiphase reaction pathways that can lead to the formation of new products. The results demonstrate that the presence of a keto group alters gas and particle phase chemistry and provide new insights into the potential effects of molecular structure on the products of the atmospheric oxidation of volatile organic compounds and subsequent formation of SOA. PMID:27508315

  9. EPR and ENDOR Investigation of Rhodosemiquinone in Bacterial Reaction Centers Formed by B-Branch Electron Transfer

    PubMed Central

    Paddock, M. L.; Flores, M.; Isaacson, R.; Shepherd, J. N.

    2010-01-01

    In photosynthetic bacteria, light-induced electron transfer takes place in a protein called the reaction center (RC) leading to the reduction of a bound ubiquinone molecule, QB, coupled with proton binding from solution. We used electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) to study the magnetic properties of the protonated semiquinone, an intermediate proposed to play a role in proton coupled electron transfer to QB. To stabilize the protonated semiquinone state, we used a ubiquinone derivative, rhodoquinone, which as a semiquinone is more easily protonated than ubisemiquinone. To reduce this low-potential quinone we used mutant RCs modified to directly reduce the quinone in the QB site via B-branch electron transfer (Paddock et al. in Biochemistry 44:6920–6928, 2005). EPR and ENDOR signals were observed upon illumination of mutant RCs in the presence of rhodoquinone. The EPR signals had g values characteristic of rhodosemiquinone (gx = 2.0057, gy = 2.0048, gz ∼ 2.0018) at pH 9.5 and were changed at pH 4.5. The ENDOR spectrum showed couplings due to solvent exchangeable protons typical of hydrogen bonds similar to, but different from, those found for ubisemiquinone. This approach should be useful in future magnetic resonance studies of the protonated semiquinone. PMID:20157643

  10. Asymmetric Bulkheads for Cylindrical Pressure Vessels

    NASA Technical Reports Server (NTRS)

    Ford, Donald B.

    2007-01-01

    Asymmetric bulkheads are proposed for the ends of vertically oriented cylindrical pressure vessels. These bulkheads, which would feature both convex and concave contours, would offer advantages over purely convex, purely concave, and flat bulkheads (see figure). Intended originally to be applied to large tanks that hold propellant liquids for launching spacecraft, the asymmetric-bulkhead concept may also be attractive for terrestrial pressure vessels for which there are requirements to maximize volumetric and mass efficiencies. A description of the relative advantages and disadvantages of prior symmetric bulkhead configurations is prerequisite to understanding the advantages of the proposed asymmetric configuration: In order to obtain adequate strength, flat bulkheads must be made thicker, relative to concave and convex bulkheads; the difference in thickness is such that, other things being equal, pressure vessels with flat bulkheads must be made heavier than ones with concave or convex bulkheads. Convex bulkhead designs increase overall tank lengths, thereby necessitating additional supporting structure for keeping tanks vertical. Concave bulkhead configurations increase tank lengths and detract from volumetric efficiency, even though they do not necessitate additional supporting structure. The shape of a bulkhead affects the proportion of residual fluid in a tank that is, the portion of fluid that unavoidably remains in the tank during outflow and hence cannot be used. In this regard, a flat bulkhead is disadvantageous in two respects: (1) It lacks a single low point for optimum placement of an outlet and (2) a vortex that forms at the outlet during outflow prevents a relatively large amount of fluid from leaving the tank. A concave bulkhead also lacks a single low point for optimum placement of an outlet. Like purely concave and purely convex bulkhead configurations, the proposed asymmetric bulkhead configurations would be more mass-efficient than is the flat

  11. Reaction of carbon tetrachloride with methane in a non-equilibrium plasma at atmospheric pressure, and characterisation of the polymer thus formed.

    PubMed

    Gaikwad, Vaibhav; Kennedy, Eric; Mackie, John; Holdsworth, Clovia; Molloy, Scott; Kundu, Sazal; Stockenhuber, Michael; Dlugogorski, Bogdan

    2014-09-15

    In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process.

  12. Process for producing organic products containing silicon, hydrogen, nitrogen, and carbon by the direct reaction between elemental silicon and organic amines and products formed thereby

    DOEpatents

    Pugar, E.A.; Morgan, P.E.D.

    1988-04-04

    A process is disclosed for producing, at a low temperature, a high purity organic reaction product consisting essentially of silicon, hydrogen, nitrogen, and carbon. The process comprises reacting together a particulate elemental high purity silicon with a high purity reactive amine reactant in a liquid state at a temperature of from about O/degree/C up to about 300/degree/C. A high purity silicon carbide/silicon nitride ceramic product can be formed from this intermediate product, if desired, by heating the intermediate product at a temperature of from about 1200-1700/degree/C for a period from about 15 minutes up to about 2 hours or the organic reaction product may be employed in other chemical uses.

  13. Bis(trifluoromethyl)methylene Addition to Vinyl-Terminated SAMs: A Gas-Phase C–C Bond-Forming Reaction on a Surface

    PubMed Central

    2014-01-01

    Vinyl-terminated self-assembled monolayers (SAMs) on silicon oxide substrates were chemically modified by the addition of a bis(trifluoromethyl)methylene group in a rare gas-phase C–C bond-forming reaction to directly generate films carrying terminal CF3 groups. The vinyl-terminated films were treated with hexafluoroacetone azine (HFAA) for modification. The films were characterized with ellipsometry, contact angle measurements, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). In this study, we find that for optimized conditions clean reactions occur on a surface between SAMs with terminal olefins and HFAA, and the product is consistent with bis(trifluoromethyl)cyclopropanation formation after nitrogen extrusion. PMID:24806554

  14. Crystalline structure of TiC ultrathin layers formed on highly oriented pyrolytic graphite by chemical reaction from Ti/graphite system

    NASA Astrophysics Data System (ADS)

    Nakatsuka, Osamu; Hisada, Kenji; Oida, Satoshi; Sakai, Akira; Zaima, Shigeaki

    2016-06-01

    We have investigated the atomic-scale reaction between a Ti thin layer and highly oriented pyrolytic graphite (HOPG) mainly by scanning tunneling microscopy. A deposited Ti layer shows an epitaxial orientation structure on a HOPG substrate even in room-temperature deposition, while the bonding between Ti and HOPG is very weak. The chemical reaction between Ti and HOPG takes place, and epitaxial TiC domains on HOPG are formed for annealing at above 600 °C. The TiC domains shows a smooth surface corresponding to the TiC(111) plane after annealing at 700 °C. The formation of TiC(001) facets and significant surface roughening of not only TiC but also HOPG substrates are observed for annealing at as high as 900 °C.

  15. New tetragonal form of reaction centers from Rhodobacter sphaeroides and the involvement of a manganese ion at a crystal contact point

    PubMed Central

    Uyeda, G.; Cámara-Artigas, A.; Williams, J. C.; Allen, J. P.

    2005-01-01

    Crystals have been obtained of wild-type reaction centers from Rhodobacter sphaeroides using manganese chloride as a precipitating agent. The crystals belong to the tetragonal space group P4222, with unit-cell parameters a = b = 207.8, c = 107.5 Å. The crystal structure has been determined to a resolution limit of 4.6 Å using a previously determined structure of the reaction center as a molecular-replacement model. The calculated electron-density maps show the presence of a manganese ion at one of the crystal contact points bridging two symmetry-related histidine residues, suggesting that the metal plays a key role in facilitating the crystallization of the protein in this form. PMID:16511142

  16. Sources of Water-soluble Organic Aerosol in the Southeastern United States - Evidence of SOA Formed Through Heterogeneous Reactions

    NASA Astrophysics Data System (ADS)

    Zhang, X.; Weber, R. J.

    2010-12-01

    Recent laboratory studies suggest partitioning of semi-volatile organic compounds (SVOCs) to liquid water followed by heterogeneous chemical transformation as a possible route to forming secondary organic aerosol (SOA). This paper will present results from observational studies of SOA formation using Water-Soluble Organic Carbon (WSOC) fraction of SOA, soluble brown carbon (e.g., light absorption spectra), organic acids and a number of aerosol source tracers in the Southeastern U.S., a region known for extensive biogenic and anthropogenic VOC emissions. Based on 24-h integrated filter measurements at 15 sites in the southeast throughout the year of 2007, a PMF analysis identified a factor characterized by the co-abundance of WSOC (58 percent of the total), oxalate (51 percent) and brown carbon (Abs365) (44 percent), which is consistent with the aqueous phase SOA formation mechanism in which water-soluble organic products from gas-phase photochemistry dissolve in liquid (fog/cloud droplets or particle water) and react further to form oligomers, light absorbing compounds, and light-weight organic acids, with oxalic acid being the most abundant one [Hecobian et al., 2010; Zhang et al., 2010]. The temporal variability of this factor correlated well with ambient temperature, possibly owing to the large impact from biogenic emissions, which are dependent on temperature and known to be significant over the southeast. PMF analysis of other data sets collected in Atlanta with online instruments during summer support these findings; as do other studies based on different data sets and data-analysis methods [Hennigan et al., 2008a; Hennigan et al., 2008b; Hennigan et al., 2008c; Hennigan et al., 2009]. Overall, we find that WSOC is largely secondary (roughly 75 to 85 percent) and estimate that 65 to 75 percent of the secondary WSOC formed in the southeast involves some form of aqueous phase chemical process. Hecobian, A., X. Zhang, M. Zheng, N. Frank, E. S. Edgerton, and R. J

  17. Decay of the compound nucleus *297118 formed in the reaction 249Cf+48Ca using the dynamical cluster-decay model

    NASA Astrophysics Data System (ADS)

    Sawhney, Gudveen; Kaur, Amandeep; Sharma, Manoj K.; Gupta, Raj K.

    2015-12-01

    The decay of the Z =118 , *297118 compound system, formed in the 249Cf+48Ca reaction, is studied for 2 n , 3 n , and 4 n emissions, by using the dynamical cluster-decay model (DCM) at compound-nucleus (CN) excitation energies ECN*=29.2 and 34.4 MeV. A parallel attempt is made to analyze the 294118 residue nucleus synthesized in the 250Cf+48Ca reaction, subsequent to the 4 n emission from the *298118 nucleus, to check the possibility of isotopic mixing in the 249Cf target used in the 249Cf+48Ca reaction. The possible role of deformations and orientations, together with different nuclear proximity potentials, is also investigated. In addition, an exclusive analysis of the mass distributions of Z =113 to 118 superheavy nuclei, formed in 48Ca -induced reactions, is explored within the DCM. A comparative importance of Prox-1977 and Prox-2000 potentials on the α -decay chains is also investigated, first by using the preformed cluster model (PCM) for spontaneous decays (T =0 ), the PCM (T =0 ), and then analyzing the possible role of excitation energy in PCM, i.e., PCM (T ≠0 ) , via the measured recoil energy of the residual 294118 nucleus left after 3 n emission from *297118 CN. The branching of α decay to the most-probable clusters is also examined for *294118 and its subsequent *290116 and *286114 parents occurring in the α -decay chain. Interestingly, the calculated decay half-lives for some clusters such as 86Kr , 84Se , and 80Ge , referring to doubly magic 208Pb or its neighboring daughter nucleus, present themselves as exciting new possibilities, though to date difficult to observe, of heavy cluster emissions in superheavy mass region.

  18. Asymmetric transformations of achiral 2,5-cyclohexadienones

    PubMed Central

    Kalstabakken, Kyle A.; Harned, Andrew M.

    2014-01-01

    Cyclohexadienones are versatile platforms for performing asymmetric synthesis as evidenced by the numerous natural product syntheses that exploit their diverse reactivity profile. However, there are few general methods available for the direct asymmetric synthesis of chiral cyclohexadienones. To circumvent this problem, several researchers have developed catalytic asymmetric methods that employ readily available achiral 2,5-cyclohexadienones as substrates. Many of these reactions are desymmetrizations in which one of the enantiotopic alkenes of an achiral dienone is transformed. Others involve selective reaction at one alkene of an unsymmetrically substituted, achiral dienone. This review will cover advances in this area over the last 20 years and the application of these strategies in complex molecule synthesis. PMID:26688596

  19. Asymmetric-Indenothiophene-Based Copolymers for Bulk Heterojunction Solar Cells with 9.14% Efficiency.

    PubMed

    Wang, Meng; Cai, Dongdong; Yin, Zhigang; Chen, Shan-Ci; Du, Cheng-Feng; Zheng, Qingdong

    2016-05-01

    The first two asymmetric-indenothiophene-based donor-acceptor copolymers (PITBT and PITFBT) are prepared through Stille coupling reactions between distannyl indenothiophene and brominated benzothiadiazole derivatives. The best performing solar cell fabricated from PITFBT exhibits a power conversion efficiency of 9.14% which demonstrates a great potential of the asymmetric indenothiophene for high-performance copolymers.

  20. Fission fragment mass distribution studies in 30Si +180Hf reaction

    NASA Astrophysics Data System (ADS)

    Shamlath, A.; Shareef, M.; Prasad, E.; Sugathan, P.; Thomas, R. G.; Jhingan, A.; Appannababu, S.; Nasirov, A. K.; Vinodkumar, A. M.; Varier, K. M.; Yadav, C.; Babu, B. R. S.; Nath, S.; Mohanto, G.; Mukul, Ish; Singh, D.; Kailas, S.

    2016-01-01

    Fission fragment mass-angle and mass ratio distributions have been measured for the 30Si + 180Hf reaction in the beam energy range 128-148 MeV. Quasifission signature is observed in this reaction, forming the compound system 210Rn. The results are compared with a very asymmetric reaction 16O + 194Pt, forming the same compound nucleus. Calculations assuming saddle point, scission point and DNS models have been performed to interpret the experimental results. The results strongly suggest the entrance channel dependence of quasifission in heavy ion collisions.

  1. Mechanisms for Two-Step Proton Transfer Reactions in the Outward-Facing Form of MATE Transporter.

    PubMed

    Nishima, Wataru; Mizukami, Wataru; Tanaka, Yoshiki; Ishitani, Ryuichiro; Nureki, Osamu; Sugita, Yuji

    2016-03-29

    Bacterial pathogens or cancer cells can acquire multidrug resistance, which causes serious clinical problems. In cells with multidrug resistance, various drugs or antibiotics are extruded across the cell membrane by multidrug transporters. The multidrug and toxic compound extrusion (MATE) transporter is one of the five families of multidrug transporters. MATE from Pyrococcus furiosus uses H(+) to transport a substrate from the cytoplasm to the outside of a cell. Crystal structures of MATE from P. furiosus provide essential information on the relevant H(+)-binding sites (D41 and D184). Hybrid quantum mechanical/molecular mechanical simulations and continuum electrostatic calculations on the crystal structures predict that D41 is protonated in one structure (Straight) and, both D41 and D184 protonated in another (Bent). All-atom molecular dynamics simulations suggest a dynamic equilibrium between the protonation states of the two aspartic acids and that the protonation state affects hydration in the substrate binding cavity and lipid intrusion in the cleft between the N- and C-lobes. This hypothesis is examined in more detail by quantum mechanical/molecular mechanical calculations on snapshots taken from the molecular dynamics trajectories. We find the possibility of two proton transfer (PT) reactions in Straight: the 1st PT takes place between side-chains D41 and D184 through a transient formation of low-barrier hydrogen bonds and the 2nd through another H(+) from the headgroup of a lipid that intrudes into the cleft resulting in a doubly protonated (both D41 and D184) state. The 1st PT affects the local hydrogen bond network and hydration in the N-lobe cavity, which would impinge on the substrate-binding affinity. The 2nd PT would drive the conformational change from Straight to Bent. This model may be applicable to several prokaryotic H(+)-coupled MATE multidrug transporters with the relevant aspartic acids. PMID:27028644

  2. Catalytic asymmetric formal synthesis of beraprost.

    PubMed

    Kobayashi, Yusuke; Kuramoto, Ryuta; Takemoto, Yoshiji

    2015-01-01

    The first catalytic asymmetric synthesis of the key intermediate for beraprost has been achieved through an enantioselective intramolecular oxa-Michael reaction of an α,β-unsaturated amide mediated by a newly developed benzothiadiazine catalyst. The Weinreb amide moiety and bromo substituent of the Michael adduct were utilized for the C-C bond formations to construct the scaffold. All four contiguous stereocenters of the tricyclic core were controlled via Rh-catalyzed stereoselective C-H insertion and the subsequent reduction from the convex face.

  3. Catalytic asymmetric formal synthesis of beraprost

    PubMed Central

    Kobayashi, Yusuke; Kuramoto, Ryuta

    2015-01-01

    Summary The first catalytic asymmetric synthesis of the key intermediate for beraprost has been achieved through an enantioselective intramolecular oxa-Michael reaction of an α,β-unsaturated amide mediated by a newly developed benzothiadiazine catalyst. The Weinreb amide moiety and bromo substituent of the Michael adduct were utilized for the C–C bond formations to construct the scaffold. All four contiguous stereocenters of the tricyclic core were controlled via Rh-catalyzed stereoselective C–H insertion and the subsequent reduction from the convex face. PMID:26734111

  4. Asymmetric twin Dark Matter

    SciTech Connect

    Farina, Marco

    2015-11-09

    We study a natural implementation of Asymmetric Dark Matter in Twin Higgs models. The mirroring of the Standard Model strong sector suggests that a twin baryon with mass around 5 GeV is a natural Dark Matter candidate once a twin baryon number asymmetry comparable to the SM asymmetry is generated. We explore twin baryon Dark Matter in two different scenarios, one with minimal content in the twin sector and one with a complete copy of the SM, including a light twin photon. The essential requirements for successful thermal history are presented, and in doing so we address some of the cosmological issues common to many Twin Higgs models. The required interactions we introduce predict signatures at direct detection experiments and at the LHC.

  5. Asymmetric twin Dark Matter

    SciTech Connect

    Farina, Marco

    2015-11-01

    We study a natural implementation of Asymmetric Dark Matter in Twin Higgs models. The mirroring of the Standard Model strong sector suggests that a twin baryon with mass around 5 GeV is a natural Dark Matter candidate once a twin baryon number asymmetry comparable to the SM asymmetry is generated. We explore twin baryon Dark Matter in two different scenarios, one with minimal content in the twin sector and one with a complete copy of the SM, including a light twin photon. The essential requirements for successful thermal history are presented, and in doing so we address some of the cosmological issues common to many Twin Higgs models. The required interactions we introduce predict signatures at direct detection experiments and at the LHC.

  6. Asymmetrically warped spacetimes

    SciTech Connect

    Csaki, C.

    2001-01-01

    We investigate spacetimes in which the speed of light along flat 4D sections varies over the extra dimensions due to different warp factors for the space and the time coordinates ('asymmetrically warped' spacetimes). The main property of such spaces is that while the induced metric is flat, implying Lorentz invariant particle physics on a brane, bulk gravitational effects will cause apparent violations of Lorentz invariance and of causality from the brane observer's point of view. An important experimentally verifiable consequence of this is that gravitational waves may travel with a speed different from the speed of light on the brane, and possibly even faster. We find the most general spacetimes of this sort, which are given by certain types of black hole spacetimes characterized by the m a s and the charge of the black hole. We show how to satisfy the junction conditions and analyze the properties of these space-times.

  7. Engineered Asymmetric Synthetic Vesicles

    NASA Astrophysics Data System (ADS)

    Lu, Li; Chiarot, Paul

    2013-11-01

    Synthetic vesicles are small, fluid-filled spheres that are enclosed by a bilayer of lipid molecules. They can be used as models for investigating membrane biology and as delivery vehicles for pharmaceuticals. In practice, it is difficult to simultaneously control membrane asymmetry, unilamellarity, vesicle size, vesicle-to-vesicle uniformity, and luminal content. Membrane asymmetry, where each leaflet of the bilayer is composed of different lipids, is of particular importance as it is a feature of most natural membranes. In this study, we leverage microfluidic technology to build asymmetric vesicles at high-throughput. We use the precise flow control offered by microfluidic devices to make highly uniform emulsions, with controlled internal content, that serve as templates to build the synthetic vesicles. Flow focusing, dielectrophoretic steering, and interfacial lipid self-assembly are critical procedures performed on-chip to produce the vesicles. Fluorescent and confocal microscopy are used to evaluate the vesicle characteristics.

  8. Iron-, Cobalt-, and Nickel-Catalyzed Asymmetric Transfer Hydrogenation and Asymmetric Hydrogenation of Ketones.

    PubMed

    Li, Yan-Yun; Yu, Shen-Luan; Shen, Wei-Yi; Gao, Jing-Xing

    2015-09-15

    Chiral alcohols are important building blocks in the pharmaceutical and fine chemical industries. The enantioselective reduction of prochiral ketones catalyzed by transition metal complexes, especially asymmetric transfer hydrogenation (ATH) and asymmetric hydrogenation (AH), is one of the most efficient and practical methods for producing chiral alcohols. In both academic laboratories and industrial operations, catalysts based on noble metals such as ruthenium, rhodium, and iridium dominated the asymmetric reduction of ketones. However, the limited availability, high price, and toxicity of these critical metals demand their replacement with abundant, nonprecious, and biocommon metals. In this respect, the reactions catalyzed by first-row transition metals, which are more abundant and benign, have attracted more and more attention. As one of the most abundant metals on earth, iron is inexpensive, environmentally benign, and of low toxicity, and as such it is a fascinating alternative to the precious metals for catalysis and sustainable chemical manufacturing. However, iron catalysts have been undeveloped compared to other transition metals. Compared with the examples of iron-catalyzed asymmetric reduction, cobalt- and nickel-catalyzed ATH and AH of ketones are even seldom reported. In early 2004, we reported the first ATH of ketones with catalysts generated in situ from iron cluster complex and chiral PNNP ligand. Since then, we have devoted ourselves to the development of ATH and AH of ketones with iron, cobalt, and nickel catalysts containing novel chiral aminophosphine ligands. In our study, the iron catalyst containing chiral aminophosphine ligands, which are expected to control the stereochemistry at the metal atom, restrict the number of possible diastereoisomers, and effectively transfer chiral information, are successful catalysts for enantioselective reduction of ketones. Among these novel chiral aminophosphine ligands, 22-membered macrocycle P2N4

  9. Status of Bates experiment 85-05: The electric form factor of the neutron from the d(e↘,e'n↘)p reaction

    NASA Astrophysics Data System (ADS)

    Madey, R.; Eden, T.; Zhang, W. M.; Anderson, B. D.; Baldwin, A. R.; Keane, D.; Manley, D. M.; Watson, J. W.; Kowalski, S.; Bertozzi, W.; Dodson, G.; Dow, K.; Farkhondeh, M.; Korsch, W.; Tieger, D.; Turchinetz, W.; Weinstein, L.; Reichelt, T.; Finn, J. M.; Beard, K. B.; Markowitz, P.; McIntyre, J.; Rutt, P.; Lourie, R.; Barkhuff, D.; Van Verst, S.; Chang, C. C.; Kelly, J. J.; Payerle, T.; Cameron, J. M.; Ni, B.; Spraker, M.; Mougey, J.; Ulmer, P.; Whitney, R.; Flanders, B. S.; Pella, P. J.; Hyde-Wright, C. E.; Jiang, W.

    1992-01-01

    The Bates E85-05 Collaboration measured the polarization of the neutron in the d(e↘,en↘)p reaction in the quasifree region with the objective of extracting the electric form factor of the neutron. Electron-neutron coincidence spectra were obtained during 567 μA-hours of integrated beam. We succeeded in operating a Mo/ller scattering polarimeter in the coincidence mode with a low-duty factor accelerator in order to measure the polarization of the electron beam.

  10. The DNA cleavage reaction of DNA gyrase. Comparison of stable ternary complexes formed with enoxacin and CcdB protein.

    PubMed

    Scheirer, K E; Higgins, N P

    1997-10-24

    The potent synthetic fluoroquinolones and the natural CcdB protein encoded by the F plasmid both inhibit bacterial growth by attacking DNA gyrase and by stimulating enzyme-induced breaks in bacterial DNA. The cleavage mechanisms of these structurally diverse compounds were analyzed by purifying and characterizing stable ternary complexes of enoxacin and CcdB protein with gyrase bound to a strong gyrase binding site from bacteriophage Mu. Three differences between enoxacin- and CcdB-derived complexes were discovered. 1) Enoxacin binds to the DNA active site and alters the breakage/reunion activity of the enzyme. CcdB binds gyrase-DNA complexes but does not influence enzymatic activity directly. 2) Complexes that produce DNA cleavage with enoxacin are reversible, whereas similar complexes made with CcdB protein are not. 3) Enoxacin stimulates cleavage of both relaxed and supercoiled forms of DNA in the absence of ATP, whereas CcdB induces cleavage only after many cycles of ATP-dependent breakage and reunion. These differences in mechanisms can be explained by a model in which enoxacin induces formation of a novel "cleavable" complex, whereas CcdB protein traps a very rare "cleaved" conformation of the enzyme.

  11. The first catalytic asymmetric thioacetalization by chiral phosphoric acid catalysis.

    PubMed

    Yu, Jin-Sheng; Wu, Wen-Biao; Zhou, Feng

    2016-02-21

    We report here the first catalytic asymmetric thioacetalization of salicylaldehyde and dithiol. Chiral phosphoric acid STRIP C5 is identified as a powerful catalyst for this reaction to afford various chiral dithioacetals in high to excellent yields and enantioselectivities under mild conditions. PMID:26810819

  12. Catalytic asymmetric Torgov cyclization: a concise total synthesis of (+)-estrone.

    PubMed

    Prévost, Sébastien; Dupré, Nathalie; Leutzsch, Markus; Wang, Qinggang; Wakchaure, Vijay; List, Benjamin

    2014-08-11

    An asymmetric Torgov cyclization, catalyzed by a novel, highly Brønsted acidic dinitro-substituted disulfonimide, is described. The reaction delivers the Torgov diene and various analogues with excellent yields and enantioselectivity. This method was applied in a very short synthesis of (+)-estrone.

  13. Asymmetric Synthesis of Spiropyrazolones by Sequential Organo- and Silver Catalysis

    PubMed Central

    Hack, Daniel; Dürr, Alexander B; Deckers, Kristina; Chauhan, Pankaj; Seling, Nico; Rübenach, Lukas; Mertens, Lucas; Raabe, Gerhard; Schoenebeck, Franziska; Enders, Dieter

    2016-01-01

    A stereoselective one-pot synthesis of spiropyrazolones through an organocatalytic asymmetric Michael addition and a formal Conia-ene reaction has been developed. Depending on the nitroalkene, the 5-exo-dig-cyclization could be achieved by silver-catalyzed alkyne activation or by oxidation of the intermediate enolate. The mechanistic pathways have been investigated using computational chemistry and mechanistic experiments. PMID:26676875

  14. Asymmetric Synthesis of Spiropyrazolones by Sequential Organo- and Silver Catalysis.

    PubMed

    Hack, Daniel; Dürr, Alexander B; Deckers, Kristina; Chauhan, Pankaj; Seling, Nico; Rübenach, Lukas; Mertens, Lucas; Raabe, Gerhard; Schoenebeck, Franziska; Enders, Dieter

    2016-01-26

    A stereoselective one-pot synthesis of spiropyrazolones through an organocatalytic asymmetric Michael addition and a formal Conia-ene reaction has been developed. Depending on the nitroalkene, the 5-exo-dig-cyclization could be achieved by silver-catalyzed alkyne activation or by oxidation of the intermediate enolate. The mechanistic pathways have been investigated using computational chemistry and mechanistic experiments. PMID:26676875

  15. Copper-catalyzed intermolecular asymmetric propargylic dearomatization of indoles.

    PubMed

    Shao, Wen; Li, He; Liu, Chuan; Liu, Chen-Jiang; You, Shu-Li

    2015-06-22

    The first copper-catalyzed intermolecular dearomatization of indoles by an asymmetric propargylic substitution reaction was developed. This method provides a highly efficient synthesis of versatile furoindoline and pyrroloindoline derivatives containing a quaternary carbon stereogenic center and a terminal alkyne moiety with up to 86 % yield and 98 % ee. PMID:25968474

  16. Asymmetric Synthesis of Spiropyrazolones by Sequential Organo- and Silver Catalysis.

    PubMed

    Hack, Daniel; Dürr, Alexander B; Deckers, Kristina; Chauhan, Pankaj; Seling, Nico; Rübenach, Lukas; Mertens, Lucas; Raabe, Gerhard; Schoenebeck, Franziska; Enders, Dieter

    2016-01-26

    A stereoselective one-pot synthesis of spiropyrazolones through an organocatalytic asymmetric Michael addition and a formal Conia-ene reaction has been developed. Depending on the nitroalkene, the 5-exo-dig-cyclization could be achieved by silver-catalyzed alkyne activation or by oxidation of the intermediate enolate. The mechanistic pathways have been investigated using computational chemistry and mechanistic experiments.

  17. Strongly asymmetric discrete Painlevé equations: The multiplicative case

    NASA Astrophysics Data System (ADS)

    Grammaticos, B.; Ramani, A.; Tamizhmani, K. M.; Tamizhmani, T.; Satsuma, J.

    2016-04-01

    We examine a class of multiplicative discrete Painlevé equations which may possess a strongly asymmetric form. When the latter occurs, the equation is written as a system of two equations the right hand sides of which have different functional forms. The present investigation focuses upon two canonical families of the Quispel-Roberts-Thompson classification which contain equations associated with the affine Weyl groups D5 ( 1 ) and E6 ( 1 ) (or groups appearing lower in the degeneration cascade of these two). Many new discrete Painlevé equations with strongly asymmetric forms are obtained.

  18. A model for the compositions of non-stoichiometric intermediate phases formed by diffusion reactions, and its application to Nb3Sn superconductors

    PubMed Central

    Xu, X.; Sumption, M. D.

    2016-01-01

    In this work we explore the compositions of non-stoichiometric intermediate phases formed by diffusion reactions: a mathematical framework is developed and tested against the specific case of Nb3Sn superconductors. In the first part, the governing equations for the bulk diffusion and inter-phase interface reactions during the growth of a compound are derived, numerical solutions to which give both the composition profile and growth rate of the compound layer. The analytic solutions are obtained with certain approximations made. In the second part, we explain an effect that the composition characteristics of compounds can be quite different depending on whether it is the bulk diffusion or grain boundary diffusion that dominates in the compounds, and that “frozen” bulk diffusion leads to unique composition characteristics that the bulk composition of a compound layer remains unchanged after its initial formation instead of varying with the diffusion reaction system; here the model is modified for the case of grain boundary diffusion. Finally, we apply this model to the Nb3Sn superconductors and propose approaches to control their compositions. PMID:26754774

  19. Effects of deformations and orientations in the fission of the actinide nuclear system 254Fm* formed in the 11B + 243Am reaction

    NASA Astrophysics Data System (ADS)

    Kaur, Manpreet; Sharma, Manoj K.; Gupta, Raj K.

    2012-12-01

    We have studied the decay of actinide nuclear system 254Fm* formed in 11B + 243Am reaction using the dynamical cluster decay model (DCM), with choices of spherical, quadrupole deformation β2 alone and higher multipole deformations β2-β4. For β2 deformations, the optimum orientations θiopt are used whereas for higher multipole deformations the compact orientations θic of decaying fragments are taken in to account. Besides static-β2 deformations, the effects of dynamical-β2 deformations are also explored. The calculated cross sections find excellent agreement with the available experimental data with spherical as well as deformed choices of fragmentations, enabling us to account for the role of important nuclear deformation effects in the 11B-induced nuclear reaction. Spontaneous decay of 254Fm with cold elongated configuration and optimum orientation is also worked out. The mass distributions of excited fermium isotopes in the neighborhood of 254Fm* are also explored. In addition, the roles of temperature, angular momentum, and fission fragment anisotropies are investigated in the context of the chosen reaction.

  20. Roles of the redox-active disulfide and histidine residues forming a catalytic dyad in reactions catalyzed by 2-ketopropyl coenzyme M oxidoreductase/carboxylase.

    PubMed

    Kofoed, Melissa A; Wampler, David A; Pandey, Arti S; Peters, John W; Ensign, Scott A

    2011-09-01

    NADPH:2-ketopropyl-coenzyme M oxidoreductase/carboxylase (2-KPCC), an atypical member of the disulfide oxidoreductase (DSOR) family of enzymes, catalyzes the reductive cleavage and carboxylation of 2-ketopropyl-coenzyme M [2-(2-ketopropylthio)ethanesulfonate; 2-KPC] to form acetoacetate and coenzyme M (CoM) in the bacterial pathway of propylene metabolism. Structural studies of 2-KPCC from Xanthobacter autotrophicus strain Py2 have revealed a distinctive active-site architecture that includes a putative catalytic triad consisting of two histidine residues that are hydrogen bonded to an ordered water molecule proposed to stabilize enolacetone formed from dithiol-mediated 2-KPC thioether bond cleavage. Site-directed mutants of 2-KPCC were constructed to test the tenets of the mechanism proposed from studies of the native enzyme. Mutagenesis of the interchange thiol of 2-KPCC (C82A) abolished all redox-dependent reactions of 2-KPCC (2-KPC carboxylation or protonation). The air-oxidized C82A mutant, as well as wild-type 2-KPCC, exhibited the characteristic charge transfer absorbance seen in site-directed variants of other DSOR enzymes but with a pK(a) value for C87 (8.8) four units higher (i.e., four orders of magnitude less acidic) than that for the flavin thiol of canonical DSOR enzymes. The same higher pK(a) value was observed in native 2-KPCC when the interchange thiol was alkylated by the CoM analog 2-bromoethanesulfonate. Mutagenesis of the flavin thiol (C87A) also resulted in an inactive enzyme for steady-state redox-dependent reactions, but this variant catalyzed a single-turnover reaction producing a 0.8:1 ratio of product to enzyme. Mutagenesis of the histidine proximal to the ordered water (H137A) led to nearly complete loss of redox-dependent 2-KPCC reactions, while mutagenesis of the distal histidine (H84A) reduced these activities by 58 to 76%. A redox-independent reaction of 2-KPCC (acetoacetate decarboxylation) was not decreased for any of the

  1. Asymmetric dynamic phase holographic grating in nematic liquid crystal

    NASA Astrophysics Data System (ADS)

    Ren, Chang-Yu; Shi, Hong-Xin; Ai, Yan-Bao; Yin, Xiang-Bao; Wang, Feng; Ding, Hong-Wei

    2016-09-01

    A new scheme for recording a dynamic phase grating with an asymmetric profile in C60-doped homeotropically aligned nematic liquid crystal (NLC) was presented. An oblique incidence beam was used to record the thin asymmetric dynamic phase holographic grating. The diffraction efficiency we achieved is more than 40%, exceeding the theoretical limit for symmetric profile gratings. Both facts can be explained by assuming that a grating with an asymmetric saw-tooth profile is formed in the NLC. Finally, physical mechanism and mathematical model for characterizing the asymmetric phase holographic grating were presented, based on the photo-refractive-like (PR-like) effect. Project supported by the Science and Technology Programs of the Educational Committee of Heilongjiang Province, China (Grant No. 12541730) and the National Natural Science Foundation of China (Grant No. 61405057).

  2. XANES-EXAFS analysis of se solid-phase reaction products formed upon contacting Se(IV) with FeS2 and FeS.

    PubMed

    Breynaert, E; Bruggeman, C; Maes, A

    2008-05-15

    The solid-phase Se speciation after short-term (3 weeks) contact of selenite [Se(IV)] oxyanions with pyrite (FeS2) and troilite (FeS) was investigated using X-ray absorption spectroscopy (XAS; X-ray absorption near-edge spectroscopy-extended X-ray absorption fine structure (XANES-EXAFS)). It was found that the nature of the sulfide mineral dictates the final speciation since respectively Se(0) and FeSe(x) were formed, meaning that the reaction mechanism is different and that these phases cannot be regarded as geochemically similar. The experimental results support the previously proposed sorption/ reduction mechanism for the reaction of selenite with pyrite. In the presence of troilite the reduction proceeds through the intermediate formation of Se(0) by reduction of selenite with dissolved sulfide. XAS data recorded for the FeS2 and FeS were compared with different Se reference phases, ranging in oxidation state from -II to +IV, used for validation of the XAS analysis methodology. This methodology can in principle be used to analyze Se phases formed in "in situ" geochemical conditions such as high-level radioactive waste disposal facilities.

  3. Metal rolling - Asymmetrical rolling process

    NASA Astrophysics Data System (ADS)

    Alexa, V.; Raţiu, S.; Kiss, I.

    2016-02-01

    The development of theory and practice related to the asymmetric longitudinal rolling process is based on the general theory of metalworking by pressure and symmetric rolling theory, to which a large number of scientists brought their contribution. The rolling of metal materials was a serious problem throughout history, either economically or technically, because the plating technologies enabled the consumption of raw materials (scarce and expensive) to be reduced, while improving the mechanical properties. Knowing the force parameters related to asymmetric rolling leads to the optimization of energy and raw material consumption. This paper presents data on symmetric rolling process, in order to comparatively highlight the particularities of the asymmetric process.

  4. Twin Higgs Asymmetric Dark Matter.

    PubMed

    García García, Isabel; Lasenby, Robert; March-Russell, John

    2015-09-18

    We study asymmetric dark matter (ADM) in the context of the minimal (fraternal) twin Higgs solution to the little hierarchy problem, with a twin sector with gauged SU(3)^{'}×SU(2)^{'}, a twin Higgs doublet, and only third-generation twin fermions. Naturalness requires the QCD^{'} scale Λ_{QCD}^{'}≃0.5-20  GeV, and that t^{'} is heavy. We focus on the light b^{'} quark regime, m_{b^{'}}≲Λ_{QCD}^{'}, where QCD^{'} is characterized by a single scale Λ_{QCD}^{'} with no light pions. A twin baryon number asymmetry leads to a successful dark matter (DM) candidate: the spin-3/2 twin baryon, Δ^{'}∼b^{'}b^{'}b^{'}, with a dynamically determined mass (∼5Λ_{QCD}^{'}) in the preferred range for the DM-to-baryon ratio Ω_{DM}/Ω_{baryon}≃5. Gauging the U(1)^{'} group leads to twin atoms (Δ^{'}-τ^{'}[over ¯] bound states) that are successful ADM candidates in significant regions of parameter space, sometimes with observable changes to DM halo properties. Direct detection signatures satisfy current bounds, at times modified by dark form factors. PMID:26430985

  5. Twin Higgs Asymmetric Dark Matter.

    PubMed

    García García, Isabel; Lasenby, Robert; March-Russell, John

    2015-09-18

    We study asymmetric dark matter (ADM) in the context of the minimal (fraternal) twin Higgs solution to the little hierarchy problem, with a twin sector with gauged SU(3)^{'}×SU(2)^{'}, a twin Higgs doublet, and only third-generation twin fermions. Naturalness requires the QCD^{'} scale Λ_{QCD}^{'}≃0.5-20  GeV, and that t^{'} is heavy. We focus on the light b^{'} quark regime, m_{b^{'}}≲Λ_{QCD}^{'}, where QCD^{'} is characterized by a single scale Λ_{QCD}^{'} with no light pions. A twin baryon number asymmetry leads to a successful dark matter (DM) candidate: the spin-3/2 twin baryon, Δ^{'}∼b^{'}b^{'}b^{'}, with a dynamically determined mass (∼5Λ_{QCD}^{'}) in the preferred range for the DM-to-baryon ratio Ω_{DM}/Ω_{baryon}≃5. Gauging the U(1)^{'} group leads to twin atoms (Δ^{'}-τ^{'}[over ¯] bound states) that are successful ADM candidates in significant regions of parameter space, sometimes with observable changes to DM halo properties. Direct detection signatures satisfy current bounds, at times modified by dark form factors.

  6. Catalytic asymmetric protonation of lithium enolates using amino acid derivatives as chiral proton sources.

    PubMed

    Mitsuhashi, Kaori; Ito, Rie; Arai, Takayoshi; Yanagisawa, Akira

    2006-04-13

    [reaction: see text] Asymmetric protonation of lithium enolates was examined using commercially available amino acid derivatives as chiral proton sources. Among the amino acid derivatives tested, Nbeta-l-aspartyl-l-phenylalanine methyl ester was found to cause significant asymmetric induction in the protonation of lithium enolates. The enantiomeric excess (up to 88% ee) of the products obtained in the presence of a catalytic amount of the chiral proton source was higher than those obtained in the stoichiometric reaction. PMID:16597150

  7. Catalytic asymmetric protonation of lithium enolates using amino acid derivatives as chiral proton sources.

    PubMed

    Mitsuhashi, Kaori; Ito, Rie; Arai, Takayoshi; Yanagisawa, Akira

    2006-04-13

    [reaction: see text] Asymmetric protonation of lithium enolates was examined using commercially available amino acid derivatives as chiral proton sources. Among the amino acid derivatives tested, Nbeta-l-aspartyl-l-phenylalanine methyl ester was found to cause significant asymmetric induction in the protonation of lithium enolates. The enantiomeric excess (up to 88% ee) of the products obtained in the presence of a catalytic amount of the chiral proton source was higher than those obtained in the stoichiometric reaction.

  8. Asymmetric threat data mining and knowledge discovery

    NASA Astrophysics Data System (ADS)

    Gilmore, John F.; Pagels, Michael A.; Palk, Justin

    2001-03-01

    Asymmetric threats differ from the conventional force-on- force military encounters that the Defense Department has historically been trained to engage. Terrorism by its nature is now an operational activity that is neither easily detected or countered as its very existence depends on small covert attacks exploiting the element of surprise. But terrorism does have defined forms, motivations, tactics and organizational structure. Exploiting a terrorism taxonomy provides the opportunity to discover and assess knowledge of terrorist operations. This paper describes the Asymmetric Threat Terrorist Assessment, Countering, and Knowledge (ATTACK) system. ATTACK has been developed to (a) data mine open source intelligence (OSINT) information from web-based newspaper sources, video news web casts, and actual terrorist web sites, (b) evaluate this information against a terrorism taxonomy, (c) exploit country/region specific social, economic, political, and religious knowledge, and (d) discover and predict potential terrorist activities and association links. Details of the asymmetric threat structure and the ATTACK system architecture are presented with results of an actual terrorist data mining and knowledge discovery test case shown.

  9. Asymmetric Ion-Pairing Catalysis

    PubMed Central

    Brak, Katrien

    2014-01-01

    Charged intermediates and reagents are ubiquitous in organic transformations. The interaction of these ionic species with chiral neutral, anionic, or cationic small molecules has emerged as a powerful strategy for catalytic, enantioselective synthesis. This review describes developments in the burgeoning field of asymmetric ion-pairing catalysis with an emphasis on the insights that have been gleaned into the structural and mechanistic features that contribute to high asymmetric induction. PMID:23192886

  10. Four-dimensional quantum study on exothermic complex-forming reactions: Cl{sup -}+CH{sub 3}Br{yields}ClCH{sub 3}+Br{sup -}

    SciTech Connect

    Hennig, Carsten; Schmatz, Stefan

    2005-06-15

    The exothermic gas-phase bimolecular nucleophilic substitution (S{sub N}2) reaction Cl{sup -}+CH{sub 3}Br ({upsilon}{sub 1}{sup '},{upsilon}{sub 2}{sup '},{upsilon}{sub 3}{sup '}){yields}ClCH{sub 3} ({upsilon}{sub 1},{upsilon}{sub 2},{upsilon}{sub 3})+Br{sup -} and the corresponding endothermic reverse reaction have been studied by time-independent quantum scattering calculations in hyperspherical coordinates on a coupled-cluster potential-energy surface. The dimensionality-reduced model takes four degrees of freedom into account [Cl-C and C-Br stretching modes (quantum numbers {upsilon}{sub 3}{sup '} and {upsilon}{sub 3}); totally symmetric modes of the methyl group, i.e., C-H stretching ({upsilon}{sub 1}{sup '} and {upsilon}{sub 1}) and umbrella bending vibrations ({upsilon}{sub 2}{sup '} and {upsilon}{sub 2})]. Diagonalization of the Hamiltonian was performed employing the Lanczos algorithm with a variation of partial reorthogonalization. A narrow grid in the total energy was employed so that long-living resonance states could be resolved and extracted. While excitation of the reactant umbrella bending mode already leads to a considerable enhancement of the reaction probability, its combination with vibrational excitation of the broken C-Br bond, (0, 1, 1), results in a strong synergic effect that can be rationalized by the similarity with the classical transitional normal mode. Exciting the C-H stretch has a non-negligible effect on the reaction probability, while for larger translational energies this mode follows the expected spectatorlike behavior. Combination of C-Br stretch and symmetric C-H, (1,0,1), stretch does not show a cooperative effect. Contrary to the spectator mode concept, energy originally stored in the C-H stretching mode is by no means conserved, but almost completely released in other modes of the reaction products. Products are most likely formed in states with a high degree of excitation in the new C-Cl bond, while the internal modes of

  11. Asymmetric planar gradiometer for rejection of uniform ambient magnetic noise

    DOEpatents

    Dantsker, Eugene; Clarke, John

    2000-01-01

    An asymmetric planar gradiometer for use in making biomagnetic measurements. The gradiometer is formed from a magnetometer which is inductively-coupled to the smaller of two connected loops patterned in a superconducting film which form a flux transformer. The magnetometer is based on a SQUID formed from a high T.sub.c superconducting material. The flux transformer and magnetometer may be formed on separate substrates, allowing the baseline to be increased relative to presently available devices.

  12. Densely Substituted L-Proline Esters as Catalysts for Asymmetric Michael Additions of Ketones to Nitroalkenes.

    PubMed

    Ruiz-Olalla, Andrea; Retamosa, María de Gracia; Cossío, Fernando P

    2015-06-01

    Homochiral methyl 4-aminopyrrolidine-2-carboxylates are readily obtained by means of asymmetric (3 + 2) cycloadditions between azomethine ylides and nitroalkenes, followed by catalytic hydrogenation of the intermediate 4-nitro cycloadducts. These 4-aminopyrrolidine-2-carboxylate esters belong to the L-series of natural amino acids and catalyze asymmetric Michael additions of ketones to nitroalkenes. However, the enantioselectivity observed with these novel unnatural organocatalysts is opposite to that obtained with L-proline. Since both 4-nitro and 4-amino L-proline esters are efficient organocatalysts of aldol reactions, these results permit to modulate asymmetric quimioselective aldol and conjugate addition reactions.

  13. Cp2ZrMeCl: A Reagent for Asymmetric Methyl Addition.

    PubMed

    Garrec, Kilian; Fletcher, Stephen P

    2016-08-01

    The use of Cp2ZrMeCl is described as a source of nucleophilic methyl in asymmetric catalysis. This easily prepared reagent is bench stable, weighable in air, and generally useful in highly enantioselective copper-catalyzed addition reactions at room temperature. Methyl is successfully (generally >90% ee) added in 1,4-additions to cyclic and acyclic α,β-unsaturated ketones to provide tertiary and quaternary centers. Examples of catalyst controlled diastereoselective 1,6-addition and dynamic kinetic asymmetric allylic alkylation reactions are also reported. The reagent is used in the catalytic asymmetric synthesis of naturally occurring fragrance (R)-(-)-muscone (82% yield, 91% ee). PMID:27458650

  14. Flexible Asymmetric Encapsulation for Dehydration-Responsive Hybrid Microfibers.

    PubMed

    Chaurasia, Ankur S; Sajjadi, Shahriar

    2016-08-01

    A new class of smart alginate microfibers with asymmetric oil encapsulates is introduced. These fibers are produced by injecting an aqueous alginate solution into an outer aqueous calcium chloride solution to form alginate fibers, which are asymmetrically loaded with oil entities through eccentrically aligned inner capillaries. The fiber morphology and its degree of asymmetry can be tuned via altering the size, location, and frequency of the oil encapsulates. These asymmetric fibers reveal significant potential for applications where conventional symmetric fibers fail to perform. It is shown how asymmetric oil-encapsulated fibers can become dehydration-sensitive, and trigger the release of encapsulates if their hydration level drops below a critical value. It is also shown how the triggered response could be switched off on demand by stabilizing the oil encapsulates. The capability of asymmetric fibers to carry and release multiple cargos in parallel is demonstrated. The fibers loaded with equal-sized spheres are more asymmetric than those containing unequal drops, have a higher tensile strength, and show better potential for a triggered response. PMID:27352241

  15. Asymmetric intramolecular α-cyclopropanation of aldehydes using a donor/acceptor carbene mimetic

    PubMed Central

    Luo, Chaosheng; Wang, Zhen; Huang, Yong

    2015-01-01

    Enantioselective α-alkylation of carbonyl is considered as one of the most important processes for asymmetric synthesis. Common alkylation agents, that is, alkyl halides, are notorious substrates for both Lewis acids and organocatalysts. Recently, olefins emerged as a benign alkylating species via photo/radical mechanisms. However, examples of enantioselective alkylation of aldehydes/ketones are scarce and direct asymmetric dialkylation remains elusive. Here we report an intramolecular α-cyclopropanation reaction of olefinic aldehydes to form chiral cyclopropane aldehydes. We demonstrate that an α-iodo aldehyde can function as a donor/acceptor carbene equivalent, which engages in a formal [2+1] annulation with a tethered double bond. Privileged bicyclo[3.1.0]hexane-type scaffolds are prepared in good optical purity using a chiral amine. The synthetic utility of the products is demonstrated by versatile transformations of the bridgehead formyl functionality. We expect the concept of using α-iodo iminium as a donor/acceptor carbene surrogate will find wide applications in chemical reaction development. PMID:26644194

  16. Rhodium-catalysed asymmetric allylic arylation of racemic halides with arylboronic acids

    NASA Astrophysics Data System (ADS)

    Sidera, Mireia; Fletcher, Stephen P.

    2015-11-01

    Csp2-Csp2 cross-coupling reactions between arylboronic acid and aryl halides are widely used in both academia and industry and are strategically important in the development of new agrochemicals and pharmaceuticals. Csp2-Csp3 cross-coupling reactions have been developed, but enantioselective variations are rare and simply retaining the stereochemistry is a problem. Here we report a highly enantioselective Csp2-Csp3 bond-forming method that couples arylboronic acids to racemic allyl chlorides. Both enantiomers of a cyclic chloride are converted into a single enantiomer of product via a dynamic kinetic asymmetric transformation. This Rh-catalysed method uses readily available and inexpensive building blocks and is mild and broadly applicable. For electron-deficient, electron-rich or ortho-substituted boronic acids better results are obtained with racemic allyl bromides. Oxygen substitution in the allyl halide is tolerated and the products can be functionalized to provide diverse building blocks. The approach fills a significant gap in the methods for catalytic asymmetric synthesis.

  17. Asymmetric Mannich reaction between (S)-N-(tert-butanesulfinyl)-3,3,3-trifluoroacetaldimine and malonic acid derivatives. Stereodivergent synthesis of (R)- and (S)-3-amino-4,4,4-trifluorobutanoic acids.

    PubMed

    Shibata, Norio; Nishimine, Takayuki; Shibata, Naoyuki; Tokunaga, Etsuko; Kawada, Kosuke; Kagawa, Takumi; Aceña, José Luis; Sorochinsky, Alexander E; Soloshonok, Vadim A

    2014-03-01

    Inorganic as well as organic base catalysis was found to be effective for diastereoselective Mannich additions of malonic acid derivatives to (SS)-N-(tert-butanesulfinyl)-3,3,3-trifluoroacetaldimine. In the presence of catalytic amounts of inorganic bases, n-BuLi or DMAP, the reaction gives the corresponding (R,SS)-β-aminomalonates in good yield and with diastereoselectivity up to 9/1 dr. In contrast, phosphazene bases favour the formation of the (S,SS)-diastereomer with selectivities as high as 99/1. Simple choosing of an appropriate base catalyst for the Mannich addition reaction allowed us to obtain enantiomerically pure (R)- or (S)-configured 3-amino-4,4,4-trifluorobutanoic acids after hydrolysis and decarboxylation of the corresponding β-aminomalonates.

  18. Plasma current resonance in asymmetric toroidal systems

    SciTech Connect

    Hazeltine, R. D.; Catto, Peter J.

    2015-09-15

    The well-known singularity in the magnetic differential equation for plasma current in an asymmetric toroidal confinement system is resolved by including in the pressure tensor corrections stemming from finite Larmor radius. The result provides an estimate of the amplitude of spikes in the parallel current that occur on rational magnetic surfaces. Resolution of the singularity is shown to depend on both the ambipolarity condition—the requirement of zero surface-averaged radial current—and the form of the magnetic differential equation near the rational surface.

  19. Sequential aldol condensation-transition metal-catalyzed addition reactions of aldehydes, methyl ketones, and arylboronic acids.

    PubMed

    Liao, Yuan-Xi; Xing, Chun-Hui; Israel, Matthew; Hu, Qiao-Sheng

    2011-04-15

    Sequential aldol condensation of aldehydes with methyl ketones followed by transition metal-catalyzed addition reactions of arylboronic acids to form β-substituted ketones is described. By using the 1,1'-spirobiindane-7,7'-diol (SPINOL)-based phosphite, an asymmetric version of this type of sequential reaction, with up to 92% ee, was also realized. Our study provided an efficient method to access β-substituted ketones and might lead to the development of other sequential/tandem reactions with transition metal-catalyzed addition reactions as the key step.

  20. Yields of beta-hydroxynitrates and dihydroxynitrates in aerosol formed from OH radical-initiated reactions of linear alkenes in the presence of NO(x).

    PubMed

    Matsunaga, Aiko; Ziemann, Paul J

    2009-01-22

    Yields of beta-hydroxynitrates and dihydroxynitrates in aerosol formed from OH radical-initiated reactions of linear C(8)-C(17) 1-alkenes and C(14)-C(17) internal alkenes in the presence of NO(x) were measured using a thermal desorption particle beam mass spectrometer coupled to a high-performance liquid chromatograph (HPLC) with UV-vis detector for identification and quantification. For 1-alkenes, total yields of beta-hydroxynitrates normalized for OH radical addition to the CC double bond increased with carbon number, primarily because of enhanced gas-to-particle partitioning, to a plateau of 0.140 +/- 0.009 in the C(14)-C(17) range, with 1-hydroxy/2-hydroxy isomer fractions of 0.7:0.3. When combined with yields measured by O'Brien et al. ( O'Brien , J. M. , Czuba , E. , Hastie , D. R. , Francisco , J. S. , and Shepson , P. S. J. Phys. Chem. A 1998 , 102 , 8903 ) for reactions of smaller alkenes, the results for both 1-alkenes and internal alkenes indicate that the branching ratios for the formation of beta-hydroxynitrates from the reactions of NO with beta-hydroxyperoxy radicals (averaged over both isomers) increase from 0.009 for C(2) up to 0.13-0.15 for C(14) and larger and are approximately half the values determined by Arey et al. ( Arey , J. , Aschmann , S. M. , Kwok , E. S. C. , and Atkinson , R. J. Phys. Chem. A 2001 , 105 , 1020 ) for the corresponding alkyl peroxy radicals. The range of branching ratios may be higher for individual isomers, but this could not be determined. It is estimated that for 1-alkenes, approximately 60-70% of OH radical addition occurred at the terminal carbon atom. Average yields of dihydroxynitrates normalized for OH radical addition were 0.039 +/- 0.006 and 0.006 +/- 0.002 for 1-alkenes and internal alkenes, with differences reflecting enhanced decomposition of beta-hydroxyalkoxy radicals formed from internal alkenes. The addition of NH(3) reduced yields significantly, apparently by altering hydrogen bonding between hydroxy

  1. Process for fabricating PBI hollow fiber asymmetric membranes for gas separation and liquid separation

    DOEpatents

    Jayaweera, Indira; Krishnan, Gopala N.; Sanjurjo, Angel; Jayaweera, Palitha; Bhamidi, Srinivas

    2016-04-26

    The invention provides methods for preparing an asymmetric hollow fiber, the asymmetric hollow fibers prepared by such methods, and uses of the asymmetric hollow fibers. One method involves passing a polymeric solution through an outer annular orifice of a tube-in-orifice spinneret, passing a bore fluid though an inner tube of the spinneret, dropping the polymeric solution and bore fluid through an atmosphere over a dropping distance, and quenching the polymeric solution and bore fluid in a bath to form an asymmetric hollow fiber.

  2. Crystal structure of a nucleoside model for the inter-strand cross-link formed by the reaction of 2'-de-oxy-guanosine and an abasic site in duplex DNA.

    PubMed

    Catalano, Michael J; Ruddraraju, Kasi Viswanatharaju; Barnes, Charles L; Gates, Kent S

    2016-05-01

    The title compound, 9-[(2R,4S,5R)-4-hy-droxy-5-(hy-droxy-meth-yl)tetra-hydro-furan-2-yl]-2-{[(2R,4S,5R)-4-meth-oxy-5-(meth-oxy-meth-yl)tetra-hydro-furan-2-yl]amino}-1H-purin-6(9H)-one, C17H25N5O7, crystallizes with two independent mol-ecules (A and B) in the asymmetric unit. In the crystal, the guanosine moieties of mol-ecules A and B are linked by N-H⋯N and O-H⋯N hydrogen-bonding inter-actions, forming ribbons which are stacked to form columns along [100]. These columns are then linked by O-H⋯O hydrogen bonds between the ribose moieties and numerous C-H⋯O inter-actions to complete the three-dimensional structure. PMID:27308004

  3. Hydrazones as Singular Reagents in Asymmetric Organocatalysis.

    PubMed

    de Gracia Retamosa, María; Matador, Esteban; Monge, David; Lassaletta, José M; Fernández, Rosario

    2016-09-12

    This Minireview summarizes strategies and developments regarding the use of hydrazones as reagents in asymmetric organocatalysis, their distinct roles in nucleophile-electrophile, cycloaddition, and cyclization reactions. The key structural elements governing the reactivity of these reagents in a preferred pathway will be discussed, as well as their different interactions with organocatalysts, leading to diverse activation modes. Along these studies, the synthetic equivalence of N-monoalkyl, N,N-dialkyl, and N-acyl hydrazones with several synthons is also highlighted. Emphasis is also put on the mechanistic studies performed to understand the observed reactivities. Finally, the functional group transformations performed from the available products has also been analyzed, highlighting the synthetic value of these methodologies, which served to access numerous families of valuable multifunctional compounds and nitrogen-containing heterocycles.

  4. Activation of carboxylic acids in asymmetric organocatalysis.

    PubMed

    Monaco, Mattia Riccardo; Poladura, Belén; Diaz de Los Bernardos, Miriam; Leutzsch, Markus; Goddard, Richard; List, Benjamin

    2014-07-01

    Organocatalysis, catalysis using small organic molecules, has recently evolved into a general approach for asymmetric synthesis, complementing both metal catalysis and biocatalysis. Its success relies to a large extent upon the introduction of novel and generic activation modes. Remarkably though, while carboxylic acids have been used as catalyst directing groups in supramolecular transition-metal catalysis, a general and well-defined activation mode for this useful and abundant substance class is still lacking. Herein we propose the heterodimeric association of carboxylic acids with chiral phosphoric acid catalysts as a new activation principle for organocatalysis. This self-assembly increases both the acidity of the phosphoric acid catalyst and the reactivity of the carboxylic acid. To illustrate this principle, we apply our concept in a general and highly enantioselective catalytic aziridine-opening reaction with carboxylic acids as nucleophiles.

  5. Asymmetric Synthesis of Spiroketals with Aminothiourea Catalysts.

    PubMed

    Yoneda, Naoki; Fukata, Yukihiro; Asano, Keisuke; Matsubara, Seijiro

    2015-12-14

    Chiral spiroketal skeletons are found as core structures in a range of bioactive compounds. These natural compounds and their analogues have attracted much attention in the field of drug discovery. However, methods for their enantioselective construction are limited, and easily available optically active spiroketals are rare. We demonstrate a novel catalytic asymmetric synthesis of spiroketal compounds that proceeds through an intramolecular hemiacetalization/oxy-Michael addition cascade mediated by a bifunctional aminothiourea catalyst. This results in spiroketal structures through the relay formation of contiguous oxacycles, in which multipoint recognition by the catalyst through hydrogen bonding imparts high enantioselectivity. This method offers facile access to spiroketal frameworks bearing an alkyl group at the 2-position, which are prevalent in insect pheromones. Optically active (2S,5S)-chalcogran, a pheromone of the six-spined spruce bark beetle, and an azide derivative could be readily synthesized from the bicyclic reaction product. PMID:26510921

  6. Asymmetric Total Synthesis of (-)-Lycospidine A.

    PubMed

    Xu, Shiyan; Zhang, Jing; Ma, Donghui; Xu, Dengyu; Xie, Xingang; She, Xuegong

    2016-09-16

    The first asymmetric total synthesis of the structurally unique Lycopodium alkaloid (-)-lycospidine A, containing an unprecedented five-membered ring, has been accomplished in only 10 steps with 21.6% overall yield from the known conveniently available sulfoxide. This protecting-group-free short synthesis relied on the use of a key amidation/aza-Prins domino cyclization reaction to rapidly construct the tricyclic skeleton and two continuous stereocenters (one of which is a bridged quaternary stereocenter). An intramolecular aldol condensation was successfully utilized to establish the unique five-membered ring, and a late-stage oxidation inspired by biosynthesis pathway was adopted to synthesize the diosphenol ring of (-)-lycospidine A. PMID:27565006

  7. Hydrazones as Singular Reagents in Asymmetric Organocatalysis.

    PubMed

    de Gracia Retamosa, María; Matador, Esteban; Monge, David; Lassaletta, José M; Fernández, Rosario

    2016-09-12

    This Minireview summarizes strategies and developments regarding the use of hydrazones as reagents in asymmetric organocatalysis, their distinct roles in nucleophile-electrophile, cycloaddition, and cyclization reactions. The key structural elements governing the reactivity of these reagents in a preferred pathway will be discussed, as well as their different interactions with organocatalysts, leading to diverse activation modes. Along these studies, the synthetic equivalence of N-monoalkyl, N,N-dialkyl, and N-acyl hydrazones with several synthons is also highlighted. Emphasis is also put on the mechanistic studies performed to understand the observed reactivities. Finally, the functional group transformations performed from the available products has also been analyzed, highlighting the synthetic value of these methodologies, which served to access numerous families of valuable multifunctional compounds and nitrogen-containing heterocycles. PMID:27552942

  8. Careful numerical study of flowfields about asymmetric external conical corners

    NASA Technical Reports Server (NTRS)

    Salas, M. D.

    1980-01-01

    A numerical study of the flowfield about asymmetrical external axial corners formed by the juncture of swept compressive wedges is presented. The geometrical configuration allows a unified treatment of external corners typical of delta wings and rectangular inlets. The study investigates how the flow transitions from a symmetrical flowfield with a cross-flow stagnation point at the corner to an asymmetrical flowfield for which the flow spills over the corner. The effects of leading-edge sweep, wedge compression, and corner radius are investigated.

  9. Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization.

    PubMed

    Trost, Barry M; Ryan, Michael C; Rao, Meera

    2016-01-01

    A full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu) complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enynes. This complex was used to synthesize a broad array of [3.1.0] and [4.1.0] bicycles. Sulfonamide- and phosphoramidate-containing products could be deprotected under reducing conditions. Catalysis performed with enantiomerically enriched propargyl alcohols revealed a matched/mismatched effect that was strongly dependent on the nature of the solvent. PMID:27559366

  10. Development of chiral sulfoxide ligands for asymmetric catalysis.

    PubMed

    Trost, Barry M; Rao, Meera

    2015-04-20

    Nitrogen-, phosphorus-, and oxygen-based ligands with chiral backbones have been the historic workhorses of asymmetric transition-metal-catalyzed reactions. On the contrary, sulfoxides containing chirality at the sulfur atom have mainly been used as chiral auxiliaries for diastereoselective reactions. Despite several distinct advantages over traditional ligand scaffolds, such as the proximity of the chiral information to the metal center and the ability to switch between S and O coordination, these compounds have only recently emerged as a versatile class of chiral ligands. In this Review, we detail the history of the development of chiral sulfoxide ligands for asymmetric catalysis. We also provide brief descriptions of metal-sulfoxide bonding and strategies for the synthesis of enantiopure sulfoxides. Finally, insights into the future development of this underutilized ligand class are discussed.

  11. Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization

    PubMed Central

    Ryan, Michael C; Rao, Meera

    2016-01-01

    Summary A full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu) complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enynes. This complex was used to synthesize a broad array of [3.1.0] and [4.1.0] bicycles. Sulfonamide- and phosphoramidate-containing products could be deprotected under reducing conditions. Catalysis performed with enantiomerically enriched propargyl alcohols revealed a matched/mismatched effect that was strongly dependent on the nature of the solvent. PMID:27559366

  12. Catalytic asymmetric total synthesis of (-)-galanthamine and (-)-lycoramine.

    PubMed

    Li, Lei; Yang, Qiao; Wang, Yuan; Jia, Yanxing

    2015-05-18

    The catalytic asymmetric total syntheses of (-)-galanthamine (1) and (-)-lycoramine (2) have been achieved by using a conceptually new strategy featuring two metal-catalyzed reactions as the key steps. A new method for the construction of 3,4-fused benzofurans has been developed through a palladium-catalyzed intramolecular Larock annulation reaction, which was successfully applied to the construction of the ABD tricyclic skeleton of 1 and 2. To achieve the asymmetric synthesis of 1 and 2, a Sc(III)/N,N'-dioxide complex was used to catalyze the enantioselective conjugate addition of 3-alkyl-substituted benzofuranone to methyl vinyl ketone for the construction of a chiral quaternary carbon center. PMID:25847447

  13. Asymmetric trienamine catalysis: new opportunities in amine catalysis.

    PubMed

    Kumar, Indresh; Ramaraju, Panduga; Mir, Nisar A

    2013-02-01

    Amine catalysis, through HOMO-activating enamine and LUMO-activating iminium-ion formation, is receiving increasing attention among other organocatalytic strategies, for the activation of unmodified carbonyl compounds. Particularly, the HOMO-raising activation concept has been applied to the greatest number of asymmetric transformations through enamine, dienamine, and SOMO-activation strategies. Recently, trienamine catalysis, an extension of amine catalysis, has emerged as a powerful tool for synthetic chemists with a novel activation strategy for polyenals/polyenones. In this review article, we discuss the initial developments of trienamine catalysis for highly asymmetric Diels-Alder reactions with different dienophiles and emerging opportunities for other types of cycloadditions and cascade reactions.

  14. Laboratory studies of carbon kinetic isotope effects on the production mechanism of particulate phenolic compounds formed by toluene photooxidation: a tool to constrain reaction pathways.

    PubMed

    Irei, Satoshi; Rudolph, Jochen; Huang, Lin; Auld, Janeen; Collin, Fabrice; Hastie, Donald

    2015-01-01

    In this study, we examined compound-specific stable carbon isotope ratios for phenolic compounds in secondary organic aerosol (SOA) formed by photooxidation of isotope-label-free toluene. SOA generated by photooxidation of toluene using a continuous-flow reactor and an 8 m(3) indoor smog chamber was collected on filters, which were extracted with acetonitrile for compound-specific analysis. Eight phenolic compounds were identified in the extracts using a gas chromatograph coupled with a mass spectrometer, and their compound-specific stable carbon isotope ratios were determined using a gas chromatograph coupled with a combustion furnace followed by an isotope ratio mass spectrometer. The majority of products, including methylnitrophenols and methylnitrocatechols, were isotopically depleted by 5-6‰ compared to the initial isotope ratio of toluene, whereas the isotope ratio for 4-nitrophenol remained identical to that of toluene. On the basis of the reaction mechanisms proposed in previous reports, stable carbon isotope ratios of these products were calculated. By comparing the observed isotope ratios with the predicted isotope ratios, we explored possible production pathways for the particulate phenolic compounds.

  15. Four-mode quantum calculations of resonance states in complex-forming bimolecular reactions: Cl{sup -}+CH{sub 3}Br

    SciTech Connect

    Schmatz, Stefan

    2005-06-15

    The vibrational resonance states of the complexes formed in the nucleophilic bimolecular substitution (S{sub N}2) reaction Cl{sup -}+CH{sub 3}Br{yields}ClCH{sub 3}+Br{sup -} were calculated by means of the filter diagonalization method employing a coupled-cluster potential-energy surface and a Hamiltonian that incorporates an optical potential and is formulated in Radau coordinates for the carbon-halogen stretching modes. The four-dimensional model also includes the totally symmetric vibrations of the methyl group (C-H stretch and umbrella bend). The vast majority of bound states and many resonance states up to the first overtone of the symmetric stretching vibration in the exit channel complex have been calculated, analyzed, and assigned four quantum numbers. The resonances are classified into entrance channel, exit channel, and delocalized states. The resonance widths fluctuate over six orders of magnitude. In addition to a majority of Feshbach-type resonances there are also exceedingly long-lived shape resonances, which are associated with the entrance channel and can only decay by tunneling. The state-selective decay of the resonances was studied in detail. The linewidths of the resonances, and thus the coupling to the energetic continuum, increase with excitation in any mode. Due to the strong mixing of the many progressions in the intermolecular stretching modes of the intermediate complexes, this increase as a function of the corresponding quantum numbers is not monotonic, but exhibits pronounced fluctuations.

  16. Catalytic reduction of NO by CO over rhodium catalysts. 2. Effect of oxygen on the nature, population, and reactivity of surface species formed under reaction conditions

    SciTech Connect

    Kondarides, D.I.; Chafik, T.; Verykios, X.E.

    2000-04-01

    The effect of oxygen on the nature, population, and reactivity of surface species formed during reduction of NO by CO over Rh/TiO{sub 2} catalysts has been examined employing FTIR and transient MS techniques. It has been found that the activity of Rh is hindered by accumulation of surface oxygen originating from NO decomposition and gas-phase oxygen in the feed. Adsorbed CO and reduced TiO{sub 2{minus}x} species in the vicinity of Rh particles act as oxygen atom scavengers and, under fuel-rich conditions, remove atomic oxygen from the surface and restore the catalytic properties. Results of the present study provide additional evidence that production of N{sub 2} is related to dissociation of adsorbed Rh-NO{sup {minus}} while production of N{sub 2}O is related to the presence of Rh(NO){sub 2}. The presence of reduced RH{sup 0} sites is necessary for the formation of both reduction products. In the absence of oxygen in the feed, surface isocyanate species are also observed under reaction conditions. Their formation requires the presence of adjacent Rh{sup 0}-CO and reduced Rh{sup 0} sites. Although these species are favored under conditions in which NO conversion to reduction products is observed, there is no evidence that they are catalytically active species.

  17. Laboratory studies of carbon kinetic isotope effects on the production mechanism of particulate phenolic compounds formed by toluene photooxidation: a tool to constrain reaction pathways.

    PubMed

    Irei, Satoshi; Rudolph, Jochen; Huang, Lin; Auld, Janeen; Collin, Fabrice; Hastie, Donald

    2015-01-01

    In this study, we examined compound-specific stable carbon isotope ratios for phenolic compounds in secondary organic aerosol (SOA) formed by photooxidation of isotope-label-free toluene. SOA generated by photooxidation of toluene using a continuous-flow reactor and an 8 m(3) indoor smog chamber was collected on filters, which were extracted with acetonitrile for compound-specific analysis. Eight phenolic compounds were identified in the extracts using a gas chromatograph coupled with a mass spectrometer, and their compound-specific stable carbon isotope ratios were determined using a gas chromatograph coupled with a combustion furnace followed by an isotope ratio mass spectrometer. The majority of products, including methylnitrophenols and methylnitrocatechols, were isotopically depleted by 5-6‰ compared to the initial isotope ratio of toluene, whereas the isotope ratio for 4-nitrophenol remained identical to that of toluene. On the basis of the reaction mechanisms proposed in previous reports, stable carbon isotope ratios of these products were calculated. By comparing the observed isotope ratios with the predicted isotope ratios, we explored possible production pathways for the particulate phenolic compounds. PMID:25490235

  18. Vertical asymmetric double quantum dots

    NASA Astrophysics Data System (ADS)

    Roßbach, R.; Reischle, M.; Beirne, G. J.; Schweizer, H.; Jetter, M.; Michler, P.

    2007-01-01

    Two layers of differently sized self-assembled InP-quantum dots (QDs) separated by a GaInP spacer layer with varying thickness were grown by metal organic vapor phase epitaxy (MOVPE). Photoluminescence measurements of the QD ensembles and of individual asymmetric double QDS show coupling due to the tunnelling of carriers.

  19. Asymmetrical Switch Costs in Children

    ERIC Educational Resources Information Center

    Ellefson, Michelle R.; Shapiron, Laura R.; Chater, Nick

    2006-01-01

    Switching between tasks produces decreases in performance as compared to repeating the same task. Asymmetrical switch costs occur when switching between two tasks of unequal difficulty. This asymmetry occurs because the cost is greater when switching to the less difficult task than when switching to the more difficult task. Various theories about…

  20. Asymmetric printing of molecules and zeolites on self assembled monolayers.

    PubMed

    Kehr, Nermin Seda; Schäfer, Andreas; Ravoo, Bart Jan; De Cola, Luisa

    2010-04-01

    Microcontact printing (mCP) is used to immobilize dyes and peptides asymmetrically, by a "peptide coupling" reaction, on monolayers of zeolite L crystals in the contact area between the stamp and the surface of the monolayer. Chemically patterned surfaces of monolayers of zeolite L crystals are obtained by using patterned stamps with different ink solutions. Additional printing of functionalized nano-objects on SAMs of zeolite L crystals is demonstrated.

  1. Asymmetric spindle pole formation in CPAP-depleted mitotic cells.

    PubMed

    Lee, Miseon; Chang, Jaerak; Chang, Sunghoe; Lee, Kyung S; Rhee, Kunsoo

    2014-02-21

    CPAP is an essential component for centriole formation. Here, we report that CPAP is also critical for symmetric spindle pole formation during mitosis. We observed that pericentriolar material between the mitotic spindle poles were asymmetrically distributed in CPAP-depleted cells even with intact numbers of centrioles. The length of procentrioles was slightly reduced by CPAP depletion, but the length of mother centrioles was not affected. Surprisingly, the young mother centrioles of the CPAP-depleted cells are not fully matured, as evidenced by the absence of distal and subdistal appendage proteins. We propose that the selective absence of centriolar appendages at the young mother centrioles may be responsible for asymmetric spindle pole formation in CPAP-depleted cells. Our results suggest that the neural stem cells with CPAP mutations might form asymmetric spindle poles, which results in premature initiation of differentiation.

  2. Gravity-induced asymmetric distribution of a plant growth hormone

    NASA Technical Reports Server (NTRS)

    Bandurski, R. S.; Schulze, A.; Momonoki, Y.

    1984-01-01

    Dolk (1936) demonstrated that gravistimulation induced an asymmetric distribution of auxin in a horizontally-placed shoot. An attempt is made to determine where and how that asymmetry arises, and to demonstrate that the endogenous auxin, indole-3-acetic acid, becomes asymmetrically distributed in the cortical cells of the Zea mays mesocotyl during 3 min of geostimulation. Further, indole-3-acetic acid derived by hydrolysis of an applied transport form of the hormone, indole-3-acetyl-myo-inositol, becomes asymmetrically distributed within 15 min of geostimulus time. From these and prior data is developed a working theory that the gravitational stimulus induces a selective leakage, or secretion, of the hormone from the vascular tissue to the cortical cells of the mesocotyl.

  3. Pentamodal behaviors and acoustic bandgaps of asymmetric pentamode elastic metamaterials

    NASA Astrophysics Data System (ADS)

    Huang, Yan; Lu, Xuegang; Liang, Gongying; Xu, Zhuo

    2016-04-01

    The asymmetric pentamode metamaterial structure which is built by connecting double-cones with different cross-section shapes (regular triangle, square, pentagon and hexagon) to form diamond lattice is proposed in this paper. Then its phonon band structure is calculated by finite-element method (FEM), and its pentamodal behaviors and acoustic bandgaps are studied in detail. Results show that in the process of adjusting geometrical parameters, the asymmetric case performs similar pentamodal behaviors [ratio of bulk modulus to shear modulus B/G and single-mode bandgap (SBG)] with the symmetric cases. And the asymmetric case not only remains the intrinsic complete bandgap (CBG) of mode 12-13 like symmetric cases, but also opens new and wide CBG of mode 10-11 and mode 14-15 for appropriate parameters. Therefore, introducing structural asymmetry should be an effective way to open CBG in pentamode elastic metamaterials.

  4. Algebraic Davis Decomposition and Asymmetric Doob Inequalities

    NASA Astrophysics Data System (ADS)

    Hong, Guixiang; Junge, Marius; Parcet, Javier

    2016-09-01

    In this paper we investigate asymmetric forms of Doob maximal inequality. The asymmetry is imposed by noncommutativity. Let {({M}, τ)} be a noncommutative probability space equipped with a filtration of von Neumann subalgebras {({M}_n)_{n ≥ 1}}, whose union {bigcup_{n≥1}{M}_n} is weak-* dense in {{M}}. Let {{E}_n} denote the corresponding family of conditional expectations. As an illustration for an asymmetric result, we prove that for {1 < p < 2} and {x in L_p({M},τ)} one can find {a, b in L_p({M},τ)} and contractions {u_n, v_n in {M}} such that {E}_n(x) = a u_n + v_n b quad and quad max big{ |a|_p,|b|_p big} ≤ c_p |x|_p. Moreover, it turns out that {a u_n} and {v_n b} converge in the row/column Hardy spaces {{H}_p^r({M})} and {{H}_p^c({M})} respectively. In particular, this solves a problem posed by the Defant and Junge in 2004. In the case p = 1, our results establish a noncommutative form of the Davis celebrated theorem on the relation betwe en martingale maximal and square functions in L 1, whose noncommutative form has remained open for quite some time. Given {1 ≤ p ≤ 2}, we also provide new weak type maximal estimates, which imply in turn left/right almost uniform convergence of {{E}_n(x)} in row/column Hardy spaces. This improves the bilateral convergence known so far. Our approach is based on new forms of Davis martingale decomposition which are of independent interest, and an algebraic atomic description for the involved Hardy spaces. The latter results are new even for commutative von Neumann algebras.

  5. Mitigation of Hydrogen Gas Generation from the Reaction of Uranium Metal with Water in K Basin Sludge and Sludge Waste Forms

    SciTech Connect

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2011-06-08

    corrosion rates in water alone and in simulated sludge were near or slightly below the metal-in-water rate while nitrate-free sludge/Aquaset II decreased rates by about a factor of 3. Addition of 1 M nitrate to simulated sludge decreased the corrosion rate by a factor of ~5 while 1 M nitrate in sludge/Aquaset II mixtures decreased the corrosion rate by ~2.5 compared with the nitrate-free analogues. Mixtures of simulated sludge with Aquaset II treated with 1 M nitrate had uranium corrosion rates about a factor of 8 to 10 lower than the water-only rate law. Nitrate was found to provide substantial hydrogen mitigation for immobilized simulant sludge waste forms containing Aquaset II or Aquaset II G clay. Hydrogen attenuation factors of 1000 or greater were determined at 60°C for sludge-clay mixtures at 1 M nitrate. Hydrogen mitigation for tests with PC and Aquaset II H (which contains PC) were inconclusive because of suspected failure to overcome induction times and fully enter into anoxic corrosion. Lessening of hydrogen attenuation at ~80°C and ~95°C for simulated sludge and Aquaset II was observed with attenuation factors around 100 to 200 at 1 M nitrate. Valuable additional information has been obtained on the ability of nitrate to attenuate hydrogen gas generation from solution, simulant K Basin sludge, and simulant sludge with immobilization agents. Details on characteristics of the associated reactions were also obtained. The present testing confirms prior work which indicates that nitrate is an effective agent to attenuate hydrogen from uranium metal corrosion in water and simulated K Basin sludge to show that it is also effective in potential candidate solidified K Basin waste forms for WIPP disposal. The hydrogen mitigation afforded by nitrate appears to be sufficient to meet the hydrogen generation limits for shipping various sludge waste streams based on uranium metal concentrations and assumed waste form loadings.

  6. Catalytic Asymmetric Arylation of α-Aryl-α-diazoacetates with Aniline Derivatives.

    PubMed

    Xu, Bin; Li, Mao-Lin; Zuo, Xiao-Dong; Zhu, Shou-Fei; Zhou, Qi-Lin

    2015-07-15

    The asymmetric arylation of diazo compounds with aniline derivatives cooperatively catalyzed by an achiral dirhodium complex and a chiral spiro phosphoric acid is reported. The reaction provides a new method for the facile synthesis of α-diarylacetates, versatile building blocks with a diaryl tertiary chiral center, in good yields (up to 95%) with high enantioselectivities (up to 97% ee). Preliminary mechanistic studies suggest that the arylation reaction proceeds via a stepwise process, in which the enantioselectivity is controlled by a chiral spiro phosphoric acid-promoted proton shift in a zwitterionic intermediate. This work represents the first asymmetric intermolecular C(sp(2))-H bond insertion reaction with arenes.

  7. Asymmetric cyanation of imines via dipeptide-derived organophosphine dual-reagent catalysis

    PubMed Central

    Wang, Hong-Yu; Zheng, Chang-Wu; Chai, Zhuo; Zhang, Jia-Xing; Zhao, Gang

    2016-01-01

    Over the past few decades, enantioselective phosphine organocatalysis has evolved rapidly into a highly efficient catalytic strategy for a range of useful reactions. However, as restricted by the traditional catalytic modes, some important reactions, such as asymmetric Strecker-type reactions, have thus far been out of reach of this strategy. Reported herein is an application of enantioselective phosphine organocatalysis for asymmetric Strecker-type reactions, enabled by a dual-reagent catalyst system in which the key organophosphorus zwitterion intermediate, generated in situ by mixing a chiral dipeptide-derived multifunctional organophosphine with methyl acrylate, is used as a highly efficient chiral Lewis base catalyst. The high efficiency of this catalytic system is demonstrated in the asymmetric cyanation of isatin-derived ketimines and azomethine aldimines as well as in the kinetic resolution of racemic 3-substituted azomethines. Mechanistic studies provide experimental evidence for the intermediacy of the putative zwitterion and its role as a catalytically active Lewis base. PMID:27625043

  8. Asymmetric cyanation of imines via dipeptide-derived organophosphine dual-reagent catalysis.

    PubMed

    Wang, Hong-Yu; Zheng, Chang-Wu; Chai, Zhuo; Zhang, Jia-Xing; Zhao, Gang

    2016-01-01

    Over the past few decades, enantioselective phosphine organocatalysis has evolved rapidly into a highly efficient catalytic strategy for a range of useful reactions. However, as restricted by the traditional catalytic modes, some important reactions, such as asymmetric Strecker-type reactions, have thus far been out of reach of this strategy. Reported herein is an application of enantioselective phosphine organocatalysis for asymmetric Strecker-type reactions, enabled by a dual-reagent catalyst system in which the key organophosphorus zwitterion intermediate, generated in situ by mixing a chiral dipeptide-derived multifunctional organophosphine with methyl acrylate, is used as a highly efficient chiral Lewis base catalyst. The high efficiency of this catalytic system is demonstrated in the asymmetric cyanation of isatin-derived ketimines and azomethine aldimines as well as in the kinetic resolution of racemic 3-substituted azomethines. Mechanistic studies provide experimental evidence for the intermediacy of the putative zwitterion and its role as a catalytically active Lewis base. PMID:27625043

  9. Asymmetric cyanation of imines via dipeptide-derived organophosphine dual-reagent catalysis

    NASA Astrophysics Data System (ADS)

    Wang, Hong-Yu; Zheng, Chang-Wu; Chai, Zhuo; Zhang, Jia-Xing; Zhao, Gang

    2016-09-01

    Over the past few decades, enantioselective phosphine organocatalysis has evolved rapidly into a highly efficient catalytic strategy for a range of useful reactions. However, as restricted by the traditional catalytic modes, some important reactions, such as asymmetric Strecker-type reactions, have thus far been out of reach of this strategy. Reported herein is an application of enantioselective phosphine organocatalysis for asymmetric Strecker-type reactions, enabled by a dual-reagent catalyst system in which the key organophosphorus zwitterion intermediate, generated in situ by mixing a chiral dipeptide-derived multifunctional organophosphine with methyl acrylate, is used as a highly efficient chiral Lewis base catalyst. The high efficiency of this catalytic system is demonstrated in the asymmetric cyanation of isatin-derived ketimines and azomethine aldimines as well as in the kinetic resolution of racemic 3-substituted azomethines. Mechanistic studies provide experimental evidence for the intermediacy of the putative zwitterion and its role as a catalytically active Lewis base.

  10. Dual task effects for asymmetric stepping on a split-belt treadmill.

    PubMed

    McFadyen, Bradford J; Hegeman, Judith; Duysens, Jacques

    2009-10-01

    Bilaterally asymmetric stepping during walking is common to a number of pathological gaits (e.g., hemiplegia, limping). In the present work, the attention level of asymmetric stepping was studied by having subjects walk on a split-belt treadmill with symmetric (2 km/h) and asymmetric (2 km/h vs 4 km/h and 2 km/h vs 6 km/h) belt speeds both with and without a dual auditory Stroop task. There was no significant change in response reaction times across walking conditions or between walking and standing. The proportion of stance phase was unchanged by the dual task during symmetric walking. Stance phase proportions, however, significantly increased during dual tasking for the limb on the faster belt for both asymmetric conditions, while they decreased for the limb on the slower belt for the most asymmetric condition. There were also small modifications to double support proportions and a main effect of dual tasking to double support proportion variability. Observed dual task changes showed interference by the cognitive task with asymmetric gait performance, suggesting that asymmetric stepping, such as seen in limping gaits, requires more attention than symmetric walking. Such attention may, in part, be due to the dynamic balance required in asymmetric limb loading and unloading. PMID:19595592

  11. Asymmetric Synthesis of 2,4,5-Trisubstituted Δ2-Thiazolines

    PubMed Central

    Bengtsson, Christoffer; Nelander, Hanna; Almqvist, Fredrik

    2013-01-01

    Δ2-Thiazolines are interesting heterocycles that display a wide variety of biological characteristics. They are also common in chiral ligands used for asymmetric syntheses and as synthetic intermediates. Herein, we present asymmetric routes to 2,4,5-trisubstituted Δ2-thiazolines. These Δ2-thiazolines were synthesized from readily accessible/commercially available α,β-unsaturated methyl esters through a Sharpless asymmetric dihydroxylation and an O→N acyl migration reaction as key steps. The final products were obtained in good yields with up to 97% enantiomeric excess. PMID:23776083

  12. Multi-component Cycloaddition Approaches in the Catalytic Asymmetric Synthesis of Alkaloid Targets†

    PubMed Central

    Perreault, Stéphane; Rovis, Tomislav

    2010-01-01

    Cycloaddition reactions are attractive strategies for rapid formation of molecular complexity in organic synthesis as multiple bonds are formed in a single process. To this end, several research groups have been actively involved in the development of catalytic methods to activate readily accessible π-components to achieve cycloadditions. However, the use of C-N π-components for the formation of heterocycles by these processes is less well developed. It has been previously demonstrated that the combination of different isocyanates with two alkynes yields pyridones of several types by metal-catalyzed [2+2+2] cycloadditions. The potential of this chemistry has been extended to alkenes as C-C π-components, allowing the formation of sp3-stereocenters. In this tutorial review directed towards [n+2+2] cycloaddition of heterocumulenes, alkynes and alkenes, the recent advances in catalytic asymmetric synthesis of indolizidine, quinolizidine and azocine skeletons are discussed. PMID:19847348

  13. [Stereocontrolled synthesis of phosphinyl dipeptide isosteres using an asymmetric center at the phosphorus atom].

    PubMed

    Yamagishi, Takehiro

    2014-01-01

    Phosphinyl dipeptide isosteres (PDIs) are important compounds for the development of potent and selective inhibitors of various aspartic proteases and Zn metalloproteases. The stereochemistry of PDIs affects their biological activity. PDIs were prepared successfully using the concept of asymmetric induction from the chiral phosphorus atom of the phosphinate moiety to the neighboring carbon atom. This methodology involves diastereoselective α-alkylation and β'-alkylation of P-chiral phosphinate derivatives, prepared through lipase-catalyzed kinetic resolution, which produces Phe-Ala type and Pro-Phe type PDIs. The synthesis of Leu-Pro type PDIs in a protected form was achieved through a cross-coupling reaction of stereodefined α-amino-H-phosphinate with alkenyl triflate, followed by diastereoselective hydrogenation of the alkene moiety. PMID:25174361

  14. Correlation between the Selectivity and the Structure of an Asymmetric Catalyst Built on a Chirally Amplified Supramolecular Helical Scaffold.

    PubMed

    Desmarchelier, Alaric; Caumes, Xavier; Raynal, Matthieu; Vidal-Ferran, Anton; van Leeuwen, Piet W N M; Bouteiller, Laurent

    2016-04-13

    For the first time, supramolecular helical rods composed of an achiral metal complex and a complementary enantiopure monomer provided a good level of enantioinduction in asymmetric catalysis. Mixtures containing an achiral ligand monomer (BTA(PPh2), 2 mol %) and an enantiopure ligand-free comonomer (ester BTA, 2.5 mol %), both possessing a complementary benzene-1,3,5-tricarboxamide (BTA) central unit, were investigated in combination with [Rh(cod)2]BArF (1 mol %) in the asymmetric hydrogenation of dimethyl itaconate. Notably, efficient chirality transfer occurs within the hydrogen-bonded coassemblies formed by BTA Ile and the intrinsically achiral catalytic rhodium catalyst, providing the hydrogenation product with up to 85% ee. The effect of the relative content of BTA Ile as compared to the ligand was investigated. The amount of chiral comonomer can be decreased down to one-fourth of that of the ligand without deteriorating the enantioselectivity of the reaction, while the enantioselectivity decreases for mixtures containing high amounts of BTA Ile. The nonlinear relationship between the amount of chiral comonomer and the enantioselectivity indicates that chirality amplification effects are at work in this catalytic system. Also, right-handed helical rods are formed upon co-assembly of the achiral rhodium complex of BTA(PPh2) and the enantiopure comonomer BTA Ile as confirmed by various spectroscopic and scattering techniques. Remarkably, the major enantiomer and the selectivity of the catalytic reaction are related to the handedness and the net helicity of the coassemblies, respectively. Further development of this class of catalysts built on chirally amplified helical scaffolds should contribute to the design of asymmetric catalysts operating with low amounts of chiral entities. PMID:26998637

  15. Asymmetric target patterns in one-dimensional oscillatory media with genuine nonlocal coupling.

    PubMed

    Plenge, F; Varela, H; Krischer, K

    2005-05-20

    We report the observation of a self-organized asymmetric wave source in a one-dimensional (1D) electrochemical system, namely, the hydrogen oxidation reaction on Pt in the presence of poisons. Numerical simulations reveal that the nonlocal migration coupling is crucial for the endogenous persistence of the perturbation that causes the asymmetry. Experiments and simulations agree perfectly for the regular and irregular variant of these asymmetric waves, manifesting the existence of nonlocal coupling induced patterns also in physical systems.

  16. Limit laws for the asymmetric inclusion process.

    PubMed

    Reuveni, Shlomi; Eliazar, Iddo; Yechiali, Uri

    2012-12-01

    The Asymmetric Inclusion Process (ASIP) is a unidirectional lattice-gas flow model which was recently introduced as an exactly solvable 'Bosonic' counterpart of the 'Fermionic' asymmetric exclusion process. An iterative algorithm that allows the computation of the probability generating function (PGF) of the ASIP's steady state exists but practical considerations limit its applicability to small ASIP lattices. Large lattices, on the other hand, have been studied primarily via Monte Carlo simulations and were shown to display a wide spectrum of intriguing statistical phenomena. In this paper we bypass the need for direct computation of the PGF and explore the ASIP's asymptotic statistical behavior. We consider three different limiting regimes: heavy-traffic regime, large-system regime, and balanced-system regime. In each of these regimes we obtain-analytically and in closed form-stochastic limit laws for five key ASIP observables: traversal time, overall load, busy period, first occupied site, and draining time. The results obtained yield a detailed limit-laws perspective of the ASIP, numerical simulations demonstrate the applicability of these laws as useful approximations.

  17. Instability of asymmetric continuous shaft system

    NASA Astrophysics Data System (ADS)

    Srinath, R.; Sarkar, Abhijit; Sekhar, A. S.

    2016-11-01

    In this work, the governing equation of asymmetric continuous shaft in inertial frame of reference is studied. In particular, determination of the parameter ranges for the stability or instability of the shaft response is the focus of the present work. The governing equations are a fourth-order coupled partial differential equations containing time dependent coefficients. The equations are non-dimensionalized in terms of two parameters related to the average moment of inertia and the difference of moments of inertia about the principal axes. Using the latter as the asymptotic parameter and employing modal superposition, a formal methodology based on perturbation methods is developed to ascertain the stability and instability characteristics. The methodology is applicable to shafts subjected to some of the classical boundary conditions viz. simply supported, cantilever, and fixed-fixed. Similar stability curves are obtained for each mode for these different boundary conditions. The novel non-dimensionalization scheme chosen leads to the stability boundaries as well as the loci of varying speeds to be in the form of straight lines. The intersection of these lines determine the stable and unstable speed ranges of different asymmetric shafts. The results are generalized for different material and geometric properties of the shaft.

  18. Limit laws for the asymmetric inclusion process.

    PubMed

    Reuveni, Shlomi; Eliazar, Iddo; Yechiali, Uri

    2012-12-01

    The Asymmetric Inclusion Process (ASIP) is a unidirectional lattice-gas flow model which was recently introduced as an exactly solvable 'Bosonic' counterpart of the 'Fermionic' asymmetric exclusion process. An iterative algorithm that allows the computation of the probability generating function (PGF) of the ASIP's steady state exists but practical considerations limit its applicability to small ASIP lattices. Large lattices, on the other hand, have been studied primarily via Monte Carlo simulations and were shown to display a wide spectrum of intriguing statistical phenomena. In this paper we bypass the need for direct computation of the PGF and explore the ASIP's asymptotic statistical behavior. We consider three different limiting regimes: heavy-traffic regime, large-system regime, and balanced-system regime. In each of these regimes we obtain-analytically and in closed form-stochastic limit laws for five key ASIP observables: traversal time, overall load, busy period, first occupied site, and draining time. The results obtained yield a detailed limit-laws perspective of the ASIP, numerical simulations demonstrate the applicability of these laws as useful approximations. PMID:23367919

  19. Explosive synchronization with asymmetric frequency distribution

    NASA Astrophysics Data System (ADS)

    Zhou, Wenchang; Chen, Lumin; Bi, Hongjie; Hu, Xin; Liu, Zonghua; Guan, Shuguang

    2015-07-01

    In this work, we study the synchronization in a generalized Kuramoto model with frequency-weighted coupling. In particular, we focus on the situations in which the frequency distributions of oscillators are asymmetric. For typical unimodal frequency distributions, such as Lorentzian, Gaussian, triangle, and even special Rayleigh, we find that the synchronization transition in the model generally converts from the first order to the second order as the central frequency shifts toward positive direction. We characterize two interesting coherent states in the system: In the former, two phase-locking clusters are formed, rotating with the same frequency. They correspond to those oscillators with relatively high frequencies while the oscillators with relatively small frequencies are not entrained. In the latter, two phase-locking clusters rotate with different frequencies, leading to the oscillation of the order parameter. We further conduct theoretical analysis to reveal the relation between the asymmetric frequency distribution and the conversion of synchronization type, and justify the coherent states observed in the system.

  20. Comparative study on sample stacking by moving reaction boundary formed with weak acid and weak or strong alkali in capillary electrophoresis: I. Theory.

    PubMed

    Cao, Chengxi; Zhang, Wei; Fan, Liuyin; Shao, Jing; Li, Si

    2011-05-15

    The condensation of low abundance zwitterion substance, such as protein and peptide, has great significance to the study on proteomics. This paper develops the theory on design of online stacking conditions of zwitterion by a moving reaction boundary (MRB) in capillary electrophoresis (CE). This concerns the choice of running and sample buffers, velocity design of MRB, and salt effect on the stacking. The theoretical results unveil that: (1) the velocity of MRB formed with weak acidic buffer and strong alkali should be set between zero and the velocity of zwitterion in the alkali phase, or no stacking occurs; (2) if a strong alkali is used to prepare the sample, a much long front plug of strong base must be injected before the alkaline sample plug for complete stacking, whereas no such front plug is needed if a weak alkali with enough high concentration and pH value is used to prepare the sample buffer; (3) the existence of salt in sample matrix has a weak effect on the stacking of zwitterion if sample is prepared with weak alkaline buffer, while has a dramatic effect on the same stacking if with a strong base buffer. In addition, the concentration of weak alkali used for preparation of sample should be set at the point, at which the velocity of MRB is as much as possible close to that of negative zwitterion. The developed theory and its computation are quantitatively proved by the experiments of zwitterion stacking by the MRB as shown in the previous and the accompanying papers. The proposed theoretic results hold obvious significances on-column stacking of low abundance zwitterions, such as amino acid, or peptides or proteins, in CE.

  1. An active site mutant of Escherichia coli cyclopropane fatty acid synthase forms new non-natural fatty acids providing insights on the mechanism of the enzymatic reaction.

    PubMed

    E, Guangqi; Drujon, Thierry; Correia, Isabelle; Ploux, Olivier; Guianvarc'h, Dominique

    2013-12-01

    We have produced and purified an active site mutant of the Escherichia coli cyclopropane fatty acid synthase (CFAS) by replacing the strictly conserved G236 within cyclopropane synthases, by a glutamate residue, which corresponds to E146 of the homologous mycolic acid methyltransferase, Hma, producing hydroxymethyl mycolic acids. The G236E CFAS mutant had less than 1% of the in vitro activity of the wild type enzyme. We expressed the G236E CFAS mutant in an E. coli (DE3) strain in which the chromosomal cfa gene had been deleted. After extraction of phospholipids and conversion into the corresponding fatty acid methyl esters (FAMEs), we observed the formation of cyclopropanated FAMEs suggesting that the mutant retained some of the normal activity in vivo. However, we also observed the formation of new C17 methyl-branched unsaturated FAMEs whose structures were determined using GC/MS and NMR analyses. The double bond was located at different positions 8, 9 or 10, and the methyl group at position 10 or 9. Thus, this new FAMEs are likely arising from a 16:1 acyl chain of a phospholipid that had been transformed by the G236E CFAS mutant in vivo. The reaction catalyzed by this G236E CFAS mutant thus starts by the methylation of the unsaturated acyl chain at position 10 or 9 yielding a carbocation at position 9 or 10 respectively. It follows then two competing steps, a normal cyclopropanation or hydride shift/elimination events giving different combinations of alkenes. This study not only provides further evidence that cyclopropane synthases (CSs) form a carbocationic intermediate but also opens the way to CSs engineering for the synthesis of non-natural fatty acids.

  2. Scaffold of Asymmetric Organic Compounds - Magnetite Plaquettes

    NASA Technical Reports Server (NTRS)

    Chan, Q. H. S.; Zolensky, M. E.; Martinez, J.

    2015-01-01

    Life on Earth shows preference towards the set of organics with particular spatial configurations, this 'selectivity' is a crucial criterion for life. With only rare exceptions, life prefers the left- (L-) form over the right- (D-) form of amino acids, resulting in an L-enantiomeric excess (L-ee). Recent studies have shown Lee for alpha-methyl amino acids in some chondrites. Since these amino acids have limited terrestrial occurrence, the origin of their stereoselectivity is nonbiological, and it seems appropriate to conclude that chiral asymmetry, the molecular characteristic that is common to all terrestrial life form, has an abiotic origin. A possible abiotic mechanism that can produce chiral asymmetry in meteoritic amino acids is their formation with the presence of asymmetric catalysts, as mineral crystallization can produce spatially asymmetric structures. Magnetite is shown to be an effective catalyst for the formation of amino acids that are commonly found in chondrites. Magnetite 'plaquettes' (or 'platelets'), first described by Jedwab, show an interesting morphology of barrel-shaped stacks of magnetite disks with an apparent dislocation-induced spiral growth that seem to be connected at the center. A recent study by Singh et al. has shown that magnetites can self-assemble into helical superstructures. Such molecular asymmetry could be inherited by adsorbed organic molecules. In order to understand the distribution of 'spiral' magnetites in different meteorite classes, as well as to investigate their apparent spiral configurations and possible correlation to molecular asymmetry, we observed polished sections of carbonaceous chondrites (CC) using scanning electron microscope (SEM) imaging. The sections were also studied by electron backscattered diffraction (EBSD) in order to reconstruct the crystal orientation along the stack of magnetite disks.

  3. Asymmetric Propargylation of Ketones using Allenylboronates Catalyzed by Chiral Biphenols

    PubMed Central

    Barnett, David S.; Schaus, Scott E.

    2011-01-01

    Chiral biphenols catalyze the enantioselective asymmetric propargylation of ketones using allenylboronates. The reaction uses 10 mol % of 3,3′-Br2-BINOL as the catalyst and allenyldioxoborolane as the nucleophile, in the absence of solvent, and under microwave irradiation to afford the homopropargylic alcohol. The reaction products are obtained in good yields (60 – 98%) and high enantiomeric ratios (3:1 – 99:1). Diastereoselective propargylations using chiral racemic allenylboronates result in good diastereoselectivities (dr > 86:14) and enantioselectivities (er > 92:8) under the catalytic conditions. PMID:21732609

  4. Asymmetric propargylation of ketones using allenylboronates catalyzed by chiral biphenols.

    PubMed

    Barnett, David S; Schaus, Scott E

    2011-08-01

    Chiral biphenols catalyze the enantioselective asymmetric propargylation of ketones using allenylboronates. The reaction uses 10 mol % of 3,3'-Br(2)-BINOL as the catalyst and allenyldioxoborolane as the nucleophile, in the absence of solvent, and under microwave irradiation to afford the homopropargylic alcohol. The reaction products are obtained in good yields (60-98%) and high enantiomeric ratios (3:1-99:1). Diastereoselective propargylations using chiral racemic allenylboronates result in good diastereoselectivities (dr >86:14) and enantioselectivities (er >92:8) under the catalytic conditions. PMID:21732609

  5. [Cu(dap)2Cl] as an efficient visible-light-driven photoredox catalyst in carbon-carbon bond-forming reactions.

    PubMed

    Pirtsch, Michael; Paria, Suva; Matsuno, Taisuke; Isobe, Hiroyuki; Reiser, Oliver

    2012-06-11

    Copper sees the light of day: [Cu(dap)(2)Cl] proved to be an excellent photoredox catalyst for atom-transfer radical addition reactions, as well as for allylation reactions (see scheme), providing an attractive alternative to commonly used iridium- and ruthenium-based catalysts.

  6. HETERODIMERIZATION OF PROPYLENE AND VINYLARENES: FUNCTIONAL GROUP COMPATIBILITY IN A HIGHLY EFFICIENT NI-CATALYZED CARBON-CARBON BOND-FORMING REACTION. (R826120)

    EPA Science Inventory

    Abstract

    Unlike heterodimerization reactions of ethylene and vinylarenes, no such synthetically useful reactions using propylene are known. We find that propylene reacts with various vinylarenes in the presence of catalytic amounts of [(allyl)NiBr]2, triphen...

  7. Stable walking with asymmetric legs.

    PubMed

    Merker, Andreas; Rummel, Juergen; Seyfarth, Andre

    2011-12-01

    Asymmetric leg function is often an undesired side-effect in artificial legged systems and may reflect functional deficits or variations in the mechanical construction. It can also be found in legged locomotion in humans and animals such as after an accident or in specific gait patterns. So far, it is not clear to what extent differences in the leg function of contralateral limbs can be tolerated during walking or running. Here, we address this issue using a bipedal spring-mass model for simulating walking with compliant legs. With the help of the model, we show that considerable differences between contralateral legs can be tolerated and may even provide advantages to the robustness of the system dynamics. A better understanding of the mechanisms and potential benefits of asymmetric leg operation may help to guide the development of artificial limbs or the design novel therapeutic concepts and rehabilitation strategies.

  8. Electron jet of asymmetric reconnection

    NASA Astrophysics Data System (ADS)

    Khotyaintsev, Yu. V.; Graham, D. B.; Norgren, C.; Eriksson, E.; Li, W.; Johlander, A.; Vaivads, A.; André, M.; Pritchett, P. L.; Retinò, A.; Phan, T. D.; Ergun, R. E.; Goodrich, K.; Lindqvist, P.-A.; Marklund, G. T.; Le Contel, O.; Plaschke, F.; Magnes, W.; Strangeway, R. J.; Russell, C. T.; Vaith, H.; Argall, M. R.; Kletzing, C. A.; Nakamura, R.; Torbert, R. B.; Paterson, W. R.; Gershman, D. J.; Dorelli, J. C.; Avanov, L. A.; Lavraud, B.; Saito, Y.; Giles, B. L.; Pollock, C. J.; Turner, D. L.; Blake, J. D.; Fennell, J. F.; Jaynes, A.; Mauk, B. H.; Burch, J. L.

    2016-06-01

    We present Magnetospheric Multiscale observations of an electron-scale current sheet and electron outflow jet for asymmetric reconnection with guide field at the subsolar magnetopause. The electron jet observed within the reconnection region has an electron Mach number of 0.35 and is associated with electron agyrotropy. The jet is unstable to an electrostatic instability which generates intense waves with E∥ amplitudes reaching up to 300 mV m-1 and potentials up to 20% of the electron thermal energy. We see evidence of interaction between the waves and the electron beam, leading to quick thermalization of the beam and stabilization of the instability. The wave phase speed is comparable to the ion thermal speed, suggesting that the instability is of Buneman type, and therefore introduces electron-ion drag and leads to braking of the electron flow. Our observations demonstrate that electrostatic turbulence plays an important role in the electron-scale physics of asymmetric reconnection.

  9. Time-asymmetric structure of gravitational radiation

    NASA Astrophysics Data System (ADS)

    Blanchet, Luc

    1993-05-01

    Gravitational radiation reaction effects in the dynamics of an isolated system arise from the use of retarded potentials for the radiation field, satisfying time-asymmetric boundary conditions imposed at past-null infinity. Part one of this paper investigates the ``antisymmetric'' component, a solution of the wave equation of the type retarded minus advanced, of the linearized gravitational field generated by an isolated system in the exterior region of the system. At linearized order such a component is well defined and is ``time odd'' in the usual post-Newtonian (PN) sense. We introduce a new linearized coordinate system which generalizes the Burke and Thorne coordinate system both in its space-time domain of validity, which is no longer limited to the near zone of the source, and in the post-Newtonian smallness of the linear antisymmetric (``time-odd'') component of the metric, for all multipolarities of antisymmetric waves. These waves (as viewed in the near zone) define a generalized radiation reaction four-tensor potential Vαβreact of the linear theory. At the 2.5 post-Newtonian approximation, the tensor potential reduces to the standard Burke-Thorne scalar potential of the lowest-order local radiation reaction force. At the 3.5 PN approximation, the potential involves scalar (V00react) and vector (V0ireact) components which are associated with subdominant radiation reaction effects such as the recoil effect. At the higher-order PN approximations, the potential is intrinsically tensorial. A nonlinear exterior metric is iteratively constructed from the new linearized metric by the method of a previous work. Part two of this paper is devoted to the near-zone reexpansion of the nonlinear iterations of the exterior metric. We use a very convenient decomposition of the integral of the retarded potentials into a particular solution involving only ``instantaneous'' potentials, and a homogeneous solution of the antisymmetric type. The former particular solution is

  10. Deformation of an asymmetric film

    NASA Astrophysics Data System (ADS)

    Geng, Jun; Selinger, Jonathan

    2010-03-01

    Recent experiments have investigated shape changes of polymer films induced by asymmetric swelling by a chemical vapor. Inspired by recent work on the shaping of elastic sheets by non-Euclidean metrics [1,2], we represent the effect of chemical vapors by a change in the target metric tensor. In this problem, unlike Refs. [1,2], the target metric is asymmetric between the two sides of the film. Changing this metric induces a curvature of the film, which may be Gaussian curvature into a sphere or mean curvature into a cylinder. We calculate the elastic energy for each of these shapes, and show that the sphere is favored for films smaller than a critical size, which depends on the film thickness, while the cylinder is favored for larger films. We compare the formalism for asymmetric films with previous theoretical work on symmetric films, and compare the predictions with experimental results. [4pt] [1] Y. Klein, E. Efrati, and E. Sharon, Science 315, 1116 (2007).[0pt] [2] E. Efrati, E. Sharon, and R. Kupferman, J. Mech. Phys. Solids 57, 762 (2009).

  11. Polyimides Derived from Novel Asymmetric Benzophenone Dianhydrides

    NASA Technical Reports Server (NTRS)

    Chuang, Chun-Hua (Inventor)

    2015-01-01

    This invention relates to the composition and processes for preparing thermoset polyimides derived from an asymmetric dianhydride, namely 2,3,3',4'-benzophenone dianhydride (a-BTDA) with at least one diamine, and a monofunctional terminal endcaps. The monofunctional terminating groups include 4-phenylethynylphthalic anhydride ester-acid derivatives, phenylethyl trimellitic anhydride (PETA) and its ester derivatives as well as 3-phenylethynylaniline. The process of polyimide composite comprises impregnating monomer reactants of dianhydride or its ester-acid derivatives, diamine and with monofunctional reactive endcaps into glass, carbon, quartz or synthetic fibers and fabrics, and then stack up into laminates and subsequently heated to between 150-375.degree. C. either at atmosphere or under pressure to promote the curing and crosslinking of the reactive endcaps to form a network of thermoset polyimides.

  12. A Simple Modeling of Asymmetric Rolling

    NASA Astrophysics Data System (ADS)

    Halloumi, A.; Desrayaud, Ch.; Montheillet, F.

    2010-06-01

    Two complementary analytical approaches and the finite difference method are proposed for modeling asymmetric rolling (ASR) of metal sheet. The first analytical model is an upper bound method based on a uniform strain field depending on one single optimization parameter, viz. the entry velocity of the sheet. Its results can be straightforwardly used for practical applications. The second model uses a more refined analytical velocity field based on the classical parabolic estimation of the material flow lines in rolling. It involves an additional optimization parameter associated with the precise form of the velocity field. Local values of strain, strain rate and self-heating temperature are easily calculated, as well as the rolling force. Finally, the finite difference method is applied to compute heat transfers between the rolls and the sheet. In conclusion, the respective advantages of the three methods are discussed.

  13. Dynamics of Complex-Forming Bimolecular Reactions: A Comparative Theoretical Study of the Reactions of H Atoms with O2((3)Σg(-)) and O2((1)Δg).

    PubMed

    Szabó, Péter; Lendvay, György

    2015-12-17

    The atomic-level mechanism of the reaction of H atoms with triplet and singlet molecular oxygen, H((2)S) + O2((3)Σg(-)) → O((3)P) + OH((2)Πg) ( R1 ) and H((2)S) + O2((1)Δg) → O((3)P) + OH((2)Πg) ( R2 ) is analyzed in terms of the topology of the potential energy surfaces (PES) of the two reactions. Both PES exhibit a deep potential well corresponding to the ground and first excited electronic state of HO2. The ground-state reaction is endothermic with no barrier on either side of the well; the excited-state reaction is exothermic with a barrier in the entrance valley of the PES. The differences of the PES are manifested in properties such as the excitation functions, which show reaction R1 to be much slower and the effect of rotational excitation on reactivity, which speeds up reaction R1 and has little effect on R2 . Numerous common dynamics features arise from the presence of the deep potential well on the PES. Such are the significant role of isomerization (for example, 90% of reactive collisions in R2 involve at least one H atom transfer from one of the O atoms to the other in reaction R2 ), which is shown to give rise to a significant rotational excitation of the product OH radicals. Common is the significant sideways scattering of the products that originates from collisions in propeller-type arrangements induced by the presence of two bands of acceptance around the O2 molecule. The HO2 complex in both reactions proves to behave nonstatistically, with signatures of the dynamics in lifetime distributions, angular distributions, opacity functions, and product quantum-state distributions. PMID:26517427

  14. Special forms in twin pregnancy - asymmetric conjoined twins.

    PubMed

    Anca, F A; Negru, A; Mihart, A E; Grigoriu, C; Bohîlțea, R E

    2015-01-01

    Twin pregnancies generally represent a high-risk pregnancy. However, monozygous twins are real challenges for obstetricians due to the complications that may occur. Among the particular cases of monozygous twins in the University Emergency Hospital of Bucharest, Department of Obstetrics and Gynecology, a monochorial monoamniotic pregnancy with conjoined twins has been described. These particular medical circumstances require a deeper understanding of the vascular anatomical particularities. An accurate diagnosis implies a most detailed description of the morphological dynamics of the fetuses with the study of the impact of the vascular anomaly on their development so that the maximum chances of survival and the best outcome for the viable fetus can be obtained. The diagnosis of the most frequently associated anomalies is also extremely important. PMID:26361519

  15. Bimolecular Coupling Reactions through Oxidatively Generated Aromatic Cations: Scope and Stereocontrol

    PubMed Central

    Cui, Yubo; Villafane, Louis A.; Clausen, Dane J.

    2013-01-01

    Chromenes, isochromenes, and benzoxathioles react with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to form stable aromatic cations that react with a range of nucleophiles. These oxidative fragment coupling reactions provide rapid access to structurally diverse heterocycles. Conducting the reactions in the presence of a chiral Brønsted acid results in the formation of an asymmetric ion pair that can provide enantiomerically enriched products in a rare example of a stereoselective process resulting from the generation of a chiral electrophile through oxidative carbon–hydrogen bond cleavage. PMID:23913987

  16. Characterization of Metastable Intermediates Formed in the Reaction Between a Mn(II) Complex and Dioxygen, Including a Crystallographic Structure of a Binuclear Mn(III)-Peroxo Species

    PubMed Central

    Coggins, Michael K.; Sun, Xianru; Kwak, Yeonju; Solomon, Edward I.; Rybak-Akimova, Elena; Kovacs, Julie A.

    2013-01-01

    Transition-metal peroxos have been implicated as key intermediates in a variety of critical biological processes involving O2. Due to their highly reactive nature, very few metal-peroxos have been characterized. The dioxygen chemistry of manganese remains largely unexplored despite the proposed involvement of a binuclear Mn-peroxo, either as a precursor to O2, or derived from O2, in both photosynthetic H2O oxidation and DNA biosynthesis, arguably two of the most fundamental processes of life. Neither of these biological intermediates has been observed. Herein we describe the dioxygen chemistry of coordinatively unsaturated [MnII(SMe2N4(6-MeDPEN))] +(1), and the characterization of intermediates formed en route to a binuclear mono-oxo bridged Mn(III) product {[MnIII(SMe2N4(6-MeDPEN)]2-(μ-O)}2+ (2), the oxo atom of which is derived from 18O2. At low-temperatures, a dioxygen intermediate, [Mn(SMe2N4(6-MeDPEN))(O2)]+ (4), is observed (by stopped-flow) to rapidly and irreversibly form in this reaction (k1(−10 °C)= 3780±180M−1s−1, ΔH1‡ = 26.4±1.7 kJ mol−1, ΔS1‡ = − 75.6±6.8 J mol−1K−1), and then convert more slowly (k2(−10 °C)= 417±3.2 M−1s−1, ΔH2‡ = 47.1±1.4 kJ mol−1, ΔS2‡ = − 15.0±5.7 J mol−1K−1) to a species 3 with isotopically sensitive stretches at νo-o (Δ18O) = 819(47) cm−1, kO–O= 3.02 mdyn/Å, and νMn-O(Δ18O) = 611(25) cm−1 consistent with a peroxo. Intermediate 3 releases approximately 0.5 equiv of H2O2 per Mn ion upon protonation, and the rate of conversion of 4 to 3 is dependent on [Mn(II)] concentration, consistent with the formation of a binuclear Mn-peroxo. This was verified by X-ray crystallography, where the peroxo of {[MnIII(SMe2N4(6-Me-DPEN)]2(trans–μ–1,2–O2)}2+ (3) is shown to be bridging between two Mn(III) ions in an end-on trans-μ-1,2-fashion. This represents the first characterized example of a binuclear Mn(III)-peroxo, and a rare case in which more than one intermediate is observed

  17. Recent Developments in the Catalytic, Asymmetric Construction of Pyrroloindolines Bearing All-Carbon Quaternary Stereocenters

    PubMed Central

    Repka, Lindsay M.; Reisman, Sarah E.

    2014-01-01

    Pyrroloindoline alkaloids constitute a large family of natural products that has inspired the development of an impressive array of new reactions to prepare the key heterocyclic motif. This synopsis will address catalytic, asymmetric reactions developed to synthesize pyrroloindolines bearing C3a all-carbon quaternary stereocenters. The methods described herein include both transition metal-catalyzed and organocatalyzed reactions that have been demonstrated suitable for the synthesis of the pyrroloindoline framework. PMID:24295135

  18. Coordinating Chiral Ionic Liquids: Design, Synthesis, and Application in Asymmetric Transfer Hydrogenation under Aqueous Conditions

    PubMed Central

    Vasiloiu, Maria; Gaertner, Peter; Zirbs, Ronald; Bica, Katharina

    2015-01-01

    Hydrophilic coordinating chiral ionic liquids with an amino alcohol substructure were developed and efficiently applied to the asymmetric reduction of ketones. Their careful design and adaptability to the desired reaction conditions allow for these chiral ionic liquids to be used as the sole source of chirality in a ruthenium-catalyzed transfer hydrogenation reaction of aromatic ketones. When used in this reaction system, these chiral ionic liquids afforded excellent yields and high enantioselectivities. PMID:26279638

  19. Transition State Models for Understanding the Origin of Chiral Induction in Asymmetric Catalysis.

    PubMed

    Sunoj, Raghavan B

    2016-05-17

    In asymmetric catalysis, a chiral catalyst bearing chiral center(s) is employed to impart chirality to developing stereogenic center(s). A rich and diverse set of chiral catalysts is now available in the repertoire of synthetic organic chemistry. The most recent trends point to the emergence of axially chiral catalysts based on binaphthyl motifs, in particular, BINOL-derived phosphoric acids and phosphoramidites. More fascinating ideas took shape in the form of cooperative multicatalysis wherein organo- and transition-metal catalysts are made to work in concert. At the heart of all such manifestations of asymmetric catalysis, classical or contemporary, is the stereodetermining transition state, which holds a perennial control over the stereochemical outcome of the catalytic process. Delving one step deeper, one would find that the origin of the stereoselectivity is delicately dependent on the relative stabilization of one transition state, responsible for the formation of the predominant stereoisomer, over the other transition state for the minor stereoisomer. The most frequently used working hypothesis to rationalize the experimentally observed stereoselectivity places an undue emphasis on steric factors and tends to regard the same as the origin of facial discrimination between the prochiral faces of the reacting partners. In light of the increasing number of asymmetric catalysts that rely on hydrogen bonding as well as other weak non-covalent interactions, it is important to take cognizance of the involvement of such interactions in the sterocontrolling transition states. Modern density functional theories offer a pragmatic and effective way to capture non-covalent interactions in transition states. Aided by the availability of such improved computational tools, it is quite timely that the molecular origin of stereoselectivity is subjected to more intelligible analysis. In this Account, we describe interesting molecular insights into the stereocontrolling

  20. Asymmetric Synthesis of the Aminocyclitol Pactamycin, a Universal Translocation Inhibitor

    PubMed Central

    Sharpe, Robert J.; Malinowski, Justin T.; Johnson, Jeffrey S.

    2014-01-01

    An asymmetric total synthesis of the aminocyclopentitol pactamycin is described, which delivers the title compound in 15 steps from 2,4-pentanedione. Critical to this approach was the exploitation of a complex symmetry-breaking reduction strategy to assemble the C1, C2, and C7 relative stereochemistry within the first four steps of the synthesis. Multiple iterations of this reduction strategy are described, and a thorough analysis of stereochemical outcomes is detailed. In the final case, an asymmetric Mannich reaction was developed to install a protected amine directly at the C2 position. Symmetry-breaking reduction of this material gave way to a remarkable series of stereochemical outcomes leading to the title compound without recourse to non-strategic downstream manipulations. This synthesis is immediately accommodating to the facile preparation of structural analogs. PMID:24245656

  1. An eight-dimensional quantum mechanical Hamiltonian for X + YCZ3 system and its applications to H + CH4 reaction

    NASA Astrophysics Data System (ADS)

    Liu, Rui; Xiong, Hongwei; Yang, Minghui

    2012-11-01

    An eight-dimensional quantum mechanical Hamiltonian has been proposed based on Palma and Clary's model in which the non-reacting CZ3 group keeps a C3v symmetry in the X + YCZ3 ↔ XY + CZ3 reaction J. Palma and D. C. Clary [J. Chem. Phys. 112, 1859 (2000), 10.1063/1.480749]. By transforming the original Cartesian coordinate system (x, s) into a scaled polar coordinate system (q, γ), the vibrational Hamiltonian of CZ3 group is expressed in a simple form with a clear physical picture. This Hamiltonian is used to investigate the H + CH4 → H2 + CH3 reaction on the Jordan-Gilbert potential energy surface. The total reaction probabilities are calculated for the initial ground state, and umbrella, bending, symmetric, and asymmetric stretching excited states of CH4 with total angular momentum J = 0. The integral cross sections for the reaction are also studied for these initial vibrational states with a centrifugal-sudden approximation. The total integral cross sections for the asymmetric stretching vibrational excited state are in good agreement with the experimental observations. The results also showed the difference of dynamical behavior between reactions from symmetric and asymmetric stretching excited states. The thermal rate constants are calculated for the temperature range T = 250-2000 K and compared with the experimental and other theoretical results.

  2. Developing novel organocatalyzed aldol reactions for the enantioselective synthesis of biologically active molecules

    PubMed Central

    Bhanushali, Mayur; Zhao, Cong-Gui

    2011-01-01

    Aldol reaction is one of the most important methods for the formation of carbon-carbon bonds. Because of its significance and usefulness, asymmetric versions of this reaction have been realized with different approaches in the past. Over the last decade, the area of organocatalysis has made significant progresses. As one of most studied reactions in organocatalyses, organocatalyzed aldol reaction has emerged as a powerful tool for the synthesis of a large number of useful products in optically enriched forms. In this review, we summarize our efforts on the development of novel organocatalyzed aldol reactions for the enantioselective synthesis of biological active molecules. Literatures closely related to our studies are also covered. PMID:21918584

  3. Design and fabrication of asymmetric nanopores using pulsed PECVD

    NASA Astrophysics Data System (ADS)

    Kelkar, Sanket S.

    Manipulating matter at nanometric length scales is important for many electronic, chemical and biological applications. Structures such as nanopores demonstrate a phenomenon known as hindered transport which can be exploited in analytical applications such as DNA sequencing, ionic transistors, and molecular sieving. Precisely controlling the size, geometry and surface characteristics of the nanopores is important for realizing these applications. In this work, we employ relatively large template structures (˜ 100 nm) produced by track-etching or electron beam lithography. The pore size is then reduced to the desired level by deposition of material using pulsed plasma enhanced chemical vapor deposition (PECVD). Pulsed PECVD has been developed as a high throughput alternative to atomic layer deposition (ALD) to deliver self-limiting growth of thin films. The goal of this thesis is to extend the application of pulsed PECVD to fabricate asymmetric nanopores. In contrast to ALD, pulsed PECVD does not result in perfectly conformal deposition profiles, and predicting the final nanostructure is more complicated. A two dimensional feature scale model was developed to predict film profile evolution. The model was built in COMSOL, and is based on a diffusion reaction framework with a spatially varying Knudsen diffusion coefficient to account for the molecular transport inside the features. A scaling analysis was used to account for ALD exposure limitations that commonly occur when coating these extremely high aspect ratio features. The model was verified by cross-section microscopy of deposition profiles on patterned cylinders and trenches. The model shows that it is possible to obtain unique nanopore morphologies in pulsed PECVD that are distinct from either steady state deposition processes such as physical vapor deposition (PVD) or conventional ALD. Polymeric track etched (TE) membrane supports with a nominal size of 100 nm were employed as model template structures to

  4. Asymmetric Schiff bases derived from diaminomaleonitrile and their metal complexes

    NASA Astrophysics Data System (ADS)

    Yang, Jianjie; Shi, Rufei; Zhou, Pei; Qiu, Qiming; Li, Hui

    2016-02-01

    Asymmetric Schiff bases, due to its asymmetric structure, can be used as asymmetric catalyst, antibacterial, and mimic molecules during simulate biological processes, etc. In recent years, research on synthesis and properties of asymmetric Schiff bases have become an increase interest of chemists. This review summarizes asymmetric Schiff bases derived from diaminomaleonitrile (DAMN) and DAMN-based asymmetric Schiff bases metal complexes. Applications of DAMN-based asymmetric Schiff bases are also discussed in this review.

  5. LG tools for asymmetric wargaming

    NASA Astrophysics Data System (ADS)

    Stilman, Boris; Yakhnis, Alex; Yakhnis, Vladimir

    2002-07-01

    Asymmetric operations represent conflict where one of the sides would apply military power to influence the political and civil environment, to facilitate diplomacy, and to interrupt specified illegal activities. This is a special type of conflict where the participants do not initiate full-scale war. Instead, the sides may be engaged in a limited open conflict or one or several sides may covertly engage another side using unconventional or less conventional methods of engagement. They may include peace operations, combating terrorism, counterdrug operations, arms control, support of insurgencies or counterinsurgencies, show of force. An asymmetric conflict can be represented as several concurrent interlinked games of various kinds: military, transportation, economic, political, etc. Thus, various actions of peace violators, terrorists, drug traffickers, etc., can be expressed via moves in different interlinked games. LG tools allow us to fully capture the specificity of asymmetric conflicts employing the major LG concept of hypergame. Hypergame allows modeling concurrent interlinked processes taking place in geographically remote locations at different levels of resolution and time scale. For example, it allows us to model an antiterrorist operation taking place simultaneously in a number of countries around the globe and involving wide range of entities from individuals to combat units to governments. Additionally, LG allows us to model all sides of the conflict at their level of sophistication. Intelligent stakeholders are represented by means of LG generated intelligent strategies. TO generate those strategies, in addition to its own mathematical intelligence, the LG algorithm may incorporate the intelligence of the top-level experts in the respective problem domains. LG models the individual differences between intelligent stakeholders. The LG tools make it possible to incorporate most of the known traits of a stakeholder, i.e., real personalities involved in

  6. Asymmetric Formal Synthesis of Azadirachtin.

    PubMed

    Mori, Naoki; Kitahara, Takeshi; Mori, Kenji; Watanabe, Hidenori

    2015-12-01

    An asymmetric formal synthesis of azadirachtin, a potent insect antifeedant, was accomplished in 30 steps to Ley's synthetic intermediate (longest linear sequence). The synthesis features: 1) rapid access to the optically active right-hand segment starting from the known 5-hydroxymethyl-2-cyclopentenone scaffold; 2) construction of the B and E rings by a key intramolecular tandem radical cyclization; 3) formation of the hemiacetal moiety in the C ring through the α-oxidation of the six-membered lactone followed by methanolysis. PMID:26474211

  7. Polyimides Derived from Novel Asymmetric Dianhydrides

    NASA Technical Reports Server (NTRS)

    Chuang, Chun-Hua (Inventor)

    2012-01-01

    This invention relates to the compositions and processes for preparing thermoset and thermoplastic polyimides derived from novel asymmetrical dianhydrides: specifically 2,3,3',4' benzophenone dianhydride (a-BTDA), and 3,4'-(hexafluoroisopropylidene)diphthalic anhydride (a-6FDA). The a-BTDA anhydride is prepared by Suzuki coupling with catalysts from a mixed anhydride of 3,4-dimethylbenzoic acid or 2,3-dimethylbenzoic acid with 2,3-dimethylphenylboronic acid or 3,4-dimethylphenylboronic acid respectively, to form 2,3,3',4'-tetramethylbenzophenone which is oxidized to form 2,3,3',4'-benzophenonetetracarboxylic acid followed by cyclodehydration to obtain a-BTDA. The a-6FDA is prepared by nucleophilic triflouoromethylation of 2,3,3',4'-tetramethylbenzophenone with trifluoromethyltrimethylsilane to form 3,4'-(trifluoromethylmethanol)-bis(o-xylene) which is converted to 3,4'-(hexafluoroisopropylidene-bis(o-xylene). The 3,4'-(hexafluoroisopropylidene)-bis(o-xylene) is oxidized to the corresponding tetraacid followed by cyclodehydration to yield a-6FDA.

  8. Rate constants for the reaction of NO and HO 2 with peroxy radicals formed from the reaction of OH, Cl or NO 3 with alkenes, dienes and α, β-unsaturated carbonyls

    NASA Astrophysics Data System (ADS)

    King, Martin D.; Thompson, Katherine C.

    Rate constants for the gas-phase reaction of NO and HO 2 radicals with 33 peroxy radicals are presented. The peroxy radicals are derived from the addition of either OH, Cl, or NO 3 radicals, followed by addition of O 2, to a series of alkenes: tetrachloroethene, ethene, 2,3-dimethyl but-2-ene, butadiene, 2,3,4,5-tetramethyl hexa-2,4-diene, 1,1,2,3,4,4-hexachlorobutadiene, but-1-ene-3-one (methyl vinyl ketone) and 2,3-dimethylpen-2-ene-4-one. The rate constants were predicted using a correlation between the singly occupied molecular orbital (SOMO) energy of the peroxy radical and the logarithm of the rate constant for reaction with NO or HO 2. A discussion of the accuracy of the method and the trends in the reactivity of the titled peroxy radicals is given. Peroxy radicals derived from halogenated alkenes have larger values of rate constants for reaction with NO relative to reaction with HO 2, indicating that they are more likely to react with NO, rather than HO 2, in the atmosphere. The reverse is true for peroxy radicals derived from alkylated alkenes.

  9. Crystal structure of a nucleoside model for the inter­strand cross-link formed by the reaction of 2′-de­oxy­guanosine and an abasic site in duplex DNA

    PubMed Central

    Catalano, Michael J.; Ruddraraju, Kasi Viswanatharaju; Barnes, Charles L.; Gates, Kent S.

    2016-01-01

    The title compound, 9-[(2R,4S,5R)-4-hy­droxy-5-(hy­droxy­meth­yl)tetra­hydro­furan-2-yl]-2-{[(2R,4S,5R)-4-meth­oxy-5-(meth­oxy­meth­yl)tetra­hydro­furan-2-yl]amino}-1H-purin-6(9H)-one, C17H25N5O7, crystallizes with two independent mol­ecules (A and B) in the asymmetric unit. In the crystal, the guanosine moieties of mol­ecules A and B are linked by N—H⋯N and O—H⋯N hydrogen-bonding inter­actions, forming ribbons which are stacked to form columns along [100]. These columns are then linked by O—H⋯O hydrogen bonds between the ribose moieties and numerous C—H⋯O inter­actions to complete the three-dimensional structure. PMID:27308004

  10. Columnar structures from asymmetrically tapered biphenylamide.

    PubMed

    Park, Soo-Jin; Hwang, Seok-Ho; Kim, Namil; Kuo, Shiao-Wei; Kim, Hak Yong; Park, Seul-Ki; Kim, Young-Jin; Nah, Changwoon; Lee, Joong Hee; Jeong, Kwang-Un

    2009-10-15

    An asymmetrically tapered N,N'-tris[[(2-dodecylaminocarbonyl)ethyl]methyl]-4-biphenylamide (asym-C(12)PhA, where n is the number of carbon atoms in the alkyl chains, n = 12) was newly designed and synthesized. In this asymmetrically tapered asym-C(12)PhA biphenylamide, H-bondable hydrophilic amide moieties are located at between a rigid hydrophobic biphenyl rod and three flexible hydrophobic alkyl chains. Computer energy minimization indicated that three-dimensional (3D) geometry of asym-C(12)PhA biphenylamide looks like a cone with dimensions of 3.01 nm in height and 1.44 nm in bottom radius. Phase transitions and supra-molecular structures were identified utilizing the combined techniques of differential scanning calorimetry, 1D wide-angle X-ray diffraction (1D WAXD), Fourier-transform infrared spectroscopy, and solid-state (13)C nuclear magnetic resonance analyses. The asym-C(12)PhA self-assembled into a highly ordered columnar mesophase just below the isotropization temperature and then transformed to 3D columnar crystalline phase (Phi(Cr)) on further cooling. Selected area electron diffractions in transmission electron microscopy (TEM) along with 1D WAXD and cross-polarized optical microscopy suggested that discotic building blocks were constructed by rotating 120 degrees of three asym-C(12)PhA with respect to neighboring ones and the tmb (top-middle-bottom) stacked discotic building blocks further self-organized into columns. These columns are laterally intercalated to form the Phi(Cr) phase. On the basis of the TEM image and polyethylene surface decoration technology, it was identified that the self-assembled asym-C(12)PhA fibers with approximately 1 mum in diameter and several millimeters in length were braids of tiny single crystals.

  11. Asymmetric angular dependence of domain wall motion in magnetic nanowires.

    PubMed

    Nam, Chunghee

    2013-03-01

    An angular dependence of domain wall (DW) motion is studied in a magnetic wire consisting of a giant-magnetoresistance spin-valve. A DW pinning site is formed by a single notch, where a conventional linear one and a specially designed tilted one are compared. The asymmetric angular dependence was found in the DW depinning behavior with the tilted notch. The geometry control of the pinning site can be useful for DW diode devices using a rotating magnetic field. PMID:23755619

  12. Mechanism for Forming B,C,N,O Rings from NH3BH3 and CO2 via Reaction Discovery Computations.

    PubMed

    Li, Maxwell W; Pendleton, Ian M; Nett, Alex J; Zimmerman, Paul M

    2016-03-01

    This study employs computational reaction finding tools to probe the unique biphilic reactivity between ammonia-borane (AB) and CO2. The results show that sequential reactions involving multiple equivalents of AB and CO2 can lead to the formation of stable nonplanar B,C,N,O-heterocycles (Cy-BCN). Cy-BCN is shown to emerge through boron-oxygen bond formation, hydroboration, dative bond formation, and single- or double-hydrogen transfers. The most kinetically facile reactions (computed at the coupled cluster singles and doubles with perturbative triples (CCSD(T)) level of theory) result from polarized nitrogen-boron double bonds whereas thermodynamic stability results from formation of covalent boron-oxygen bonds. An important structure, HCOOBHNH2 (DHFAB), contains both of these features and is the key intermediate involved in generation of Cy-BCN. Crucially, it is shown that favorable boron-oxygen bond formation results in production of Cy-BCN species that are more stable than polyaminoboranes. These types of reaction intermediates could serve as building blocks in the formation of B,N-codoped graphene oxide (BCN). PMID:26844585

  13. THERMAL DESORPTION MASS SPECTROMETRIC ANALYSIS OF ORGANIC AEROSOL FORMED FROM REACTIONS OF 1-TETRADECENE AND O3 IN THE PRESENCE OF ALCOHOLS AND CARBOXYLIC ACIDS. (R826235)

    EPA Science Inventory

    The chemistry of secondary organic aerosol formation from reactions of
    1-tetradecene and O3 in dry air in the presence of excess alcohols
    and carboxylic acids was investigated in an environmental chamber using a
    thermal desorption particle beam mass spec...

  14. LC/MS/MS structure elucidation of reaction intermediates formed during the TiO2 photocatalysis of microcystin-LR

    EPA Science Inventory

    Microcystin-LR (MC-LR), a cyanotoxin and emerging drinking water contaminant, was treated with TiO(2) photocatalysts immobilized on stainless steel plates as an alternative to nanoparticles in slurry. The reaction intermediates of MC-LR were identified with mass spectrometry (MS)...

  15. Migration in asymmetric, random environments

    NASA Astrophysics Data System (ADS)

    Deem, Michael; Wang, Dong

    Migration is a key mechanism for expansion of communities. As a population migrates, it experiences a changing environment. In heterogeneous environments, rapid adaption is key to the evolutionary success of the population. In the case of human migration, environmental heterogeneity is naturally asymmetric in the North-South and East-West directions. We here consider migration in random, asymmetric, modularly correlated environments. Knowledge about the environment determines the fitness of each individual. We find that the speed of migration is proportional to the inverse of environmental change, and in particular we find that North-South migration rates are lower than East-West migration rates. Fast communication within the population of pieces of knowledge between individuals, similar to horizontal gene transfer in genetic systems, can help to spread beneficial knowledge among individuals. We show that increased modularity of the relation between knowledge and fitness enhances the rate of evolution. We investigate the relation between optimal information exchange rate and modularity of the dependence of fitness on knowledge. These results for the dependence of migration rate on heterogeneity, asymmetry, and modularity are consistent with existing archaeological facts.

  16. Asymmetric Laguerre-Gaussian beams

    NASA Astrophysics Data System (ADS)

    Kovalev, A. A.; Kotlyar, V. V.; Porfirev, A. P.

    2016-06-01

    We introduce a family of asymmetric Laguerre-Gaussian (aLG) laser beams. The beams have been derived via a complex-valued shift of conventional LG beams in the Cartesian plane. While propagating in a uniform medium, the first bright ring of the aLG beam becomes less asymmetric and the energy is redistributed toward peripheral diffraction rings. The projection of the orbital angular momentum (OAM) onto the optical axis is calculated. The OAM is shown to grow quadratically with increasing asymmetry parameter of the aLG beam, which equals the ratio of the shift to the waist radius. Conditions for the OAM becoming equal to the topological charge have been derived. For aLG beams with zero radial index, we have deduced an expression to define the intensity maximum coordinates and shown the crescent-shaped intensity pattern to rotate during propagation. Results of the experimental generation and rotation of aLG beams agree well with theoretical predictions.

  17. Excitons in asymmetric quantum wells

    NASA Astrophysics Data System (ADS)

    Grigoryev, P. S.; Kurdyubov, A. S.; Kuznetsova, M. S.; Ignatiev, I. V.; Efimov, Yu. P.; Eliseev, S. A.; Petrov, V. V.; Lovtcius, V. A.; Shapochkin, P. Yu.

    2016-09-01

    Resonance dielectric response of excitons is studied for the high-quality InGaAs/GaAs heterostructures with wide asymmetric quantum wells (QWs). To highlight effects of the QW asymmetry, we have grown and studied several heterostructures with nominally square QWs as well as with triangle-like QWs. Several quantum confined exciton states are experimentally observed as narrow exciton resonances. A standard approach for the phenomenological analysis of the profiles is generalized by introducing different phase shifts for the light waves reflected from the QWs at different exciton resonances. Good agreement of the phenomenological fit to the experimentally observed exciton spectra for high-quality structures allowed us to reliably obtain parameters of the exciton resonances: the exciton transition energies, the radiative broadenings, and the phase shifts. A direct numerical solution of the Schrödinger equation for the heavy-hole excitons in asymmetric QWs is used for microscopic modeling of the exciton resonances. Remarkable agreement with the experiment is achieved when the effect of indium segregation is taken into account. The segregation results in a modification of the potential profile, in particular, in an asymmetry of the nominally square QWs.

  18. Intramolecular coupling of eta/sup 2/-iminoacyl groups at group 4 metal centers: a kinetic study of the carbon-carbon double-bond-forming reaction

    SciTech Connect

    Durfee, L.D.; McMullen, A.K.; Rothwell, I.P.

    1988-03-02

    The series of bis(eta/sup 2/-iminoacyl) compounds of general formula M(OAr)/sub 2/(eta/sup 2/-R'NCR)/sub 2/ (M = Ti, Zr, Hf; OAr = 2,6-diisopropyl- and 2,6-di-tert-butylphenoxide; R = CH/sub 3/, CH/sub 2/Ph; R' = various substituted phenyls) undergo intramolecular coupling on thermolysis to produce the corresponding enediamide derivatives M(OAr)/sub 2/(R'NC(R) = C(R)NR'). A kinetic study of the reaction in hydrocarbon solvents has shown it to be first order. The reaction is metal dependent with the rate decreasing in the order Ti > Zr > Hf. The rate of the reaction is also dependent on the steric and electronic nature of the nitrogen substituent (R'). The use of the bulky aryl group 2,6-dimethylphenyl retards the reaction, while the use of various 3- and 4-substituted phenyls (3-F, 3-OMe, 4-OMe, 4-Cl, 4-NMe/sub 2/) shows the reaction to be accelerated by electron-withdrawing substituents. A sigma plot based on kinetic data obtained at 67/sup 0/C and 77/sup 0/C yielded rho values of 0.83 (R = 0.97) and 0.84 (R = 0.95), respectively. Both the steric and electronic dependence of the reactivity on the nitrogen substituents is discussed mechanistically and used to rationalize the much more facile intramolecular coupling observed for the related eta/sup 2/-acyl (eta/sup 2/-OCR) functionalities.

  19. Dynamics of fission and heavy ion reactions

    SciTech Connect

    Nix, J.R.; Sierk, A.J.

    1984-05-01

    Recent advances in a unified macroscopic-microscopic description of large-amplitude collective nuclear motion such as occurs in fission and heavy ion reactions are discussed. With the goal of finding observable quantities that depend upon the magnitude and mechanism of nuclear dissipation, one-body dissipation and two-body viscosity within the framework of a generalized Fokker-Planck equation for the time dependence of the distribution function in phase space of collective coordinates and momenta are considered. Proceeding in two separate directions, the generalized Hamilton equations of motion for the first moments of the distribution function with a new shape parametrization and other technical innovations are first solved. This yields the mean translational fission-fragment kinetic energy and mass of a third fragment that sometimes forms between the two end fragments, as well as the energy required for fusion in symmetric heavy-ion reactions and the mass transfer and capture cross section in asymmetric heavy-ion reactions. In a second direction, we specialize to an inverted-oscillator fission barrier and use Kramers' stationary solution to calculate the mean time from the saddle point to scission for a heavy-ion-induced fission reaction for which experimental information is becoming available. 25 references.

  20. Structural and preliminary molecular dynamics studies of the Rhodobacter sphaeroides reaction center and its mutant form L(M196)H + H(M202)L

    NASA Astrophysics Data System (ADS)

    Klyashtorny, V. G.; Fufina, T. Yu.; Vasilieva, L. G.; Shuvalov, V. A.; Gabdulkhakov, A. G.

    2014-07-01

    Pigment-protein interactions are responsible for the high efficiency of the light-energy transfer and conversion in photosynthesis. The reaction center (RC) from the purple bacterium Rhodobacter sphaeroides is the most convenient model for studying the mechanisms of primary processes of photosynthesis. Site-directed mutagenesis can be used to study the effect of the protein environment of electron-transfer cofactors on the optical properties, stability, pigment composition, and functional activity of RC. The preliminary analysis of RC was performed by computer simulation of the amino acid substitutions L(M196)H + H(M202)L at the pigment-protein interface and by estimating the stability of the threedimensional structure of the mutant RC by the molecular dynamics method. The doubly mutated reaction center was overexpressed, purified, and crystallized. The three-dimensional structure of this mutant was determined by X-ray crystallography and compared with the molecular dynamics model.