Sample records for asymmetric transfer hydrogenation

  1. Organocatalytic asymmetric transfer hydrogenation of imines

    NARCIS (Netherlands)

    de Vries, Johannes G.; Mrsic, Natasa; Mršić, Nataša


    The asymmetric organocatalytic transfer hydrogenation of imines can be accomplished in good yields with high enantioselectivities through the use of BINOL-derived phosphoric acids as catalysts and Hantzsch esters or benzothiazoles as the hydride source. The same method can also be applied to the

  2. Current Topics in the Asymmetric Transfer Hydrogenation of Imines

    Czech Academy of Sciences Publication Activity Database

    Januščák, J.; Václavík, Jiří; Šot, P.; Pecháček, J.; Vilhanová, B.; Kuzma, Marek; Kačer, P.


    Roč. 109, č. 7 (2015), s. 492-498 ISSN 0009-2770 R&D Projects: GA ČR GAP106/12/1276; GA MŠk(CZ) LO1509 Institutional support: RVO:61388971 Keywords : asymmetric transfer hydrogenation * ruthenium * isoquinoline Subject RIV: EE - Microbiology, Virology Impact factor: 0.279, year: 2015

  3. Catalytic Asymmetric Transfer Hydrogenation of Imines: Recent Advances. (United States)

    Foubelo, Francisco; Yus, Miguel


    In this review article recent developments in the asymmetric transfer hydrogenation of imines from 2008 up to today are presented. The main methodology involves either metal-catalyzed procedures in the presence of a chiral ligand or organocatalyzed technologies using a Hantzsch ester and a chiral BINOL-derived phosphoric acid. The most important procedures are collected, paying special attention to the application of this methodology in synthetic organic chemistry. Copyright © 2015 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Enantioselective synthesis of anti-β-hydroxy-α-amido esters by asymmetric transfer hydrogenation in emulsions. (United States)

    Seashore-Ludlow, Brinton; Villo, Piret; Somfai, Peter


    Herein, we present two methods for an asymmetric transfer hydrogenation through the dynamic kinetic resolution of α-amido-β-ketoesters. These procedures yield the corresponding anti-β-hydroxy-α-amido esters in good yields and with good diastereo- and enantioselectivities. First, the scope of the reduction of α-amido-β-ketoesters by using triethylammonium formate azeotrope is examined. Then, an emulsion technology with sodium formate is explored, which allows for broader substrate scope, faster reaction times, and lower catalyst loading. Furthermore, these reactions are operationally simple and can be set up in air. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Asymmetric Transfer Hydrogenation of Ketones with Modified Grubbs Metathesis Catalysts : On the Way to a Tandem Process

    NARCIS (Netherlands)

    Renom-Carrasco, Marc; Gajewski, Piotr; Pignataro, Luca; de Vries, Johannes G.; Piarulli, Umberto; Gennari, Cesare; Lefort, Laurent


    Herein, we report the successful transformation of a 1(st) generation Grubbs metathesis catalyst into an asymmetric transfer hydrogenation (ATH) catalyst. Upon addition of a chiral amine ligand, an alcohol and a base, the 1(st) generation Hoveyda-Grubbs catalyst (HG-I) was found to promote the

  6. Osmium pyme complexes for fast hydrogenation and asymmetric transfer hydrogenation of ketones. (United States)

    Baratta, Walter; Ballico, Maurizio; Del Zotto, Alessandro; Siega, Katia; Magnolia, Santo; Rigo, Pierluigi


    The osmium compound trans,cis-[OsCl2(PPh3)2(Pyme)] (1) (Pyme=1-(pyridin-2-yl)methanamine), obtained from [OsCl2(PPh3)3] and Pyme, thermally isomerizes to cis,cis-[OsCl2(PPh3)(2)(Pyme)] (2) in mesitylene at 150 degrees C. Reaction of [OsCl2(PPh3)3] with Ph2P(CH2)(4)PPh2 (dppb) and Pyme in mesitylene (150 degrees C, 4 h) leads to a mixture of trans-[OsCl2(dppb)(Pyme)] (3) and cis-[OsCl2(dppb)(Pyme)] (4) in about an 1:3 molar ratio. The complex trans-[OsCl2(dppb)(Pyet)] (5) (Pyet=2-(pyridin-2-yl)ethanamine) is formed by reaction of [OsCl2(PPh3)3] with dppb and Pyet in toluene at reflux. Compounds 1, 2, 5 and the mixture of isomers 3/4 efficiently catalyze the transfer hydrogenation (TH) of different ketones in refluxing 2-propanol and in the presence of NaOiPr (2.0 mol %). Interestingly, 3/4 has been proven to reduce different ketones (even bulky) by means of TH with a remarkably high turnover frequency (TOF up to 5.7 x 10(5) h(-1)) and at very low loading (0.05-0.001 mol %). The system 3/4 also efficiently catalyzes the hydrogenation of many ketones (H2, 5.0 atm) in ethanol with KOtBu (2.0 mol %) at 70 degrees C (TOF up to 1.5 x 10(4) h(-1)). The in-situ-generated catalysts prepared by the reaction of [OsCl2(PPh3)3] with Josiphos diphosphanes and (+/-)-1-alkyl-substituted Pyme ligands, promote the enantioselective TH of different ketones with 91-96 % ee (ee=enantiomeric excess) and with a TOF of up to 1.9 x 10(4) h(-1) at 60 degrees C.

  7. Hydrophilic pyrazine-based phosphane ligands: synthesis and application in asymmetric hydride transfer and H2-hydrogenation of acetophenone

    NARCIS (Netherlands)

    Nikishkin, N.; Huskens, Jurriaan; Verboom, Willem


    Pyrazine-based hydrophilic phosphanes are useful ligands for the ruthenium- and rhodium-catalyzed hydrogenations of acetophenone under hydride transfer and dihydrogen conditions. The effect of alcohol additives on the catalytic, enantioselective aqueous hydrogenation of acetophenone is examined with

  8. Enantioselective synthesis of aziridines using asymmetric transfer hydrogenation as a precursor for chiral derivatives used as bonding agent for rocket solid propellants

    Directory of Open Access Journals (Sweden)

    Aparecida M. Kawamoto


    Full Text Available A rapid, expedient and enantioselective method for the synthesis of beta-hydroxy amines and monosubstituted aziridines in up to 99% e.e., via asymmetric transfer hydrogenation of a-amino ketones and cyclisation through treatment with tosyl chloride and base, is described. (1R,2R-N-(para-toluenesulfonyl-1,2-ethylenediamine with formic acid has been utilised as a ligand for the Ruthenium (II catalysed enantioselective transfer hydrogenation of the ketones.The chiral 2-methyl aziridine, which is a potentially more efficient bonding agent for Rocket Solid Propellant has been successfully achieved.

  9. Asymmetric hydrogenation using monodentate phosphoramidite ligands

    NARCIS (Netherlands)

    Minnaard, Adriaan J.; Feringa, Ben L.; Lefort, Laurent; De Vries, Johannes G.


    Monodentate phosphoramidites are excellent ligands for Rh-catalyzed asymmetric hydrogenations of substituted olefins. Enantioselectivities between 95 and 99% were obtained in the asymmetric hydrogenation of protected alpha- and beta-dehydroamino acids and esters, itaconic acid and esters, aromatic

  10. Synthesis and use of an asymmetric transfer hydrogenation catalyst based on iron(II) for the synthesis of enantioenriched alcohols and amines. (United States)

    Zuo, Weiwei; Morris, Robert H


    The catalytic hydrogenation of prochiral ketones and imines is an advantageous approach to the synthesis of enantioenriched alcohols and amines, respectively, which are two classes of compounds that are highly prized in pharmaceutical, fragrance and flavoring chemistry. This hydrogenation reaction is generally carried out using ruthenium-based catalysts. Our group has developed an alternative synthetic route that is based on the environmentally friendlier iron-based catalysis. This protocol describes the three-part synthesis of trans-[amine(imine)diphosphine]chlorocarbonyliron(II) tetrafluoroborate templated by iron salts and starting from commercially available chemicals, which provides the precatalyst for the efficient asymmetric transfer hydrogenation of ketones and imines. The use of the enantiopure (S,S) catalyst to reduce prochiral ketones to the (R)-alcohol in good to excellent yields and enantioenrichment is also detailed, as well as the reduction to the amine in very high yield and enantiopurity of imines substituted at the nitrogen with the N-(diphenylphosphinoyl) group (-P(O)Ph2). Although the best ruthenium catalysts provide alcohols in higher enantiomeric excess (ee) than the iron complex catalyst used in this protocol, they do so on much longer time scales or at higher catalyst loadings. This protocol can be completed in 2 weeks.

  11. Asymmetric transfer hydrogenation of ketones in aqueous solution catalyzed by Rhodium(III) complexes with C2-symmetric fluorene-ligands containing chiral (1R,2R)-cyclohexane-1,2-diamine

    Energy Technology Data Exchange (ETDEWEB)

    Montalvo-Gonzalez, Ruben [Universidad Autonoma de Nayarit, Tepic, Nay (Mexico). Unidad Academica de Ciencias Quimico Biologicas y Farmaceuticas; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy, E-mail: somanatha@sundown.sdsu.ed [Instituto Tecnologico de Tijuana, B.C. (Mexico). Centro de Graduados e Investigacion


    Two C{sub 2}-symmetric bis(sulfonamide) ligands containing fluorene-chiral (1R, 2R)-cyclohexane-1,2-diamine were complexed to Rh{sup III}(Cp{sup *}) and used as catalyst to reduce aromatic ketones. The corresponding chiral secondary alcohols were obtained in 87-100% ee and 85-99% yield, under asymmetric transfer hydrogenation (ATH) conditions using aqueous sodium formate as the hydride source. With acetophenone, 94% ee and 86-97% yield was achieved with substrate/catalyst (S/C) ratio of 10,000. (author)

  12. Homogenous asymmetric hydrogenation: Recent trends and industrial applications. (United States)

    Palmer, Andreas M; Zanotti-Gerosa, Antonio


    Recent advances in the field of homogeneous asymmetric hydrogenation are presented in this review. An analysis of academic literature published in the past 2 years highlights significant advances in the asymmetric hydrogenation of functional groups that previously were considered difficult to hydrogenate, as well as the emergence of novel concepts in catalysis, such as the use of non-traditional metals, phosphine-free catalysts and chiral counterions. An analysis of industry publications from 2009 and 2010 highlights more established applications of asymmetric hydrogenation reactions; these are discussed with a particular focus on practical aspects, such as catalyst selection, experimental conditions and the removal of metal residues.

  13. Asymmetric transfer of auditory perceptual learning

    Directory of Open Access Journals (Sweden)

    Sygal eAmitay


    Full Text Available Perceptual skills can improve dramatically even with minimal practice. A major and practical benefit of learning, however, is in transferring the improvement on the trained task to untrained tasks or stimuli, yet the mechanisms underlying this process are still poorly understood. Reduction of internal noise has been proposed as a mechanism of perceptual learning, and while we have evidence that frequency discrimination (FD learning is due to a reduction of internal noise, the source of that noise was not determined. In this study, we examined whether reducing the noise associated with neural phase locking to tones can explain the observed improvement in behavioural thresholds. We compared FD training between two tone durations (15 and 100 ms that straddled the temporal integration window of auditory nerve fibers upon which computational modeling of phase locking noise was based. Training on short tones resulted in improved FD on probe tests of both the long and short tones. Training on long tones resulted in improvement only on the long tones. Simulations of FD learning, based on the computational model and on signal detection theory, were compared with the behavioral FD data. We found that improved fidelity of phase locking accurately predicted transfer of learning from short to long tones, but also predicted transfer from long to short tones. The observed lack of transfer from long to short tones suggests the involvement of a second mechanism. Training may have increased the temporal integration window which could not transfer because integration time for the short tone is limited by its duration. Current learning models assume complex relationships between neural populations that represent the trained stimuli. In contrast, we propose that training-induced enhancement of the signal-to-noise ratio offers a parsimonious explanation of learning and transfer that easily accounts for asymmetric transfer of learning.

  14. Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond

    Indian Academy of Sciences (India)

    Ultrafast Dynamics of Chemical Reactions in Condensed Phase: Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond · PowerPoint Presentation · Slide 3 · Slide 4 · Slide 5 · Slide 6 · Slide 7 · Slide 8 · Slide 9 · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Slide 16 · Slide 17 · Slide 18 · Slide 19.

  15. Rhodium-Catalyzed Asymmetric Hydrogenation of α,β-Unsaturated Carbonyl Compounds via Thiourea Hydrogen Bonding. (United States)

    Wen, Jialin; Jiang, Jun; Zhang, Xumu


    The strategy of secondary interaction enables enantioselectivity for homogeneous hydrogenation. By introducing hydrogen bonding of substrates with thiourea from the ligand, α,β-unsaturated carbonyl compounds, such as amides and esters, are hydrogenated with high enantiomeric excess. The substrate scope for this chemical transformation is broad with various substituents at the β-position. Control experiments revealed that each unit of the ligand ZhaoPhos is irreplaceable. No nonlinear effect was observed for this Rh/ZhaoPhos-catalyzed asymmetric hydrogenation.

  16. Practical Aspects and Mechanism of Asymmetric Hydrogenation with Chiral Half-Sandwich Complexes

    Directory of Open Access Journals (Sweden)

    Petr Kačer


    Full Text Available This review is oriented toward the asymmetric transfer hydrogenation (ATH of imines regarding mostly fundamental, yet important topics from the practical point of view. Development of analytical methods for the monitoring of ATH (i.e., kinetics and stereoselectivity belongs to those topics, as well as studies on the influence of reaction conditions and structural variations on the reaction performance. The second part is devoted to the reaction mechanism with the emphasis on imine ATH and catalyst behaviour under acidic conditions. The review also addresses the asymmetric hydrogenation (AH of ketones and imines using molecular hydrogen and the application of ATH in pharmaceutical projects. The contributions of our group to each area are included.

  17. Asymmetric radiation transfer based on linear light-matter interaction (United States)

    Jia, Zi-xun; Shuai, Yong; Zhang, Jia-hui; Tan, He-ping


    In this paper, asymmetric radiation transfer based on linear light-matter interaction has been proposed. Two naturally different numerical methods, finite difference time domain (FDTD) and rigorous coupled wave analysis (RCWA), are utilized to verify that asymmetric radiation transfer can exist for linear plasmonic meta-material. The overall asymmetry has been introduced to evaluate bifacial transmission. Physics for the asymmetric optical responses have been understood via electromagnetic field distributions. Dispersion relation for surface plasmon polariton (SPP) and temporal coupled mode theory (TCMT) have been employed to verify the physics discussed in the paper. Geometric effects and the disappearing of asymmetric transmission have also been investigated. The results gained herein broaden the cognition of linear optical system, facilitate the design of novel energy harvesting device.

  18. Control of systems with asymmetric bounds using linear programming: application to a hydrogen reformer

    Directory of Open Access Journals (Sweden)


    Full Text Available This paper studies controller design for feedback systems in the presence of asymmetrically bounded signals, using a case study. An asymmetric objective functional is used to consider the asymmetrically bounded signals, which makes possible to derive a linear programming problem. Solving this LP makes possible to design controllers that minimize certain outputs, fulfilling at the same time hard constraints on certain signals. The method is presented by application to a hydrogen reformer, a system in petrochemical plants that produces hydrogen from hydrocarbons: a mixed sensitivity problem is stated and solved, with an additional constraint given by the asymmetric limitations on the magnitude and rate of the control signal, and the asymmetricity in the disturbances.

  19. Air-water transfer of hydrogen sulfide

    DEFF Research Database (Denmark)

    Yongsiri, C.; Vollertsen, J.; Rasmussen, M. R.


    The emissions process of hydrogen sulfide was studied to quantify air–water transfer of hydrogen sulfide in sewer networks. Hydrogen sulfide transfer across the air–water interface was investigated at different turbulence levels (expressed in terms of the Froude number) and pH using batch...... experiments. By means of the overall mass–transfer coefficient (KLa), the transfer coefficient of hydrogen sulfide (KLaH2S), referring to total sulfide, was correlated to that of oxygen (KLaO2) (i.e., the reaeration coefficient). Results demonstrate that both turbulence and pH in the water phase play...... a significant role for KLaH2S. An exponential expression is a suitable representation for the relationship between KLaH2S and the Froude number at all pH values studied (4.5 to 8.0). Because of the dissociation of hydrogen sulfide, KLaH2S increased with decreasing pH at a constant turbulence level. Relative...

  20. A Mixed Ligand Approach for the Asymmetric Hydrogenation of 2-Substituted Pyridinium Salts

    NARCIS (Netherlands)

    Renom-Carrasco, Marc; Gajewski, Piotr; Pignataro, Luca; de Vries, Johannes G.; Piarulli, Umberto; Gennari, Cesare; Lefort, Laurent


    Herein we describe a new methodology for the asymmetric hydrogenation (AH) of 2-substituted pyridinium salts. An iridium catalyst based on a mixture of a chiral monodentate phosphoramidite and an achiral phosphine was shown to hydrogenate N-benzyl-2-arylpyiridinium bromides to the corresponding

  1. Assisted Tandem Catalysis : Metathesis Followed by Asymmetric Hydrogenation from a Single Ruthenium Source

    NARCIS (Netherlands)

    Renom-Carrasco, Marc; Gajewski, Piotr; Pignataro, Luca; de Vries, Johannes G.; Piarulli, Umberto; Gennari, Cesare; Lefort, Laurent


    Here we report the first example of a tandem metathesis-asymmetric hydrogenation protocol where the prochiral olefin generated by metathesis is hydrogenated with high enantioselectivity by an in situ formed chiral ruthenium catalyst. We show that either the ruthenium metathesis catalysts or the

  2. Signal transfer within a cultured asymmetric cortical neuron circuit (United States)

    Isomura, Takuya; Shimba, Kenta; Takayama, Yuzo; Takeuchi, Akimasa; Kotani, Kiyoshi; Jimbo, Yasuhiko


    Objective. Simplified neuronal circuits are required for investigating information representation in nervous systems and for validating theoretical neural network models. Here, we developed patterned neuronal circuits using micro fabricated devices, comprising a micro-well array bonded to a microelectrode-array substrate. Approach. The micro-well array consisted of micrometre-scale wells connected by tunnels, all contained within a silicone slab called a micro-chamber. The design of the micro-chamber confined somata to the wells and allowed axons to grow through the tunnels bidirectionally but with a designed, unidirectional bias. We guided axons into the point of the arrow structure where one of the two tunnel entrances is located, making that the preferred direction. Main results. When rat cortical neurons were cultured in the wells, their axons grew through the tunnels and connected to neurons in adjoining wells. Unidirectional burst transfers and other asymmetric signal-propagation phenomena were observed via the substrate-embedded electrodes. Seventy-nine percent of burst transfers were in the forward direction. We also observed rapid propagation of activity from sites of local electrical stimulation, and significant effects of inhibitory synapse blockade on bursting activity. Significance. These results suggest that this simple, substrate-controlled neuronal circuit can be applied to develop in vitro models of the function of cortical microcircuits or deep neural networks, better to elucidate the laws governing the dynamics of neuronal networks.

  3. Local heat transfer in an in-line tube bundle with asymmetrical flow

    DEFF Research Database (Denmark)

    Meyer, Knud Erik


    Measurements of the local heat transfer in themiddle of a small in-line tube bundle with longitudinal to transverse pitches of $1.5\\times 1.8$ are performed at a Reynolds number of $30\\,000$. Asymmetrical distributions of the local heat transfer are found. The distributions are in good agreement...... with earlier flow measurements. The mean heat transfer rate is only little affected bythe asymmetrical conditions....

  4. New mechanistic aspects of the asymmetric homogeneous hydrogenation of alkenes. (United States)

    Brown, J M; Giernoth, R


    Progress in homogeneous catalysis depends upon an understanding of the reaction mechanism; in asymmetric catalysis this entails an insight into the origins of enantioselectivity. Significant advances have been made in the area of alkene reduction catalyzed by rhodium or ruthenium complexes, which has been in tandem with the development of new, more effective ligands for the reaction. The combination of quantum chemical calculations and direct spectroscopic observation of catalytic intermediates has proved powerful in this regard.

  5. Highly enantioselective synthesis of chiral cyclic allylic amines via Rh-catalyzed asymmetric hydrogenation. (United States)

    Zhou, Ming; Liu, Tang-Lin; Cao, Min; Xue, Zejian; Lv, Hui; Zhang, Xumu


    Highly regioselective and enantioselective asymmetric hydrogenation of cyclic dienamides catalyzed by an Rh-DuanPhos complex has been developed, which provides a readily accessible method for the synthesis of chiral cyclic allylic amines in excellent enantioselectivities (up to 99% ee). The products are valuable chiral building blocks and could be easily transformed to multisubstituted cyclohexane derivatives.

  6. Phosphonium salts as chiral phase-transfer catalysts: asymmetric Michael and Mannich reactions of 3-aryloxindoles. (United States)

    He, Rongjun; Ding, Changhua; Maruoka, Keiji


    It's a PTC: A highly efficient reaction of 3-aryloxindoles in an asymmetric Michael addition was achieved by using a quaternary tetraalkylphosphonium salt as a chiral phase-transfer catalyst (PTC). The products were obtained in quantitative yields high ee values. The reaction of 3-aryloxindoles in an asymmetric Mannich reaction using the same catalyst also proved to be feasible.

  7. NHC-Cu(I) catalysed asymmetric conjugate silyl transfer to unsaturated lactones: application in kinetic resolution. (United States)

    Pace, Vittorio; Rae, James P; Harb, Hassan Y; Procter, David J


    The scope of the asymmetric silyl transfer to unsaturated lactones utilising a C2-symmetric NHC-Cu(I) catalyst has been established and kinetic resolutions mediated by silyl transfer have been used to prepare enantiomerically enriched anti-4,5-disubstituted 5-membered lactones. The method has been exploited in an expedient synthesis of (+)-blastmycinone.

  8. The effect of hydrogen-like impurity on RbCl asymmetric quantum dot qubit (United States)

    Liang, Z.-H.; Qi, B.; Xiao, J.-L.


    We study the eigenenergies and eigenfunctions of the ground and the first excited states of an electron, which is strongly coupled to longintudinal-optical phonon in an asymmetric quantum dot with a hydrogen-like impurity by using variational method of Pekar type. A single qubit can be realized in this two-level quantum system. The electron probability density oscillates in the asymmetric quantum dot with a certain period of T 0 = 10.958 fs when the electron is in the superposition state of the ground and the first excited states. Moreover, due to the presence of the different harmonic potentials, the dependence way of the probability density of the electron on the coordinate of z is different from that on the coordinates of x and y. It is found that the oscillating period increases with decreasing Coulombic impurity potential and the polaron radius.

  9. Asymmetric Hydrogen Bonding Catalysis for the Synthesis of Dihydroquinazoline-Containing Antiviral, Letermovir. (United States)

    Chung, Cheol K; Liu, Zhijian; Lexa, Katrina W; Andreani, Teresa; Xu, Yingju; Ji, Yining; DiRocco, Daniel A; Humphrey, Guy R; Ruck, Rebecca T


    A weak Brønsted acid-catalyzed asymmetric guanidine aza-conjugate addition reaction has been developed. C2-symmetric, dual hydrogen-bond donating bistriflamides are shown to be highly effective in activating α,β-unsaturated esters toward the intramolecular addition of a pendant guanidinyl nucleophile. Preliminary mechanistic investigation, including density functional theory calculations and kinetics studies, support a conjugate addition pathway as more favorable energetically than an alternative electrocyclization pathway. This methodology has been successfully applied to the synthesis of the 3,4-dihydroquinazoline-containing antiviral, Letermovir, and a series of analogues.

  10. Non-Classical C–H···X Hydrogen Bonding and Its Role in Asymmetric Organocatalysis

    KAUST Repository

    Ajitha, Manjaly John


    Non-classical hydrogen bonds (NCHBs) have attracted significant interest in the past decade particularly because of their important role in asymmetric catalytic systems. These weak interactions (< 4 kcal/mol) offer much flexibility in the preorganization of molecular entities required to achieve high enantioselectivity. Herein, we review some recent important organocatalytic asymmetric reactions where a NCHB serves as a critical factor in determining the stereoselectivity.

  11. A simple setup for transfer hydrogenations in flow chemistry


    Wirth, Thomas; Hutchings, Matthew


    By using a packed-bed reactor with a palladium/charcoal catalyst and ammonium formate or triethylsilane as hydrogen/hydride source, various functional groups including nitro groups, azides and alkenes can be efficiently reduced by a transfer hydrogenation process under mild conditions in a simple flow system.

  12. Catalytic transfer-hydrogenations of olefins in glycerol

    Directory of Open Access Journals (Sweden)

    Adi Wolfson


    Full Text Available Glycerol has been successfully employed as a green solvent and hydrogen donor in the biphasic catalytic transfer-hydrogenation of olefins over Pd/C to yield the corresponding paraffins and dihydroxyacetone, respectively. The use of glycerol eased product separation and catalyst recycling and allowed for microwave-assisted reactions.

  13. Heat transfer analysis of liquid piston compressor for hydrogen applications

    DEFF Research Database (Denmark)

    Kermani, Nasrin Arjomand; Rokni, Masoud


    A hydrogen compression technology using liquid as the compression piston is investigated from heat transfer point of view. A thermodynamic model, simulating a single compression stroke, is developed to investigate the heat transfer phenomena inside the compression chamber. The model is developed...... and through the walls, is investigated and compared with the adiabatic case. The results show that depending on heat transfer correlation, the hydrogen temperature reduces slightly between 0.2% and 0.4% compared to the adiabatic case, at 500bar, due to the large wall resistance and small contact area...... at the interface. Moreover, the results of the sensitivity analysis illustrates that increasing the total heat transfer coefficients at the interface and the wall, together with compression time, play key roles in reducing the hydrogen temperature. Increasing the total heat transfer coefficient at the interface...

  14. Charge-Transfer in Time-Dependent Density Functional Theory: Insights from the Asymmetric Hubbard Dimer

    CERN Document Server

    Fuks, J I


    We show that an asymmetric two-fermion two-site Hubbard model illustrates the essential features of long-range charge-transfer dynamics in a real-space molecule. We apply a resonant field that transfers one fermion from one site to the other. Via constrained search we find the exact ground-state exchange-correlation functional, and use it to propagate the Kohn-Sham system, giving the first "adiabatically-exact" calculation of time-resolved charge-transfer. This propagation fails to properly transfer charge. We analyze why by comparing the exact and adiabatically-exact potentials and discuss the role of the derivative discontinuity. The implication for real-space molecules is that even the best possible adiabatic approximation, despite capturing non-local step features relevant to dissociation and charge-transfer excitations, cannot capture fully time-resolved charge-transfer dynamics.

  15. Transition Metal-Catalyzed Regioselective Asymmetric Mono-hydrogenation of Dienes and Polyenes. (United States)

    Margarita, Cristiana; Rabten, Wangchuk; Andersson, Pher G


    Organic compounds containing multiple C=C bonds are attractive substrates for catalytic asymmetric hydrogenation. The full saturation of prochiral double bonds, controlling the creation of two or more stereocenters in one step, is obviously a remarkable goal. However, another fascinating and useful option is to selectively introduce a new defined stereogenic center, while leaving other double bonds untouched. Thus, the retained functionalities can be further exploited in synthesis. Examples of regio- and enantioselective mono-hydrogenations of polyolefins are highlighted in this Concept article, and are divided according to the nature of the reduced double bond and the transition-metal catalyst used. Alkenes bearing coordinating functional groups are often preferentially hydrogenated by Rh- and Ru-complexes, while the more recently developed Ir-based catalysts promote the selective saturation on alkyl-substituted olefins. Relevant applications of this effective methodology in the synthesis of natural products are included to demonstrate its value in organic synthesis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Enantioselective synthesis of alcohols and amines by iridium-catalyzed hydrogenation, transfer hydrogenation, and related processes. (United States)

    Bartoszewicz, Agnieszka; Ahlsten, Nanna; Martín-Matute, Belén


    The preparation of chiral alcohols and amines by using iridium catalysis is reviewed. The methods presented include the reduction of ketones or imines by using hydrogen (hydrogenations), isopropanol, formic acid, or formate (transfer hydrogenations). Also dynamic and oxidative kinetic resolutions leading to chiral alcohols and amines are included. Selected literature reports from early contributions to December 2012 are discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Synthesis of N-phenyl β-amino acids via iridium-catalyzed asymmetric hydrogenation using mixed monodentate ligands

    NARCIS (Netherlands)

    Mrsic, Natasa; Panella, Lavinia; Minnaard, Adriaan J.; Feringa, Ben L.; de Vries, Johannes G.


    The iridium-catalyzed asymmetric hydrogenation of N-phenyl-beta-dehydroamino acid derivatives was examined using monodentate phosphoramidite ligands. The highest yields and enantioselectivities were obtained using a mixed ligand approach with PipPhos L1 and achiral triphenylphosphine (full

  18. Intermolecular Hydrogen Transfer in Isobutane Hydrate

    Directory of Open Access Journals (Sweden)

    Takeshi Sugahara


    Full Text Available Electron spin resonance (ESR spectra of butyl radicals induced with γ-ray irradiation in the simple isobutane (2-methylpropane hydrate (prepared with deuterated water were investigated. Isothermal annealing results of the γ-ray-irradiated isobutane hydrate reveal that the isobutyl radical in a large cage withdraws a hydrogen atom from the isobutane molecule through shared hexagonal-faces of adjacent large cages. During this “hydrogen picking” process, the isobutyl radical is apparently transformed into a tert-butyl radical, while the sum of isobutyl and tert-butyl radicals remains constant. The apparent transformation from isobutyl to tert-butyl radicals is an irreversible first-order reaction and the activation energy was estimated to be 35 ± 3 kJ/mol, which was in agreement with the activation energy (39 ± 5 kJ/mol of hydrogen picking in the γ-ray-irradiated propane hydrate with deuterated water.

  19. Transfer Hydrogenation: Employing a Simple, In Situ Prepared Catalytic System

    KAUST Repository

    Ang, Eleanor Pei Ling


    Transfer hydrogenation has been recognized to be an important synthetic method in both academic and industrial research to obtain valuable products including alcohols. Transition metal catalysts based on precious metals, such as Ru, Rh and Ir, are typically employed for this process. In recent years, iron-based catalysts have attracted considerable attention as a greener and more sustainable alternative since iron is earth abundant, inexpensive and non-toxic. In this work, a combination of iron disulfide with chelating bipyridine ligand was found to be effective for the transfer hydrogenation of a variety of ketones to the corresponding alcohols in the presence of a simple base. It provided a convenient and economical way to conduct transfer hydrogenation. A plausible role of sulfide next to the metal center in facilitating the catalytic reaction is demonstrated.

  20. Mechanism of Pd(NHC)-catalyzed transfer hydrogenation of alkynes. (United States)

    Hauwert, Peter; Boerleider, Romilda; Warsink, Stefan; Weigand, Jan J; Elsevier, Cornelis J


    The transfer semihydrogenation of alkynes to (Z)-alkenes shows excellent chemo- and stereoselectivity when using a zerovalent palladium(NHC)(maleic anhydride)-complex as precatalyst and triethylammonium formate as hydrogen donor. Studies on the kinetics under reaction conditions showed a broken positive order in substrate and first order in catalyst and hydrogen donor. Deuterium-labeling studies on the hydrogen donor showed that both hydrogens of formic acid display a primary kinetic isotope effect, indicating that proton and hydride transfers are separate rate-determining steps. By monitoring the reaction with NMR, we observed the presence of a coordinated formate anion and found that part of the maleic anhydride remains coordinated during the reaction. From these observations, we propose a mechanism in which hydrogen transfer from coordinated formate anion to zerovalent palladium(NHC)(MA)(alkyne)-complex is followed by migratory insertion of hydride, after which the product alkene is liberated by proton transfer from the triethylammonium cation. The explanation for the high selectivity observed lies in the competition between strongly coordinating solvent and alkyne for a Pd(alkene)-intermediate.

  1. Gas diffusion electrodes improve hydrogen gas mass transfer for a hydrogen oxidizing bioanode. (United States)

    Rodenas, Pau; Zhu, Fangqi; Ter Heijne, Annemiek; Sleutels, Tom; Saakes, Michel; Buisman, Cees


    Bioelectrochemical systems (BESs) are capable of recovery of metals at a cathode through oxidation of organic substrate at an anode. Recently, also hydrogen gas was used as an electron donor for recovery of copper in BESs. Oxidation of hydrogen gas produced a current density of 0.8 A m-2 and combined with Cu2+ reduction at the cathode, produced 0.25 W m-2. The main factor limiting current production was the mass transfer of hydrogen to the biofilm due to the low solubility of hydrogen in the anolyte. Here, the mass transfer of hydrogen gas to the bioanode was improved by use of a gas diffusion electrode (GDE). With the GDE, hydrogen was oxidized to produce a current density of 2.9 A m-2 at an anode potential of -0.2 V. Addition of bicarbonate to the influent led to production of acetate, in addition to current. At a bicarbonate concentration of 50 mmol L-1, current density increased to 10.7 A m-2 at an anode potential of -0.2 V. This increase in current density could be due to oxidation of formed acetate in addition to oxidation of hydrogen, or enhanced growth of hydrogen oxidizing bacteria due to the availability of acetate as carbon source. The effect of mass transfer was further assessed through enhanced mixing and in combination with the addition of bicarbonate (50 mmol L-1) current density increased further to 17.1 A m-2. Hydrogen gas may offer opportunities as electron donor for bioanodes, with acetate as potential intermediate, at locations where excess hydrogen and no organics are available. © 2017 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

  2. Transfer hydrogenation reactions catalyzed by chiral half-sandwich ...

    Indian Academy of Sciences (India)

    oxidoreductases catalyze transfer hydrogenation of car- ... ruthenium(II) complexes containing (S)-N-substituted- ... 2. Experimental. 2.1 Materials and methods. All reactions and manipulations were routinely per- formed under a nitrogen atmosphere using standard. Schlenk techniques in oven-dried glassware. L-Proline,.

  3. palladium-catalysed transfer hydrogenation of alkenes in the ...

    African Journals Online (AJOL)

    ABSTRACT. Catalytic transfer hydrogenation using palladiumfll) chloride, zinc powder and various organic acids proved effective for the reduction of a variety of alkenes at ambient temperature and atmospheric pressure. The method was found to be convenient, economical and uses a stable nonpyrophoric catalyst.

  4. Hydrogen transfer reaction of cyclohexanone with 2-propanol ...

    Indian Academy of Sciences (India)


    Addition of ceria into zinc oxide was found to increase the catalytic activity for hydrogen transfer reaction. The catalytic activity also depended on the method of preparation. Citrate process results in uniformly dispersed mixed oxide with higher catalytic activity. Keywords. Cyclohexanone; ceria; ZnO; diffuse reflectance; EPR.

  5. Development of atom-economical catalytic asymmetric reactions under proton transfer conditions: construction of tetrasubstituted stereogenic centers and their application to therapeutics. (United States)

    Kumagai, Naoya


    The development of atom-economical catalytic asymmetric reactions based on two distinct sets of catalyst, a rare earth metal/amide-based ligand catalyst and a soft Lewis acid/hard Brønsted base catalyst, is reviewed. These catalytic systems exhibit high catalytic activity and stereoselectivity by harnessing a cooperative catalysis through hydrogen bond/metal coordination and soft-soft interactions/hard-hard interactions, respectively. The effectiveness of these cooperative catalysts is clearly delineated by the high stereoselectivity in reactions with highly coordinative substrates, and the specific activation of otherwise low-reactive pronucleophiles under proton transfer conditions. The rare earth metal/amide-based ligand catalyst was successfully applied to catalytic asymmetric aminations, nitroaldol (Henry) reactions, Mannich-type reactions, and conjugate addition reactions, generating stereogenic tetrasubstituted centers. Catalytic asymmetric amination and anti-selective catalytic asymmetric nitroaldol reactions were successfully applied to the efficient enantioselective synthesis of therapeutic candidates, such as AS-3201 and the β(3)-adrenoreceptor agonist, showcasing the practical utility of the present protocols. The soft Lewis acid/hard Brønsted base cooperative catalyst was specifically developed for the chemoselective activation of soft Lewis basic allylic cyanides and thioamides, which are otherwise low-reactive pronucleophiles. The cooperative action of the catalyst allowed for efficient catalytic generation of active carbon nucleophiles in situ, which were integrated into subsequent enantioselective additions to carbonyl-type electrophiles.

  6. Experimental and theoretical analysis of asymmetric induction in heterogeneous catalysis: diastereoselective hydrogenation of chiral alpha-hydroxyketones over Pt catalyst. (United States)

    Busygin, Igor; Taskinen, Antti; Nieminen, Ville; Toukoniitty, Esa; Stillger, Thomas; Leino, Reko; Murzin, Dmitry Yu


    Assessing the origin of asymmetric induction in heterogeneously catalyzed hydrogenation is a challenging task. In this work, hydrogenation of a chiral compound, (R)-1-hydroxy-1-phenyl-2-propanone [(R)-PAC], in toluene over cinchonidine modified and unmodified Pt/Al(2)O(3) was studied. To reveal the detailed reaction mechanism and the origin of stereoselectivity in the Pt-catalyzed hydrogenation of the CO double bond, the structures and energies of several adsorption modes of (R)-PAC as well as whole reaction paths for hydrogenation were investigated on Pt(111) by density functional theory (DFT). In agreement with experimental results, the theoretically obtained potential energy profiles for the studied hydrogenation mechanisms implied that (1R,2S)-1-phenyl-1,2-propanediol is formed in excess with respect to the other diastereomeric product diol, (1R,2R)-1-phenyl-1,2-propanediol. Generally, if the elementary hydrogen addition step was thermodynamically more favorable on one of the two diastereotopic faces, it was also kinetically preferred on the same face, and vice versa. Pairwise addition of hydrogen was the most energetically favorable mechanism. Adsorption and hydrogenation of other structurally similar chiral alpha-hydroxyketones, (R)-3-hydroxy-2-butanone and (R)-2-hydroxy-1-cyclohexanone, were also studied computationally on Pt(111). The results showed that cluster model DFT calculations can be used to assess (dia)stereoselectivity in metal-catalyzed hydrogenation of even such complex organic molecules as studied here.

  7. Transfer of chirality in new supramolecular complexes as design principle for future asymmetric catalysts


    Degenbeck, Helmut


    During the course of the thesis libraries of chiral (1,2)-diamines and prochiral 2,2’-biphenol derivatives were synthesised. The transfer of chirality from the diamine to the biphenol moiety mediated either by hydrogen bonding or coordination to a metal centre (ZnII, CuII) was demonstrated by CD (circular dicroism). The behaviour in solution of the hydrogen bonded complexes was investigated by NMR spectroscopy, UV-vis and ITC titrations (determination of association constants. The determinati...

  8. Design of Asymmetrical Relay Resonators for Maximum Efficiency of Wireless Power Transfer

    Directory of Open Access Journals (Sweden)

    Bo-Hee Choi


    Full Text Available This paper presents a new design method of asymmetrical relay resonators for maximum wireless power transfer. A new design method for relay resonators is demanded because maximum power transfer efficiency (PTE is not obtained at the resonant frequency of unit resonator. The maximum PTE for relay resonators is obtained at the different resonances of unit resonator. The optimum design of asymmetrical relay is conducted by both the optimum placement and the optimum capacitance of resonators. The optimum placement is found by scanning the positions of the relays and optimum capacitance can be found by using genetic algorithm (GA. The PTEs are enhanced when capacitance is optimally designed by GA according to the position of relays, respectively, and then maximum efficiency is obtained at the optimum placement of relays. The capacitance of the second resonator to nth resonator and the load resistance should be determined for maximum efficiency while the capacitance of the first resonator and the source resistance are obtained for the impedance matching. The simulated and measured results are in good agreement.

  9. Cryogenic Propellant Storage and Transfer Engineering Development Unit Hydrogen Tank (United States)

    Werkheiser, Arthur


    The Cryogenic Propellant Storage and Transfer (CPST) project has been a long-running program in the Space Technology Mission Directorate to enhance the knowledge and technology related to handling cryogenic propellants, specifically liquid hydrogen. This particular effort, the CPST engineering development unit (EDU), was a proof of manufacturability effort in support of a flight article. The EDU was built to find and overcome issues related to manufacturability and collect data to anchor the thermal models for use on the flight design.

  10. Engineering and Probing Topological Properties of Dirac Semimetal Films by Asymmetric Charge Transfer. (United States)

    Villanova, John W; Barnes, Edwin; Park, Kyungwha


    Dirac semimetals (DSMs) have topologically robust three-dimensional Dirac (doubled Weyl) nodes with Fermi-arc states. In heterostructures involving DSMs, charge transfer occurs at the interfaces, which can be used to probe and control their bulk and surface topological properties through surface-bulk connectivity. Here we demonstrate that despite a band gap in DSM films, asymmetric charge transfer at the surface enables one to accurately identify locations of the Dirac-node projections from gapless band crossings and to examine and engineer properties of the topological Fermi-arc surface states connecting the projections, by simulating adatom-adsorbed DSM films using a first-principles method with an effective model. The positions of the Dirac-node projections are insensitive to charge transfer amount or slab thickness except for extremely thin films. By varying the amount of charge transfer, unique spin textures near the projections and a separation between the Fermi-arc states change, which can be observed by gating without adatoms.

  11. Skill transfer from symmetric and asymmetric bimanual training using a robotic system to single limb performance

    Directory of Open Access Journals (Sweden)

    Trlep Matic


    Full Text Available Abstract Background Humans are capable of fast adaptation to new unknown dynamics that affect their movements. Such motor learning is also believed to be an important part of motor rehabilitation. Bimanual training can improve post-stroke rehabilitation outcome and is associated with interlimb coordination between both limbs. Some studies indicate partial transfer of skills among limbs of healthy individuals. Another aspect of bimanual training is the (asymmetry of bimanual movements and how these affect motor learning and possibly post-stroke rehabilitation. Methods A novel bimanual 2-DOF robotic system was used for both bimanual and unimanual reaching movements. 35 young healthy adults participated in the study. They were divided into 5 test groups that performed movements under different conditions (bimanual or unimanual movements and symmetric or asymmetric bimanual arm loads. The subjects performed a simple tracking exercise with the bimanual system. The exercise was developed to stimulate motor learning by applying a velocity-dependent disturbance torque to the handlebar. Each subject performed 255 trials divided into three phases: baseline without disturbance torque, training phase with disturbance torque and evaluation phase with disturbance torque. Results Performance was assessed with the maximal values of rotation errors of the handlebar. After exposure to disturbance torque, the errors decreased for both unimanual and bimanual training. Errors in unimanual evaluation following the bimanual training phase were not significantly different from errors in unimanual evaluation following unimanual training. There was no difference in performance following symmetric or asymmetric training. Changing the arm force symmetry during bimanual movements from asymmetric to symmetric had little influence on performance. Conclusions Subjects could adapt to an unknown disturbance torque that was changing the dynamics of the movements. The learning

  12. Nitranilic acid hexahydrate, a novel benchmark system of the Zundel cation in an intrinsically asymmetric environment: spectroscopic features and hydrogen bond dynamics characterised by experimental and theoretical methods. (United States)

    Molčanov, Krešimir; Stare, Jernej; Vener, Mikhail V; Kojić-Prodić, Biserka; Mali, Gregor; Grdadolnik, Jože; Mohaček-Grošev, Vlasta


    Nitranilic acid (2,5-dihydroxy-3,6-dinitro-2,5-cyclohexadiene-1,4-dione) as a strong dibasic acid in acidic aqueous media creates the Zundel cation, H5O2(+). The structural unit in a crystal comprises (H5O2)2(+) (2,5-dihydroxy-3,6-dinitro-1,4-benzoquinonate)(2-) dihydrate where the Zundel cation reveals no symmetry, being an ideal case for studying proton dynamics and its stability. The Zundel cation and proton transfer dynamics are studied by variable-temperature X-ray diffraction, IR and solid-state NMR spectroscopy, and various quantum chemical methods, including periodic DFT calculations, ab initio molecular dynamics simulation, and quantization of nuclear motion along three fully coupled internal coordinates. The Zundel cation features a short H-bond with the O···O distance of 2.433(2) Å with an asymmetric placement of hydrogen. The proton potential is of a single well type and, due to the non-symmetric surroundings, of asymmetric shape. The formation of the Zundel cation is facilitated by the electronegative NO2 groups. The employed spectroscopic techniques supported by calculations confirm the presence of a short H-bond with a complex proton dynamics.

  13. Electrochemical proton-coupled electron transfer of an osmium aquo complex: theoretical analysis of asymmetric tafel plots and transfer coefficients. (United States)

    Ludlow, Michelle K; Soudackov, Alexander V; Hammes-Schiffer, Sharon


    Electrochemical proton-coupled electron transfer of an osmium aquo complex attached to a self-assembled monolayer on a gold electrode is studied with a recently developed theoretical formulation. The calculated hydrogen/deuterium kinetic isotope effect for the standard rate constant, the cathodic transfer coefficient at zero overpotential, and the Tafel plot are in excellent agreement with experimental data. The input quantities to the heterogeneous rate constant expressions were calculated with density functional theory in conjunction with dielectric continuum models, and no parameters were fit to experimental data. The theoretical calculations indicate that the asymmetry of the Tafel plot and the deviation of the transfer coefficient at zero overpotential from the standard value of one-half arise from the change in the equilibrium proton donor-acceptor distance upon electron transfer. The direction of the asymmetry and deviation from one-half is determined by the sign of this distance change, and the magnitude of these effects is determined by the magnitude of this distance change, as well as the reorganization energy and the distance dependence of the overlap between the initial and final proton vibrational wave functions. This theory provides experimentally testable predictions for the impact of specific system properties on the qualitative behavior of the Tafel plots.

  14. Hydrogen-bond-mediated asymmetric cascade reaction of stable sulfur ylides with nitroolefins: scope, application and mechanism. (United States)

    Lu, Liang-Qiu; Li, Fang; An, Jing; Cheng, Ying; Chen, Jia-Rong; Xiao, Wen-Jing


    A hydrogen-bond-mediated asymmetric [4+1] annulation/rearrangement cascade of stable sulfur ylides and nitroolefins was developed. This reaction provides a facile route to enantioenriched 4,5-substituted oxazolidinones in moderate to excellent isolated yields (65-96 %) with excellent stereocontrol (up to more than 95:5 d.r. and 97:3 e.r.). This methodology was successfully applied to the concise synthesis of two bioactive molecules. The stereocontrolled modes and mechanism have been proposed to explain the origin of this stereochemistry. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Biooxidation of Primary Alcohols to Aldehydes through Hydrogen Transfer Employing Janibacter terrae

    NARCIS (Netherlands)

    Orbegozo, Thomas; Vries, Johannes G. de; Kroutil, Wolfgang


    Chemoselective oxidations still represent a challenge for chemists. Lyophilized cells of Janibacter terrae were employed for the chemoselective oxidation of primary alcohols to the corresponding aldehydes by hydrogen transfer with the use of acetaldehyde as the hydrogen acceptor. Secondary alcohol

  16. Common Hydrogen Bond Interactions in Diverse Phosphoryl Transfer Active Sites (United States)

    Summerton, Jean C.; Martin, Gregory M.; Evanseck, Jeffrey D.; Chapman, Michael S.


    Phosphoryl transfer reactions figure prominently in energy metabolism, signaling, transport and motility. Prior detailed studies of selected systems have highlighted mechanistic features that distinguish different phosphoryl transfer enzymes. Here, a top-down approach is developed for comparing statistically the active site configurations between populations of diverse structures in the Protein Data Bank, and it reveals patterns of hydrogen bonding that transcend enzyme families. Through analysis of large samples of structures, insights are drawn at a level of detail exceeding the experimental precision of an individual structure. In phosphagen kinases, for example, hydrogen bonds with the O3β of the nucleotide substrate are revealed as analogous to those in unrelated G proteins. In G proteins and other enzymes, interactions with O3β have been understood in terms of electrostatic favoring of the transition state. Ground state quantum mechanical calculations on model compounds show that the active site interactions highlighted in our database analysis can affect substrate phosphate charge and bond length, in ways that are consistent with prior experimental observations, by modulating hyperconjugative orbital interactions that weaken the scissile bond. Testing experimentally the inference about the importance of O3β interactions in phosphagen kinases, mutation of arginine kinase Arg280 decreases kcat, as predicted, with little impact upon KM. PMID:25238155

  17. The Combinatorial Approach to Asymmetric Hydrogenation : Phosphoramidite Libraries, Ruthenacycles, and Artificial Enzymes

    NARCIS (Netherlands)

    Vries, Johannes G. de; Lefort, Laurent


    For a more general implementation of asymmetric catalysis in the production of fine chemicals, the screening for new catalysts and ligands must be dramatically accelerated. This is possible with a high-throughput experimentation (HTE) approach. However, implementation of this technology requires the

  18. Transfer hydrogenation of olefin from alcohol using a hydrogen-absorbing alloy (CaNi{sub 5}) catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Imamura, H.; Tanaka, T.; Sakata, Y.; Tsuchiya, S. [Yamaguchi Univ., Ube (Japan). Faculty of Engineering


    Gas-phase reactions between 2-butene and 2-propanol on a hydrogen-absorbing alloy CaNi{sub 5} have been studied in the temperature range of 393 to 473 K. CaNi{sub 5} showed interesting characteristics as an active catalyst for the transfer hydrogenation of butene from propanol as a hydrogen donor. 2-Propanol was effectively dehydrogenated to yield acetone, in which the dissociated hydrogen was completely absorbed by CaNi{sub 5} to form the metal hydride. When the alloy was hydrided to some extent, butene was effectively hydrogenated by the absorbed hydrogen in the metal hydride to produce butane. The overall reaction was expressed as catalytic transfer hydrogenation through the formation of metal hydride intermediates (CaNi{sub 5}H{sub n}). Catalytic transfer hydrogenation on CaNi{sub 5} occurred at 423 K via hydriding of CaNi{sub 5} by 2-propanol dehydrogenation with subsequent dehydriding for the hydrogenation of 2-butene, rather than the direct reaction between 2-butene and 2-propanol on the alloy. (orig.)

  19. Wagging motion of hydrogen-bonded wire in the excited-state multiple proton transfer process of 7-hydroxyquinoline·(NH3)3 cluster. (United States)

    Liu, Yu-Hui; Lan, Sheng-Cheng; Li, Chun-Ran


    In this work, the dynamics of hydrogen bonds (as well as the hydrogen-bonded wire) in excited-state tautomerization of 7-hydroxyquinoline·(NH3)3 (7HQ·(NH3)3) cluster has been investigated by using time-dependent density functional theory (TDDFT). It shows that upon an excitation, the hydrogen bond between -OH group in 7-hydroxyquinoline (7HQ) and NH3 moiety would extremely strengthened in S1 state, which could effectively facilitate the releasing of the proton from the phenolic group of 7HQ moiety to the hydrogen-bonded wire and the forming an Eigen-like cationic wire (NH3···NH4(+)···NH3) in the cluster. To fulfill the different optimal angles of NH4(+) in the wire, a wagging motion of hydrogen-bonded wire would occur in excited state. Moreover, the wagging motion of the hydrogen-bonded wire would effectively promote excited-state proton transfer reaction. As the results, an excited-state multiple proton transfer (ESMPT) mechanism containing two concerted and asymmetrical processes has been proposed for the proton transfer dynamics of 7HQ·(NH3)3 cluster. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. I62− Anion Composed of Two Asymmetric Triiodide Moieties: A Competition between Halogen and Hydrogen Bond

    Directory of Open Access Journals (Sweden)

    Martin van Megen


    Full Text Available The reaction of 1,8-diaminooctane with hydroiodic acid in the presence of iodine gave a new polyiodide-containing salt: 1,8-diaminiumoctane bis(triiodide, (H3N-(CH28-NH3[I3]2. The title compound has been characterized by crystallographic and spectroscopic methods. The polyiodide ion is the first example of a hydrogen bonded I62− dianion consisting of two very asymmetric triiodide components with I−I distances of 2.7739(4 and 3.1778(4 Å interacting by a weak halogen bond (I···I: 3.5017(2 Å. The structural parameters of the triiodide anions, derived from X-ray crystallographic data, are in good agreement with the Raman and Far-IR spectroscopic results.

  1. Bipolar spin-filtering effect in B- or N-doped zigzag graphene nanoribbons with asymmetric edge hydrogenation (United States)

    Wang, Li-hua; Zhang, Zi-zhen; Zhao, Jian-Guo; Ding, Bing-jun; Guo, Yong; Jin, Chun


    The spin transport properties of zigzag graphene nanoribbon (ZGNR) hetero-junctions, in which ZGNR electrodes are doped with B or N atoms, are investigated based on spin-polarized density functional theory and non-equilibrium Green's function. ZGNRs are C-H2 bonded at one edge and C-H bonded at the other edge to form asymmetric edge hydrogenation. The spin-polarized currents of ZGNR-based nano-devices with an odd or even number of the zigzag-shaped chains show a perfect bipolar spin-filtering effect on parallel and anti-parallel magnetic configurations. This study provides insights into the design of high-performance graphene-based spin filters.

  2. A Mixed-Ligand Approach Enables the Asymmetric Hydrogenation of an α-Isopropylcinnamic Acid en Route to the Renin Inhibitor Aliskiren

    NARCIS (Netherlands)

    Boogers, Jeroen A.F.; Felfer, Ulfried; Kotthaus, Martina; Lefort, Laurent; Steinbauer, Gerhard; Vries, André H.M. de; Vries, Johannes G. de


    An asymmetric hydrogenation process for an α-isopropyl dihydrocinnamic acid derivative, an intermediate for the renin inhibitor aliskiren, has been developed using a rhodium catalyst ligated with a chiral monodentate phosphoramidite and a nonchiral phosphine. Whereas catalysts based on two

  3. Understanding Hydrogen Atom Transfer: from Bond Strengths to Marcus Theory (United States)



    CONSPECTUS Hydrogen atom transfer (HAT) is one of the most fundamental chemical reactions: A–H + B → A + H–B. It is a key step in a wide range of chemical, environmental, and biological processes. Traditional HAT involves p-block radicals such as tBuO• abstracting H• from organic molecules. More recently, it has been recognized that many transition metal species undergo HAT. This has led to a broader perspective, with HAT viewed as one type of proton-coupled electron transfer (PCET). When transition metal complexes oxidize substrates by removing H• (≡ e– and H+), typically the electron transfers to the metal and the proton transfers to a ligand. Two examples are shown in the Figure: iron-imidazolinate and vanadium-oxo complexes. Although such reagents do not “look like” main group radicals, they have the same pattern of reactivity. For instance, their HAT rate constants parallel the A–H bond strengths within a series of similar reactions. Just like main group radicals, they abstract H• much faster from O–H bonds than from C–H bonds of the same strength. This shows that driving force is not the only determinant of reactivity. We have found that HAT reactivity is well described using a Marcus-theory approach. In the simplest model, the cross relation, kAH/B = (kAH/AkBH/BKeqf)½, predicts the rate constant for AH + B in terms of the self-exchange rate constants (kAH/A for AH + A) and the equilibrium constant. For a variety of transition metal oxidants, kAH/B is predicted within one or two orders of magnitude with only a few exceptions. For 36 organic reactions of oxyl radicals, kAH/B is predicted with an average deviation of a factor of 3.8, and within a factor of 5 for all but six of the reactions. These reactions involve both O–H or C–H bonds, occur either in water or organic solvents, and over a range of 1028 in Keq and 1013 in kAH/B. The treatment of organic reactions of O–H bonds includes the well-established kinetic solvent

  4. Microscale Enhancement of Heat and Mass Transfer for Hydrogen Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

    Drost, Kevin [Oregon State Univ., Corvallis, OR (United States); Jovanovic, Goran [Oregon State Univ., Corvallis, OR (United States); Paul, Brian [Oregon State Univ., Corvallis, OR (United States)


    The document summarized the technical progress associated with OSU’s involvement in the Hydrogen Storage Engineering Center of Excellence. OSU focused on the development of microscale enhancement technologies for improving heat and mass transfer in automotive hydrogen storage systems. OSU’s key contributions included the development of an extremely compact microchannel combustion system for discharging hydrogen storage systems and a thermal management system for adsorption based hydrogen storage using microchannel cooling (the Modular Adsorption Tank Insert or MATI).

  5. Amino acid based phosphoramidite ligands for the rhodium-catalyzed asymmetric hydrogenation

    NARCIS (Netherlands)

    Breuil, P.A.R.; Reek, J.N.H.


    Two sets of amino acid based phosphoramidite ligands with either a BINOL backbone (S-b-1a-e and Rb-1a) or a flexible biphenol backbone (2a-c and 2f) were synthesized and evaluated in the rhodium-catalyzed hydrogenation of different functionalized alkenes: dimethyl itaconate (3), methyl

  6. Asymmetric hydrogenation of aromatic ketones by new recyclable ionic tagged ferrocene-ruthenium catalyst system. (United States)

    Xu, Di; Zhou, Zhi-Ming; Dai, Li; Tang, Li-Wei; Zhang, Jun


    Newly developed ferrocene-oxazoline-phosphine ligands containing quaternary ammonium ionic groups exhibited excellent catalytic performance for the ruthenium-catalyzed hydrogenation of aromatic ketonic substrates to give chiral secondary alcohols with high levels of conversions and enantioselectivities. Simple manipulation process, water tolerance, high activity and good recyclable property make this catalysis practical and appealing. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Evidence for Coherent Transfer of para-Hydrogen-Induced Polarization at Low Magnetic Fields

    NARCIS (Netherlands)

    Kiryutin, A.S.; Yurkovskaya, A.V.; Kaptein, R.|info:eu-repo/dai/nl/074334603; Vieth, H.-M.; Ivanov, K.L.


    We have investigated the mechanism of para-hydrogen-induced polarization (PHIP) transfer from the original strongly aligned protons to other nuclei at low external magnetic fields. Although it is known that PHIP is efficiently transferred at low fields, the nature of the transfer mechanism, that is,

  8. Differential isotopic enrichment to facilitate characterization of asymmetric multimeric proteins using hydrogen/deuterium exchange mass spectrometry. (United States)

    Goswami, Devrishi; Tuske, Steve; Pascal, Bruce D; Bauman, Joseph D; Patel, Disha; Arnold, Eddy; Griffin, Patrick R


    Hydrogen/deuterium exchange (HDX) coupled to mass spectrometry has emerged as a powerful tool for analyzing the conformational dynamics of protein-ligand and protein-protein interactions. Recent advances in instrumentation and methodology have expanded the utility of HDX for the analysis of large and complex proteins; however, asymmetric dimers with shared amino acid sequence present a unique challenge for HDX because assignment of peptides with identical sequence to their subunit of origin remains ambiguous. Here we report the use of differential isotopic labeling to facilitate HDX analysis of multimers using HIV-1 reverse transcriptase (RT) as a model. RT is an asymmetric heterodimer of 51 kDa (p51) and 66 kDa (p66) subunits. The first 440 residues of p51 and p66 are identical. In this study differentially labeled RT was reconstituted from isotopically enriched ((15)N-labeled) p51 and unlabeled p66. To enable detection of (15)N-deuterated RT peptides, the software HDX Workbench was modified to follow a 100% (15)N model. Our results demonstrated that (15)N enrichment of p51 did not affect its conformational dynamics compared to unlabeled p51, but (15)N-labeled p51 did show different conformational dynamics than p66 in the RT heterodimer. Differential HDX-MS of isotopically labeled RT in the presence of the non-nucleoside reverse transcriptase inhibitor (NNRTI) efavirenz (EFV) showed subunit-specific perturbation in the rate of HDX consistent with previously published results and the RT-EFV cocrystal structure.

  9. Chemical utilization of hydrogen from fluctuating energy sources – Catalytic transfer hydrogenation from charged Liquid Organic Hydrogen Carrier systems


    Geburtig, Denise; Preuster, Patrick; Bösmann, Andreas; Müller, Karsten; Wasserscheid, Peter


    Liquid Organic Hydrogen Carrier (LOHC) systems offer a very attractive way for storing and distributing hydrogen from electrolysis using excess energies from solar or wind power plants. In this contribution, an alternative, high-value utilization of such hydrogen is proposed namely its use in steady-state chemical hydrogenation processes. We here demonstrate that the hydrogen-rich form of the LOHC system dibenzyltoluene/perhydro-dibenzyltoluene can be directly applied as sole source of hydrog...

  10. Numerical Radiative Transfer and the Hydrogen Reionization of the Universe (United States)

    Petkova, M.


    ) simulation code GADGET. It is based on a fast, robust and photon-conserving integration scheme where the radiation transport problem is approximated in terms of moments of the transfer equation and by using a variable Eddington tensor as a closure relation, following the "OTVET"-suggestion of Gnedin & Abel. We derive a suitable anisotropic diffusion operator for use in the SPH discretization of the local photon transport, and we combine this with an implicit solver that guarantees robustness and photon conservation. This entails a matrix inversion problem of a huge, sparsely populated matrix that is distributed in memory in our parallel code. We solve this task iteratively with a conjugate gradient scheme. Finally, to model photon sink processes we consider ionization and recombination processes of hydrogen, which is represented with a chemical network that is evolved with an implicit time integration scheme. We present several tests of our implementation, including single and multiple sources in static uniform density fields with and without temperature evolution, shadowing by a dense clump, and multiple sources in a static cosmological density field. All tests agree quite well with analytical computations or with predictions from other radiative transfer codes, except for shadowing. However, unlike most other radiative transfer codes presently in use for studying reionization, our new method can be used on-the-fly during dynamical cosmological simulations, allowing simultaneous treatments of galaxy formation and the reionization process of the Universe. We carry out hydrodynamical simulations of galaxy formation that simultaneously follow radiative transfer of hydrogen-ionizing photons, based on the optically-thin variable Eddington tensor approximation as implemented in the GADGET code. We consider only star-forming galaxies as sources and examine to what extent they can yield a reasonable reionization history and thermal state of the intergalactic medium at redshifts

  11. Iron Phthalocyanine as New Efficient Catalyst for Catalytic Transfer Hydrogenation of Simple Aldehydes and Ketones

    Czech Academy of Sciences Publication Activity Database

    Bata, P.; Notheisz, F.; Klusoň, Petr; Zsigmond, A.


    Roč. 29, JAN 2015 (2015), s. 45-49 ISSN 0268-2605 Institutional support: RVO:67985858 Keywords : heterogenized complexes * catalytic transfer hydrogenation * reusable catalyst Subject RIV: CC - Organic Chemistry Impact factor: 2.452, year: 2015

  12. Charge Transfer Interaction and Hydrogen Bonding between Vitamine K1 and Dihydrovitamine K1 (United States)

    Nagahira, Yukio; Matsuki, Kazunori; Fukutome, Hideo


    We studied visible and infrared spectra, in particular their temperature dependence, of Vitamine K1 oil dissolving dihydrovitamine K1. Vitamine K1 and dihydrovitamine K1 were found to form charge transfer complexes and hydrogen bonds in the mixture. A co-crystal of Dihydrovitamine K1 and Vitamine K1 with charge transfer interaction and hydrogen bonding was shown to grow in a narrow temperature range near -20°C.

  13. An Asymmetric Redox Arylation: Chirality Transfer from Sulfur to Carbon through a Sulfonium [3,3]-Sigmatropic Rearrangement. (United States)

    Kaldre, Dainis; Maryasin, Boris; Kaiser, Daniel; Gajsek, Oliver; González, Leticia; Maulide, Nuno


    A general, asymmetric redox arylation of ynamides and thioalkynes with chiral sulfoxides is reported. This is the first example of a general 1,4-chirality transfer from sulfur to a carbon stereocenter through a sulfonium [3,3]-sigmatropic rearrangement. This reaction delivers α-arylated thioesters and amides under mild conditions in an atom-economical manner. The products are formed in high yields with enantiomeric ratios up to 99.5:0.5. Quantum chemical calculations suggest a mechanism for the chirality transfer from sulfur to carbon and explain the experimentally observed correlation of the enantioselectivity with both the catalyst and the substrate. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Iridium-Catalyzed Asymmetric Hydrogenation of Ketones with Accessible and Modular Ferrocene-Based Amino-phosphine Acid (f-Ampha) Ligands. (United States)

    Yu, Jianfei; Long, Jiao; Yang, Yuhong; Wu, Weilong; Xue, Peng; Chung, Lung Wa; Dong, Xiu-Qin; Zhang, Xumu


    A series of tridentate ferrocene-based amino-phosphine acid (f-Ampha) ligands have been successfully developed. The f-Ampha ligands are extremely air stable and exhibited excellent performance in the Ir-catalyzed asymmetric hydrogenation of ketones (full conversions, up to >99% ee, and 500 000 TON). DFT calculations were performed to elucidate the reaction mechanism and the importance of the -COOH group. Control experiments also revealed that the -COOH group played a key role in this reaction.

  15. Reverse knowledge and technology transfer: imbalances caused by cognitive barriers in asymmetric relationships

    NARCIS (Netherlands)

    Millar-Schijf, Carla C.J.M.; Choi, Chong-Ju


    An imbalance exists in almost any type of knowledge and technology transfer due to the information asymmetry of the relationship. However, this is especially the case for reverse technology and knowledge transfer which is epitomised for us by "transfers from an MNC's subsidiary to its headquarters".

  16. Hydrogen-bond dynamics and proton transfer in nanoconfinement

    NARCIS (Netherlands)

    van der Loop, T.H.


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

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


    Erli Sugiono; Magnus Rueping


    Summary A continuous-flow asymmetric organocatalytic photocyclization?transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Br?nsted acid catalysis. The photocylization and subsequent reduction was performed with catalytic amount of chiral BINOL derived phosphoric acid diester and Hantzsch dihydropyridine as hydrogen source providing ...

  18. A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines. (United States)

    Sugiono, Erli; Rueping, Magnus


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

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

    Directory of Open Access Journals (Sweden)

    Erli Sugiono


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

  20. Heat transfer comparison between methane and hydrogen in a spark ignited engine

    Energy Technology Data Exchange (ETDEWEB)

    Sierens, Roger; Demuynck, Joachim; Paepe, Michel de; Verhelst, Sebastian [Ghent Univ. (Belgium)


    Hydrogen is one of the alternative fuels which are being investigated at Ghent University. NO{sub x} emissions will occur at high engine loads and they are a constraint for power and efficiency optimization. The formation of NO{sub x} emissions is temperature dependent. Consequently, the heat transfer from the burning gases to the cylinder walls has to be accurately modelled if precise computer calculations of the emissions are wanted. Several engine heat transfer models exist but they have been cited to be inaccurate for hydrogen. We have measured the heat flux in a spark ignited engine with a commercially available heat flux sensor. This paper investigates the difference between the heat transfer of hydrogen and a fossil fuel, in this case methane. Measurements with the same indicated power output are compared and the effect of the heat loss on the indicated efficiency is investigated. The power output of hydrogen combustion is lowered by burning lean in contrast to using a throttle in the case of methane. Although the peak in the heat flux of hydrogen is 3 times higher compared to methane for a high engine power output, the indicated efficiency is only 3% lower. The heat loss for hydrogen at a low engine load is smaller than that of methane which results in a higher indicated efficiency. The richness of the hydrogen-air mixture has a great influence on the heat transfer process in contrast to the in-cylinder mass in the case of methane. (orig.)

  1. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Eisch, J.J.


    The ultimate objective of this research is to uncover new catalytic processes for the liquefaction of coal and for upgrading coal-derived fuels by removing undesirable organosulfur, organonitrogen and organooxygen constituents. Basic to both the liquefaction of coal and the purification of coal liquids is the transfer of hydrogen from such sources as dihydrogen, metal hydrides or partially reduced aromatic hydrocarbons to the extensive aromatic rings in coal itself or to aromatic sulfides, amines or ethers. Accordingly, this study is exploring how such crucial hydrogen-transfer processes might be catalyzed by soluble, low-valent transition metal complexes and/or Lewis acids under moderate conditions of temperature and pressure. By learning the mechanism whereby H{sub 2}, metal hydrides or partially hydrogenated aromatics do transfer hydrogen to model aromatic compounds, with the aid of homogeneous, bimetallic catalysts, we hope to identify new methods for producing superior fuels from coal.

  2. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Eisch, J.J.


    The ultimate objective of this research is to uncover new catalytic processes for the liquefaction of coal and for upgrading coal-derived fuels by removing undesirable organosulfur, organonitrogen and organooxygen constituents. Basic to both the liquefaction of coal and the purification of coal liquids is the transfer of hydrogen from such sources as dihydrogen, metal hydrides or partially reduced aromatic hydrocarbons to the extensive aromatic rings in coal itself or to aromatic sulfides, amines or ethers. Accordingly, this study is exploring how such crucial hydrogen-transfer processes might be catalyzed by soluble, low-valent transition metal complexes and/or Lewis acids under moderate conditions of temperature and pressure. By learning the mechanism whereby H{sub 2}, metal hydrides or partially hydrogenated aromatics do transfer hydrogen to model aromatic compounds, with the aid of homogeneous, bimetallic catalysts, we hope to identify new methods for producing superior fuels from coal.

  3. Numerical simulation of heat transfer to separation tio2/water nanofluids flow in an asymmetric abrupt expansion

    Directory of Open Access Journals (Sweden)

    Oon Cheen Sean


    Full Text Available Flow separation and reattachment of 0.2% TiO2 nanofluid in an asymmetric abrupt expansion is studied in this paper. Such flows occur in various engineering and heat transfer applications. Computational fluid dynamics package (FLUENT is used to investigate turbulent nanofluid flow in the horizontal double-tube heat exchanger. The meshing of this model consists of 43383 nodes and 74891 elements. Only a quarter of the annular pipe is developed and simulated as it has symmetrical geometry. Standard k-epsilon second order implicit, pressure based-solver equation is applied. Reynolds numbers between 17050 and 44545, step height ratio of 1 and 1.82 and constant heat flux of 49050 W/m2 was utilized in the simulation. Water was used as a working fluid to benchmark the study of the heat transfer enhancement in this case. Numerical simulation results show that the increase in the Reynolds number increases the heat transfer coefficient and Nusselt number of the flowing fluid. Moreover, the surface temperature will drop to its lowest value after the expansion and then gradually increase along the pipe. Finally, the chaotic movement and higher thermal conductivity of the TiO2 nanoparticles have contributed to the overall heat transfer enhancement of the nanofluid compare to the water.

  4. Muon transfer from muonic hydrogen to heavier atoms; Transfert de charge muonique

    Energy Technology Data Exchange (ETDEWEB)

    Dupays, A


    This work concerns muon transfer from muonic hydrogen to heavier atoms. Recently, a method of measurement of the hyperfine structure of ground-state muonic hydrogen based on the collision energy dependence of the muon transfer rate to oxygen has been proposed. This proposal is based on measurements which where performed at the Paul Scherrer Institute in the early nineties which indicate that the muon transfer from muonic hydrogen to oxygen increases by a factor of 4 going from thermal to 0.12 eV energies. The motivation of our calculations was to confirm this behaviour. To study the collision energy dependence of the muon transfer rate, we have used a time-independent close-coupling method. We have set up an hyperspherical elliptic formalism valid for nonzero total angular momentum which allows accurate computations of state-to-state reactive and charge exchange processes. We have applied this formalism to muon-transfer process to oxygen and neon. The comparison with experimental results is in both cases excellent. Finally, the neon transfer rate dependence with energy suggests to use neon instead of oxygen to perform a measurement of the hyperfine structure of muonic hydrogen. The results of accurate calculations of the muon transfer rates from muonic protium and deuterium atoms to nitrogen, oxygen and neon are also reported. Very good agreement with measured rates is obtained and for the three systems, the isotopic effect is perfectly reproduced. (author)

  5. Sharpening coarse-to-fine stereo vision by perceptual learning: asymmetric transfer across the spatial frequency spectrum. (United States)

    Li, Roger W; Tran, Truyet T; Craven, Ashley P; Leung, Tsz-Wing; Chat, Sandy W; Levi, Dennis M


    Neurons in the early visual cortex are finely tuned to different low-level visual features, forming a multi-channel system analysing the visual image formed on the retina in a parallel manner. However, little is known about the potential 'cross-talk' among these channels. Here, we systematically investigated whether stereoacuity, over a large range of target spatial frequencies, can be enhanced by perceptual learning. Using narrow-band visual stimuli, we found that practice with coarse (low spatial frequency) targets substantially improves performance, and that the improvement spreads from coarse to fine (high spatial frequency) three-dimensional perception, generalizing broadly across untrained spatial frequencies and orientations. Notably, we observed an asymmetric transfer of learning across the spatial frequency spectrum. The bandwidth of transfer was broader when training was at a high spatial frequency than at a low spatial frequency. Stereoacuity training is most beneficial when trained with fine targets. This broad transfer of stereoacuity learning contrasts with the highly specific learning reported for other basic visual functions. We also revealed strategies to boost learning outcomes 'beyond-the-plateau'. Our investigations contribute to understanding the functional properties of the network subserving stereovision. The ability to generalize may provide a key principle for restoring impaired binocular vision in clinical situations.

  6. Hydrogen-driven asymmetric reduction of hydroxyacetone to (R-1,2-propanediol by Ralstonia eutropha transformant expressing alcohol dehydrogenase from Kluyveromyces lactis

    Directory of Open Access Journals (Sweden)

    Oda Takahiro


    Full Text Available Abstract Background Conversion of industrial processes to more nature-friendly modes is a crucial subject for achieving sustainable development. Utilization of hydrogen-oxidation reactions by hydrogenase as a driving force of bioprocess reaction can be an environmentally ideal method because the reaction creates no pollutants. We expressed NAD-dependent alcohol dehydrogenase from Kluyveromyces lactis in a hydrogen-oxidizing bacterium: Ralstonia eutropha. This is the first report of hydrogen-driven in vivo coupling reaction of the alcohol dehydrogenase and indigenous soluble NAD-reducing hydrogenase. Asymmetric reduction of hydroxyacetone to (R-1,2-propanediol, which is a commercial building block for antibacterial agents, was performed using the transformant as the microbial cell catalyst. Results The two enzymes coupled in vitro in vials without a marked decrease of reactivity during the 20 hr reaction because of the hydrogenase reaction, which generates no by-product that affects enzymes. Alcohol dehydrogenase was expressed functionally in R. eutropha in an activity level equivalent to that of indigenous NAD-reducing hydrogenase under the hydrogenase promoter. The hydrogen-driven in vivo coupling reaction proceeded only by the transformant cell without exogenous addition of a cofactor. The decrease of reaction velocity at higher concentration of hydroxyacetone was markedly reduced by application of an in vivo coupling system. Production of (R-1,2-propanediol (99.8% e.e. reached 67.7 g/l in 76 hr with almost a constant rate using a jar fermenter. The reaction velocity under 10% PH2 was almost equivalent to that under 100% hydrogen, indicating the availability of crude hydrogen gas from various sources. The in vivo coupling system enabled cell-recycling as catalysts. Conclusions Asymmetric reduction of hydroxyacetone by a coupling reaction of the two enzymes continued in both in vitro and in vivo systems in the presence of hydrogen. The in vivo

  7. Transfer Hydrogenation in Open-Shell Nucleotides — A Theoretical Survey

    Directory of Open Access Journals (Sweden)

    Florian Achrainer


    Full Text Available The potential of a larger number of sugar models to act as dihydrogen donors in transfer hydrogenation reactions has been quantified through the calculation of hydrogenation energies of the respective oxidized products. Comparison of the calculated energies to hydrogenation energies of nucleobases shows that many sugar fragment radicals can reduce pyrimidine bases such as uracil in a strongly exothermic fashion. The most potent reducing agent is the C3' ribosyl radical. The energetics of intramolecular transfer hydrogenation processes has also been calculated for a number of uridinyl radicals. The largest driving force for such a process is found for the uridin-C3'-yl radical, whose rearrangement to the C2'-oxidized derivative carrying a dihydrouracil is predicted to be exothermic by 61.1 kJ/mol in the gas phase.

  8. Insights into the Hydrogen-Atom Transfer of the Blue Aroxyl. (United States)

    Bächle, Josua; Marković, Marijana; Kelterer, Anne-Marie; Grampp, Günter


    An experimental and theoretical study on hydrogen-atom transfer dynamics in the hydrogen-bonded substituted phenol/phenoxyl complex of the blue aroxyl (2,4,6-tri-tert-butylphenoxyl) is presented. The experimental exchange dynamics is determined in different organic solvents from the temperature-dependent alternating line-width effect in the continuous-wave ESR spectrum. From bent Arrhenius plots, effective tunnelling contributions with parallel heavy-atom motion are concluded. To clarify the transfer mechanism, reaction paths for different conformers of the substituted phenol/phenoxyl complex are modelled theoretically. Various DFT and post-Hartree-Fock methods including multireference methods are applied. From the comparison of experimental and theoretical data it is concluded that the system favours concerted hydrogen-atom transfer along a parabolic reaction path caused by heavy-atom motion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. An S-N2-model for proton transfer in hydrogen-bonded systems

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens


    A new mechanism of proton transfer in donor-acceptor complexes with long hydrogen bonds is suggested. The transition is regarded as totally adiabatic. Two closest water molecules that move synchronously by hindered translation to and from the reaction complex are crucial. The water molecules induce...... a shift of the proton from the donor to the acceptor with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor and acceptor. Expressions for the activation barrier and kinetic hydrogen isotope effect are derived. The general scheme is illustrated with the use...

  10. Assuring process safety in the transfer of hydrogen cyanide manufacturing technology. (United States)

    Maxwell, Gary R; Edwards, Victor H; Robertson, Mark; Shah, Kamal


    This paper outlines the critical issues to be addressed in the transfer of hydrogen cyanide (HCN) manufacturing technology to a licensee. Process safety management (PSM) is of critical importance because of the toxicity, flammability and reactivity of HCN. The critical issues are based on experience that DuPont has gained (1) while safely manufacturing hydrogen cyanide for over 50 years, and (2) while DuPont has safely licensed HCN technology to other firms at locations around the world. DuPont's HCN experience has been combined with Aker Kvaerner's project engineering experience to insure the safe transfer of HCN technology to a licensee.

  11. Effects of surface residual species in SBA-16 on encapsulated chiral (1S,2S)-DPEN-RuCl2(TPP)2 in asymmetric hydrogenation of acetophenone (United States)

    Shi, Xiufeng; Xing, Bin; Fan, Binbin; Xue, Zhaoteng; Li, Ruifeng


    The SBA-16 obtained by different routes of elimination of organic templates were used as the hosts for encapsulation of chiral Ru complex (1S,2S)-DPEN-RuCl2(TPP)2 ( 1) (DPEN = 1,2-diphenylethylene-diamine, TPP = triphenyl phosphine). The methods for removing templates had distinct effects on the amount of residual template in SBA-16, which made the SBA-16 with different surface and structure properties. 1 encapsulated in SBA-16 extracted with the mixture of pyridine and ethanol showed higher activity and enantioselectivity for acetophenone asymmetric hydrogenation.

  12. Ir-Catalyzed Asymmetric and Regioselective Hydrogenation of Cyclic Allylsilanes and Generation of Quaternary Stereocenters via the Hosomi-Sakurai Allylation. (United States)

    Rabten, Wangchuk; Margarita, Cristiana; Eriksson, Lars; Andersson, Pher G


    A number of cyclic dienes containing the allylsilane moiety were prepared by a Birch reduction and subjected to iridium-catalyzed regioselective and asymmetric hydrogenation, which provided chiral allylsilanes in high conversion and enantiomeric excess (up to 99 % ee). The compounds were successively used in the Hosomi-Sakurai allylation with various aldehydes employing TiCl 4 as Lewis acid, providing adducts with two additional stereogenic centers in excellent diastereoselectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Turning symmetric an asymmetric hydrogen bond with the inclusion of nuclear quantum effects: the case of the [CN···H···NC]- complex. (United States)

    Moreno, Diego V; González, Sergio A; Reyes, Andrés


    Nuclear quantum effects (NQE) on the geometry, energy, and electronic structure of the [CN·L·NC](-) complex (L = H, D, T) are investigated with the recently developed APMO/MP2 code. This code implements the nuclear molecular orbital approach (NMO) at the Hartree-Fock (HF) and MP2 levels of theory for electrons and quantum nuclei. In a first study, we examined the H/D/T isotope effects on the geometry and electronic structure of the CNH molecule at NMO/HF and NMO/MP2 levels of theory. We found that when increasing the hydrogen nuclear mass there is a reduction of the R(N-H) bond distance and an increase of the electronic population on the hydrogen atom. Our calculated bond distances are in good agreement with experimental and other theoretical results. In a second investigation, we explored the hydrogen NQE on the geometry of [CNHNC](-) complex at the NMO/HF and NMO/MP2 levels of theory. We discovered that while a NMO/HF calculation presented an asymmetric hydrogen bond, the NMO/MP2 calculation revealed a symmetric H-bond. We also examined the H/D/T isotope effects on the geometry and stabilization energy of the [CNHNC](-) complex. We noted that gradual increases in hydrogen mass led to reductions of the R(NN) distance and destabilization of the hydrogen bond (H-bond). A discussion of these results is given in terms of the hydrogen nuclear delocalization effects on the electronic structure and energy components. To the best of our knowledge, this is the first ab initio NMO study that reveals the importance of including nuclear quantum effects in conventional electronic structure calculations for an enhanced description of strong-low-barrier H-bonded systems.

  14. In tandem or alone: a remarkably selective transfer hydrogenation of alkenes catalyzed by ruthenium olefin metathesis catalysts. (United States)

    Zieliński, Grzegorz Krzysztof; Samojłowicz, Cezary; Wdowik, Tomasz; Grela, Karol


    A system for transfer hydrogenation of alkenes, composed of a ruthenium metathesis catalyst and HCOOH, is presented. This operationally simple system can be formed directly after a metathesis reaction to effect hydrogenation of the metathesis product in a single-pot. These hydrogenation conditions are applicable to a wide range of alkenes and offer remarkable selectivity.

  15. Hydrogen Transfer during Liquefaction of Elbistan Lignite to Biomass; Total Reaction Transformation Approach (United States)

    Koyunoglu, Cemil; Karaca, Hüseyin


    Given the high cost of the tetraline solvent commonly used in liquefaction, the use of manure with EL is an important factor when considering the high cost of using tetraline as a hydrogen transfer source. In addition, due to the another cost factor which is the catalyst prices, red mud (commonly used, produced as a byproduct in the production of aluminium) is reduced cost in the work of liquefaction of coal, biomass, even coal combined biomass, corresponding that making the EL liquefaction an agenda for our country is another important factor. Conditions for liquefaction experiments conducted for hydrogen transfer from manure to coal; Catalyst concentration of 9%, liquid/solid ratio of 3/1, reaction time of 60 min, fertilizer/lignite ratio of 1/3, and the reaction temperature of 400 °C, the stirred speed of 400 rpm and the initial nitrogen pressure of 20 bar was fixed. In order to demonstrate the hydrogen, transfer from manure to coal, coal is used solely, by using tetraline (also known as a hydrogen carrier) and distilled water which is not hydrogen donor as a solvent in the co-liquefaction of experiments, and also the liquefaction conditions are carried out under an inert (N2) gas atmosphere. According to the results of the obtained liquefaction test; using tetraline solvent the total liquid product conversion percentage of the oil + gas conversion was 38.3 %, however, the results of oil+gas conversion obtained using distilled water and EL combined with manure the total liquid product conversion percentage was 7.4 %. According to the results of calorific value and elemental analysis, only the ratio of (H/C)atomic of coal obtained by using tetraline increased with the liquefaction of manure and distilled water. The reason of the increase in the amount of hydrogen due to hydrogen transfer from the manure on the solid surface of the coal, and also on the surface of the inner pore of the coal during the liquefaction, brings about the evaluation of the coal as a

  16. Efficient Energy Transfer in Supramolecular, Hydrogen-Bonded Polypyridylruthenium-Osmium Complexes

    NARCIS (Netherlands)

    Rau, Sven; Schäfer, Bernhard; Schebesta, Sebastian; Grüßing, André; Poppitz, Wolfgang; Walther, Dirk; Duati, Marco; Browne, Wesley R.; Vos, Johannes G.

    Hydrogen bond association between ruthenium bibenzimidazole and carboxylated polypyridylosmium complexes results in stable supramolecular aggregates. The determined stability constant of logK approximate to 6 +/- 0.3 allows efficient energy transfer from the ruthenium to the osmium moiety. (C)

  17. Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds (United States)

    One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

  18. Energy Transfer with Hydrogen and Superconductivity - The Review of the First Experimental Results (United States)

    Vysotsky, V. S.; Antyukhov, I. V.; Firsov, V. P.; Blagov, E. V.; Kostyuk, V. V.; Nosov, A. A.; Fetisov, S. S.; Zanegin, S. Yu.; Rachuk, V. S.; Katorgin, B. I.

    The transfer of massive amounts of both electrical and chemical power over long distances will present a major challenge for the global energy enterprise in future. Attraction of hydrogen is apparent as a chemical energy agent, possessing among the highest energy density content of various common fuels, whose combustive "waste" is simply water. The usage of "gratis" cold to cool a superconducting cable made of proper superconductor permits to deliver extra electrical power with the same line. This, rather old theoretical idea recently found its experimental realization. The team of Russian institutes and organizations with using Italian-produced MgB2 wire has made and successfully tested two hybrid energy transfer lines with liquid hydrogen as a chemical source of power and superconducting cable as a source of electricity. The first line has been tested in 2011. It has length ∼10 m, maximum liquid hydrogen flow ∼250 g/s and maximum current of MgB2 superconducting cable 2600 A @ 20K. This test was the first experimental proof of conception of the hybrid energy transfer line. The second line has been tested in October 2013. It has length ∼30 m. The new MgB2 cable has critical current at 21 K ∼3500 A and successfully passed high voltage DC test of 50 kV. New hydrogen cryostat has three sections with different types of thermal insulation in each section. The idea of hybrid energy transfer is formulated and details of first experiments are reviewed.

  19. Laboratory Measurements of Charge Transfer on Atomic Hydrogen at Thermal Energies (United States)

    Havener, C. C.; Vane, C. R.; Krause, H. F.; Stancil, P. C.; Mroczkowski, T.; Savin, D. W.


    We describe our ongoing program to measure velocity dependent charge transfer (CT) cross sections for selected ions on atomic hydrogen using the ion-aloin merged-beams apparatus at Oak Ridge Natioiial Laboralory. Our focus is on those ions for which CT plays an important role in determining the ionization structure, line emis sion, and thermal structure of observed cosmic photoionized plasmas.

  20. Heat and mass transfer rates during flow of dissociated hydrogen gas over graphite surface (United States)

    Nema, V. K.; Sharma, O. P.


    To improve upon the performance of chemical rockets, the nuclear reactor has been applied to a rocket propulsion system using hydrogen gas as working fluid and a graphite-composite forming a part of the structure. Under the boundary layer approximation, theoretical predictions of skin friction coefficient, surface heat transfer rate and surface regression rate have been made for laminar/turbulent dissociated hydrogen gas flowing over a flat graphite surface. The external stream is assumed to be frozen. The analysis is restricted to Mach numbers low enough to deal with the situation of only surface-reaction between hydrogen and graphite. Empirical correlations of displacement thickness, local skin friction coefficient, local Nusselt number and local non-dimensional heat transfer rate have been obtained. The magnitude of the surface regression rate is found low enough to ensure the use of graphite as a linear or a component of the system over an extended period without loss of performance.

  1. Note: Charge transfer in a hydrated peptide group is determined mainly by its intrinsic hydrogen-bond energetics

    Energy Technology Data Exchange (ETDEWEB)

    Mirkin, Noemi G.; Krimm, Samuel [LSA Biophysics, University of Michigan, 930 N. University Ave., Ann Arbor, Michigan 48109-1055 (United States)


    Charge transfer in a hydrogen-bonded N-methylacetamide(H{sub 2}O){sub 3} system is obtained from ωB97X-D/6-31++G** and CHelpG atomic charge calculations of individual peptide-water interactions as well as that of the entire complex. In the latter, the electron transfer to water is 0.19 e, influenced primarily by the hydrogen bonds to the C=O group. The values of such charge transfer are paralleled by the corresponding intrinsic hydrogen-bond energies. These results support the desirability of incorporating charge transfer in molecular mechanics energy functions.

  2. Bias-voltage dependence of perpendicular spin-transfer torque in asymmetric MgO-based magnetic tunnel junctions

    KAUST Repository

    Oh, Se Chung


    Spin-transfer torque (STT) allows the electrical control of magnetic states in nanostructures. The STT in magnetic tunnel junctions (MTJs) is of particular importance owing to its potential for device applications. It has been demonstrated that the MTJ has a sizable perpendicular STT (, field-like torque), which substantially affects STT-driven magnetization dynamics. In contrast to symmetric MTJs where the bias dependence of is quadratic, it is theoretically predicted that the symmetry breaking of the system causes an extra linear bias dependence. Here, we report experimental results that are consistent with the predicted linear bias dependence in asymmetric MTJs. The linear contribution is quite significant and its sign changes from positive to negative as the asymmetry is modified. This result opens a way to design the bias dependence of the field-like term, which is useful for device applications by allowing, in particular, the suppression of the abnormal switching-back phenomena. © 2009 Macmillan Publishers Limited. All rights reserved.

  3. Asymmetric angular dependence of spin-transfer torques in CoFe/Mg-B-O/CoFe magnetic tunnel junctions

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Ling, E-mail:; Xu, Zhi-Jun, E-mail:; Zuo, Xian-Jun; Yang, Ze-Jin, E-mail: [Department of Applied Physics, College of Science, Zhejiang University of Technology, Hangzhou 310023 (China); Gao, Qing-He [College of Science, Northeastern University, Shenyang 110004, China, Information Engineering College, Liaoning University of Traditional Chinese Medicine, Shenyang 110847 (China); Linghu, Rong-Feng, E-mail: [School of Physics and Electronics Sciences, Guizhou Education University, Guiyang 550018 (China); Guo, Yun-Dong, E-mail: [College of Engineering and Technology, Neijiang Normal University, Neijiang 641112 (China)


    Using a first-principles noncollinear wave-function-matching method, we studied the spin-transfer torques (STTs) in CoFe/Mg-B-O/CoFe(001) magnetic tunnel junctions (MTJs), where three different types of B-doped MgO in the spacer are considered, including B atoms replacing Mg atoms (Mg{sub 3}BO{sub 4}), B atoms replacing O atoms (Mg{sub 4}BO{sub 3}), and B atoms occupying interstitial positions (Mg{sub 4}BO{sub 4}) in MgO. A strong asymmetric angular dependence of STT can be obtained both in ballistic CoFe/Mg{sub 3}BO{sub 4} and CoFe/Mg{sub 4}BO{sub 4} based MTJs, whereas a nearly symmetric STT curve is observed in the junctions based on CoFe/Mg{sub 4}BO{sub 3}. Furthermore, the asymmetry of the angular dependence of STT can be suppressed significantly by the disorder of B distribution. Such skewness of STTs in the CoFe/Mg-B-O/CoFe MTJs could be attributed to the interfacial resonance states induced by the B diffusion into MgO spacer.

  4. Asymmetric Chemoenzymatic Reductive Acylation of Ketones by a Combined Iron-Catalyzed Hydrogenation-Racemization and Enzymatic Resolution Cascade

    KAUST Repository

    El-Sepelgy, Osama


    A general and practical process for the conversion of prochiral ketones into the corresponding chiral acetates has been realized. An iron carbonyl complex is reported to catalyze the hydrogenation-dehydrogenation-hydrogenation of prochiral ketones. By merging the iron-catalyzed redox reactions with enantioselective enzymatic acylations a wide range of benzylic, aliphatic and (hetero)aromatic ketones, as well as diketones, were reductively acylated. The corresponding products were isolated with high yields and enantioselectivities. The use of an iron catalyst together with molecular hydrogen as the hydrogen donor and readily available ethyl acetate as acyl donor make this cascade process highly interesting in terms of both economic value and environmental credentials.

  5. Catalytic Transfer Hydrogenation of Biomass-Derived Carbonyls over Hafnium-Based Metal-Organic Frameworks. (United States)

    Corma, Avelino; García-García, Pilar; Rojas-Buzo, Sergio


    A series of highly crystalline, porous, hafnium-based metal-organic frameworks (MOFs) have shown to catalyze the transfer hydrogenation reaction of levulinic ester to produce γ-valerolactone using isopropanol as hydrogen donor and the results are compared with the zirconium-based counterparts. The role of the metal center in Hf-MOFs has been identified and reaction parameters optimized. NMR studies with isotopically labeled isopropanol evidences that the transfer hydrogenation occurs via a direct intermolecular hydrogen transfer route. The catalyst, Hf-MOF-808, can be recycled several times with only a minor decrease in catalytic activity. Generality of the procedure was shown by accomplishing the transformation with aldehydes, ketones and α,β-unsaturated carbonyl compounds. The combination of Hf-MOF-808 with the Brønsted acidic Al-Beta zeolite gives the four-step one-pot transformation of furfural to γ-valerolactone in good yield of 72%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Asymmetric fluorocyclizations of alkenes. (United States)

    Wolstenhulme, Jamie R; Gouverneur, Véronique


    CONSPECTUS: The vicinal fluorofunctionalization of alkenes is an attractive transformation that converts feedstock olefins into valuable cyclic fluorinated molecules for application in the pharmaceutical, agrochemical, medical, and material sectors. The challenges associated with asymmetric fluorocyclizations induced by F(+) reagents are distinct from other types of halocyclizations. Processes initiated by the addition of an F(+) reagent onto an alkene do not involve the reversible formation of bridged fluoronium ions but generate acyclic β-fluorocationic intermediates. This mechanistic feature implies that fluorocyclizations are not stereospecific. A discontinuity exists between the importance of this class of fluorocyclization and the activation modes currently available to implement successful catalysis. Progress toward fluorocyclization has been achieved by investing in neutral and cationic [NF] reagent development. The body of work on asymmetric fluorination using chiral cationic [NF](+) reagents prepared by fluorine transfer from the dicationic [NF](2+) reagent Selectfluor to quinuclidines, inspired the development of asymmetric F(+)-induced fluorocyclizations catalyzed by cinchona alkaloids; for catalysis, the use of N-fluorobenzenesulfonimide, which is less reactive than Selectfluor, ensures that the achiral F(+) source remains unreactive toward the alkene. These organocatalyzed enantioselective fluorocyclizations can be applied to indoles to install the fluorine on a quaternary benzylic stereogenic carbon center and to afford fluorinated analogues of natural products featuring the hexahydropyrrolo[2,3-b]indole or the tetrahydro-2H-furo[2,3-b]indole skeleton. In an alternative approach, the poor solubility of dicationic Selectfluor bis(tetrafluoroborate) in nonpolar solvent was exploited with anionic phase transfer catalysis as the operating activation mode. Exchange of the tetrafluoroborate ions of Selectfluor with bulky lipophilic chiral anions (e

  7. TD-DFT study on electron transfer mobility and intramolecular hydrogen bond of substituted indigo derivatives (United States)

    Ma, Chi; Li, Hui; Yang, Yonggang; Li, Donglin; Liu, Yufang


    The density functional theory (DFT) and time-dependent density functional theory (TDDFT) method were carried out to investigate the ground and excited states of indigo and its derivative molecules. The results demonstrate that the intramolecular hydrogen bond I is weakened and the intramolecular hydrogen bond II is strengthened upon photo-excitation to the S1 state. In the absorption spectra, the substitution at R4R4, of indigo causes a significant redshift. In addition, the halogen substitution obviously increases the electron transfer mobility of indigo. It is proved that the halogen substitution may be a new method to design high performance organic semiconductors.

  8. Quantitative dissection of hydrogen bond-mediated proton transfer in the ketosteroid isomerase active site (United States)

    Sigala, Paul A.; Fafarman, Aaron T.; Schwans, Jason P.; Fried, Stephen D.; Fenn, Timothy D.; Caaveiro, Jose M. M.; Pybus, Brandon; Ringe, Dagmar; Petsko, Gregory A.; Boxer, Steven G.; Herschlag, Daniel


    Hydrogen bond networks are key elements of protein structure and function but have been challenging to study within the complex protein environment. We have carried out in-depth interrogations of the proton transfer equilibrium within a hydrogen bond network formed to bound phenols in the active site of ketosteroid isomerase. We systematically varied the proton affinity of the phenol using differing electron-withdrawing substituents and incorporated site-specific NMR and IR probes to quantitatively map the proton and charge rearrangements within the network that accompany incremental increases in phenol proton affinity. The observed ionization changes were accurately described by a simple equilibrium proton transfer model that strongly suggests the intrinsic proton affinity of one of the Tyr residues in the network, Tyr16, does not remain constant but rather systematically increases due to weakening of the phenol–Tyr16 anion hydrogen bond with increasing phenol proton affinity. Using vibrational Stark spectroscopy, we quantified the electrostatic field changes within the surrounding active site that accompany these rearrangements within the network. We were able to model these changes accurately using continuum electrostatic calculations, suggesting a high degree of conformational restriction within the protein matrix. Our study affords direct insight into the physical and energetic properties of a hydrogen bond network within a protein interior and provides an example of a highly controlled system with minimal conformational rearrangements in which the observed physical changes can be accurately modeled by theoretical calculations. PMID:23798390

  9. Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol with Recyclable Al-Zr@Fe Mixed Oxides

    DEFF Research Database (Denmark)

    He, Jian; Li, Hu; Riisager, Anders


    A series of magnetic, acid/base bifunctional Al–Zr@Fe3O4 catalysts were successfully prepared by a facile coprecipitation method and utilized in the catalytic transfer hydrogenation (CTH) of furfural to furfuryl alcohol with 2-propanol as hydrogen source. The physicochemical properties and morpho......A series of magnetic, acid/base bifunctional Al–Zr@Fe3O4 catalysts were successfully prepared by a facile coprecipitation method and utilized in the catalytic transfer hydrogenation (CTH) of furfural to furfuryl alcohol with 2-propanol as hydrogen source. The physicochemical properties...... with a Al3+/Zr4+/Fe3O4 molar ratio of 21:9:3 was found to exhibit a high furfuryl alcohol yield of 90.5 % in the CTH from furfural at 180 °C after 4 h with a comparatively low activation energy of 45.3 kJ mol−1, as calculated from the Arrhenius equation. Moreover, leaching and recyclability tests confirmed...

  10. Direct time-resolved spectroscopic investigation of intramolecular hydrogen atom transfer of deoxyblebbistatin (United States)

    Li, Ming-De; Zhu, Ruixue; Lee Phillips, David


    The photophysics and photochemistry of deoxyblebbistatin was investigated using femtosecond time-resolved transient absorption spectroscopy. An ultrafast intramolecular hydrogen atom transfer (IHAT) appears to take place via the first singlet excited state of deoxyblebbistatin within 8 ps. Absorption and fluorescence photochemical results indicate the IHAT process leads to mainly conversion of deoxyblebbistatin into an enol form final product which was observed and characterized by resonance Raman spectroscopy.

  11. Ruthenium(II) pincer complexes with oxazoline arms for efficient transfer hydrogenation reactions

    KAUST Repository

    Chen, Tao


    Well-defined P NN CN pincer ruthenium complexes bearing both strong phosphine and weak oxazoline donors were developed. These easily accessible complexes exhibit significantly better catalytic activity in transfer hydrogenation of ketones compared to their PN 3P analogs. These reactions proceed under mild and base-free conditions via protonation- deprotonation of the \\'NH\\' group in the aromatization-dearomatization process. © 2012 Elsevier Ltd. All rights reserved.

  12. Three-dimensional simulation of an argon–hydrogen DC non-transferred arc plasma torch


    Guo, Z; Yin, S; Liao, H; Gu, S


    Simulations of a DC non-transferred arc plasma torch operating with argon–hydrogen have been performed by using a three-dimensional model. An artificially high electrical conductivity layer is employed to allow the current passing through the low temperature region near the anode wall. A new way by using two equations to describe the current density distribution is developed. Besides, a new method for determining the location of the arc-root attachment is proposed, in which the minimum total ...

  13. Enantioselective Iridium Catalyzed Carbonyl Allylation from the Alcohol or Aldehyde Oxidation Level via Transfer Hydrogenative Coupling of Allyl Acetate: Departure from Chirally Modified Allyl Metal Reagents in Carbonyl Addition


    Kim, In Su; Ngai, Ming-Yu; Krische, Michael J.


    Under the conditions of transfer hydrogenation employing an iridium catalyst generated in situ from [Ir(cod)Cl]2, the chiral phosphine ligands (R)-BINAP or (R)-Cl,MeO-BIPHEP and m-nitrobenzoic acid, allyl acetate couples to allylic alcohols 1a-1c, aliphatic alcohols 1d-1l and benzylic alcohols 1m-1u to furnish products of carbonyl allylation 3a-3u with exceptional levels of asymmetric induction. The very same set of optically enriched carbonyl allylation products 3a-3u are accessible from ena...

  14. Reactivity of hydropersulfides toward the hydroxyl radical unraveled: disulfide bond cleavage, hydrogen atom transfer, and proton-coupled electron transfer. (United States)

    Anglada, Josep M; Crehuet, Ramon; Adhikari, Sarju; Francisco, Joseph S; Xia, Yu


    Hydropersulfides (RSSH) are highly reactive as nucleophiles and hydrogen atom transfer reagents. These chemical properties are believed to be key for them to act as antioxidants in cells. The reaction involving the radical species and the disulfide bond (S-S) in RSSH, a known redox-active group, however, has been scarcely studied, resulting in an incomplete understanding of the chemical nature of RSSH. We have performed a high-level theoretical investigation on the reactions of the hydroxyl radical (˙OH) toward a set of RSSH (R = -H, -CH 3 , -NH 2 , -C(O)OH, -CN, and -NO 2 ). The results show that S-S cleavage and H-atom abstraction are the two competing channels. The electron inductive effect of R induces selective ˙OH substitution at one sulfur atom upon S-S cleavage, forming RSOH and ˙SH for the electron donating groups (EDGs), whereas producing HSOH and ˙SR for the electron withdrawing groups (EWGs). The H-Atom abstraction by ˙OH follows a classical hydrogen atom transfer (hat) mechanism, producing RSS˙ and H 2 O. Surprisingly, a proton-coupled electron transfer (pcet) process also occurs for R being an EDG. Although for RSSH having EWGs hat is the leading channel, S-S cleavage can be competitive or even dominant for the EDGs. The overall reactivity of RSSH toward ˙OH attack is greatly enhanced with the presence of an EDG, with CH 3 SSH being the most reactive species found in this study (overall rate constant: 4.55 × 10 12 M -1 s -1 ). Our results highlight the complexity in RSSH reaction chemistry, the extent of which is closely modulated by the inductive effect of the substituents in the case of the oxidation by hydroxyl radicals.

  15. Liquid oxygen/liquid hydrogen boost/vane pump for the advanced orbit transfer vehicles auxiliary propulsion system (United States)

    Gluzek, F.; Mokadam, R. G.; To, I. H.; Stanitz, J. D.; Wollschlager, J.


    A rotating, positive displacement vane pump with an integral boost stage was designed to pump saturated liquid oxygen and liquid hydrogen for auxiliary propulsion system of orbit transfer vehicle. This unit is designed to ingest 10% vapor by volume, contamination free liquid oxygen and liquid hydrogen. The final pump configuration and the predicted performance are included.

  16. Manipulating the Energetics and Rates of Electron Transfer in Rhodobacter capsulatus Reaction Centers with Asymmetric Pigment Content. (United States)

    Faries, Kaitlyn M; Dylla, Nicholas P; Hanson, Deborah K; Holten, Dewey; Laible, Philip D; Kirmaier, Christine


    Seemingly redundant parallel pathways for electron transfer (ET), composed of identical sets of cofactors, are a cornerstone feature of photosynthetic reaction centers (RCs) involved in light-energy conversion. In native bacterial RCs, both A and B branches house one bacteriochlorophyll (BChl) and one bacteriopheophytin (BPh), but the A branch is used exclusively. Described herein are the results obtained for two Rhodobacter capsulatus RCs with an unnaturally high degree of cofactor asymmetry, two BPh on the RC's B side and two BChl on the A side. These pigment changes derive, respectively, from the His(M180)Leu mutation [a BPh (Φ B ) replaces the B-side BChl (B B )], and the Leu(M212)His mutation [a BChl (β A ) replaces the A-side BPh (H A )]. Additionally, Tyr(M208)Phe was employed to disfavor ET to the A branch; in one mutant, Val(M131)Glu creates a hydrogen bond to H B to enhance ET to H B . In both Φ B mutants, the decay kinetics of the excited primary ET donor (P*) resolve three populations with lifetimes of ∼9 ps (50-60%), ∼40 ps (10-20%), and ∼200 ps (20-30%), with P + Φ B - formed predominantly from the 9 ps fraction. The 50-60% yield of P + Φ B - is the highest yet observed for a Φ B -containing RC. The results provide insight into factors needed for efficient multistep ET.

  17. Coolant-side heat-transfer rates for a hydrogen-oxygen rocket and a new technique for data correlation (United States)

    Schacht, R. L.; Quentmeyer, R. J.


    An experimental investigation was conducted to determine the coolant-side, heat transfer coefficients for a liquid cooled, hydrogen-oxygen rocket thrust chamber. Heat transfer rates were determined from measurements of local hot gas wall temperature, local coolant temperature, and local coolant pressure. A correlation incorporating an integration technique for the transport properties needed near the pseudocritical temperature of liquid hydrogen gives a satisfactory prediction of hot gas wall temperatures.

  18. Scanning Tunneling Microscopy Measurements of the Full Cycle of a Heterogeneous Asymmetric Hydrogenation Reaction on Chirally Modified Pt(111)

    DEFF Research Database (Denmark)

    Demers-Carpentier, Vincent; Goubert, Guillaume; Masini, Federico


    protrusion compared to TFAP in dimer structures. They are attributed to a half-hydrogenated intermediate. The introduction of H2 to a mixture of (R)-NEA and TFAP on Pt(111) leads to the removal of TFAP without any change in the population of the modifier, as required for an efficient chirally modified...

  19. Intra- and interspecies transfer and expression of Rhizobium japonicum hydrogen uptake genes and autotrophic growth capability. (United States)

    Lambert, G R; Cantrell, M A; Hanus, F J; Russell, S A; Haddad, K R; Evans, H J


    Cosmids containing hydrogen uptake genes have previously been isolated in this laboratory. Four new cosmids that contain additional hup gene(s) have now been identified by conjugal transfer of a Rhizobium japonicum 122DES gene bank into a Tn5-generated Hup(-) mutant and screening for the acquisition of Hup activity. The newly isolated cosmids, pHU50-pHU53, contain part of the previously isolated pHU1 but extend as far as 20 kilobases beyond its border. pHU52 complements five of six Hup(-) mutants and confers activity on several Hup(-) wild-type R. japonicum strains in the free-living state and where tested in nodules. Transconjugants obtained from interspecies transfer of pHU52 to Rhizobium meliloti 102F28, 102F32, and 102F51 and Rhizobium leguminosarum 128C53 showed hydrogen-dependent methyleneblue reduction, performed the oxyhydrogen reaction, and showed hydrogen-dependent autotrophic growth by virtue of the introduced genes. The identity of the presumptive transconjugants was confirmed by antibiotic-resistance profiles and by plant nodulation tests.

  20. Liquid Acquisition Device Hydrogen Outflow Testing on the Cryogenic Propellant Storage and Transfer Engineering Design Unit (United States)

    Zimmerli, Greg; Statham, Geoff; Garces, Rachel; Cartagena, Will


    As part of the NASA Cryogenic Propellant Storage and Transfer (CPST) Engineering Design Unit (EDU) testing with liquid hydrogen, screen-channel liquid acquisition devices (LADs) were tested during liquid hydrogen outflow from the EDU tank. A stainless steel screen mesh (325x2300 Dutch T will weave) was welded to a rectangular cross-section channel to form the basic LAD channel. Three LAD channels were tested, each having unique variations in the basic design. The LADs fed a common outflow sump at the aft end of the 151 cu. ft. volume aluminum tank, and included a curved section along the aft end and a straight section along the barrel section of the tank. Wet-dry sensors were mounted inside the LAD channels to detect when vapor was ingested into the LADs during outflow. The use of warm helium pressurant during liquid hydrogen outflow, supplied through a diffuser at the top of the tank, always led to early breakdown of the liquid column. When the tank was pressurized through an aft diffuser, resulting in cold helium in the ullage, LAD column hold-times as long as 60 minutes were achieved, which was the longest duration tested. The highest liquid column height at breakdown was 58 cm, which is 23 less than the isothermal bubble-point model value of 75 cm. This paper discusses details of the design, construction, operation and analysis of LAD test data from the CPST EDU liquid hydrogen test.

  1. Muon molecular formation and transfer rate in solid hydrogen-deuterium mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Jacot-Guillarmod, R. [Fribourg Univ. (Switzerland); Bailey, J.M. [Chester Technology (United Kingdom); Beer, G.A.; Knowles, P.E.; Mason, G.R.; Olin, A. [Victoria Univ., BC (Canada); Beveridge, J.L.; Marshall, G.M.; Mulhauser, F. [British Columbia Univ., Vancouver, BC (Canada). TRIUMF Facility; Fujiwara, M.C. [British Columbia Univ., Vancouver, BC (Canada); Huber, T.M. [Gustavus Adolphus Coll., St. Peter, MN (United States); Kammel, P.; Zmeskal, J. [Oesterreichische Akademie der Wissenschaften, Vienna (Austria); Kunselman, A.R. [Wyoming Univ., Laramie, WY (United States); Martoff, C.J. [Temple Univ., Philadelphia, PA (United States); Petitjean, C. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Wozniak, J. [Akademia Gorniczo-Hutnicza, Cracow (Poland). Inst. of Physics and Nuclear Technology


    In an experiment at TRIUMF to study muon-catalyzed fusion and associated atomic and molecular effects, negative muons were stopped in a solid protium hydrogen layer containing a small amount of deuterium. Most of the resulting {mu}H atoms disappeared by formation of HH{mu} molecules or by muon transfer to a deuteron. The {mu}D can drift almost freely through the hydrogen layer due to the Ramsauer-Townsend effect and may even leave the layer. If a thin neon layer is frozen atop the hydrogen, the exiting muonic atoms will very rapidly release their muon to a neon atom. The analysis of the time structure of the neon X-rays is used to determine the rates of the slower processes involved in the evolution of the {mu}H. This analysis has been performed with the help of Monte Carlo calculations, which simulate the kinetics of both {mu}H and {mu}D atoms in the hydrogen mixtures. (orig.). 23 refs.

  2. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction. Quarterly summary, June 1, 1991--August 31, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Eisch, J.J.


    The ultimate objective of this research is to uncover new catalytic processes for the liquefaction of coal and for upgrading coal-derived fuels by removing undesirable organosulfur, organonitrogen and organooxygen constituents. Basic to both the liquefaction of coal and the purification of coal liquids is the transfer of hydrogen from such sources as dihydrogen, metal hydrides or partially reduced aromatic hydrocarbons to the extensive aromatic rings in coal itself or to aromatic sulfides, amines or ethers. Accordingly, this study is exploring how such crucial hydrogen-transfer processes might be catalyzed by soluble, low-valent transition metal complexes and/or Lewis acids under moderate conditions of temperature and pressure. By learning the mechanism whereby H{sub 2}, metal hydrides or partially hydrogenated aromatics do transfer hydrogen to model aromatic compounds, with the aid of homogeneous, bimetallic catalysts, we hope to identify new methods for producing superior fuels from coal.

  3. A continuous flow strategy for the coupled transfer hydrogenation and etherification of 5-(hydroxymethyl)furfural using Lewis acid zeolites. (United States)

    Lewis, Jennifer D; Van de Vyver, Stijn; Crisci, Anthony J; Gunther, William R; Michaelis, Vladimir K; Griffin, Robert G; Román-Leshkov, Yuriy


    Hf-, Zr- and Sn-Beta zeolites effectively catalyze the coupled transfer hydrogenation and etherification of 5-(hydroxymethyl)furfural with primary and secondary alcohols into 2,5-bis(alkoxymethyl)furans, thus making it possible to generate renewable fuel additives without the use of external hydrogen sources or precious metals. Continuous flow experiments reveal nonuniform changes in the relative deactivation rates of the transfer hydrogenation and etherification reactions, which impact the observed product distribution over time. We found that the catalysts undergo a drastic deactivation for the etherification step while maintaining catalytic activity for the transfer hydrogenation step. (119) Sn and (29) Si magic angle spinning (MAS) NMR studies show that this deactivation can be attributed to changes in the local environment of the metal sites. Additional insights were gained by studying effects of various alcohols and water concentration on the catalytic reactivity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Polymer-Supported Cinchona Alkaloid-Derived Ammonium Salts as Recoverable Phase-Transfer Catalysts for the Asymmetric Synthesis of α-Amino Acids

    Directory of Open Access Journals (Sweden)

    Carmen Nájera


    Full Text Available Alkaloids such as cinchonidine, quinine and N-methylephedrine have been N-alkylated using polymeric benzyl halides or co-polymerized and then N-alkylated, thus affording a series of polymer-supported chiral ammonium salts which have been employed as phase-transfer catalysts in the asymmetric benzylation of an N-(diphenylmethyleneglycine ester. These new polymeric catalysts can be easily recovered by simple filtration after the reaction and reused. The best ee’s were achieved when Merrifield resin-anchored cinchonidinium ammonium salts were employed.

  5. Amide-Phosphonium Salt as Bifunctional Phase Transfer Catalyst for Asymmetric 1,6-Addition of Malonate Esters to para-Quinone Methides. (United States)

    Ge, Luo; Lu, Xuehe; Cheng, Cang; Chen, Jie; Cao, Weiguo; Wu, Xiaoyu; Zhao, Gang


    Asymmetric 1,6-addition of malonates to para-quinone methides has been developed by using amide-phosphonium salts derived from easily available chiral α-amino acids as bifunctional phase transfer catalysts. Stabilized para-quinone methides with various substituents on the phenyl ring were reacted with diphenyl malonates to give functionalized diaryl methines in excellent yields and high to excellent ee's. Furthermore, to show the utility of this methodology, a gram scale synthesis of an 1,6-addition adduct and its further elaboration into the key intermediate for synthesis of GPR40 agonists were also described.

  6. Mathematical Model of Non-stationary Heat Conduction in the Wall: Asymmetric Problem with the Boundary Conditions of Imperfect Heat Transfer

    Directory of Open Access Journals (Sweden)

    Charvátová Hana


    Full Text Available This paper deals with the study of a non-stationary heat conduction in the solid wall. It is focused on mathematical modelling of its asymmetric heating and cooling by imperfect heat transfer to both sides of the wall. It describes method used for deriving of the long time analytical solution describing temperature distribution in the heated (cooled wall by use Laplace transform and verification of its validity by numerical calculation with COMSOL Multiphysics software. In the tested example, the maximum difference between analytical and numerical solution was about 3.5 % considering the possible maximum and minimum temperatures in the wall under the given conditions.

  7. Microscopic models for proton transfer in water and strongly hydrogen-bonded complexes with a single-well proton potential

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens


    A new mechanism and formalism for proton transfer in donor-acceptor complexes with long hydrogen bonds introduced recently [1], is applied to a proton transfer in liquid water. "Structural diffusion" of hydroxonium ions is regarded as totally adiabatic process, with synchronous hindered translation...

  8. Mesoporous Silica-Supported Sulfonyldiamine Ligand for Microwave-Assisted Transfer Hydrogenation

    Directory of Open Access Journals (Sweden)

    Shaheen M. Sarkar


    Full Text Available N-Sulfonyl-1,2-diamine ligands, derived from 1,2-diaminocyclohexane and 1,2-diaminopropane, were immobilized onto mesoporous SBA-15 silica. The SBA-15-supported sulfonyldiamine-Ru complex was prepared in situ under microwave heating at 60 W for 3 min. The prepared sulfonyldiamine-Ru complex was used as an efficient catalyst for the transfer hydrogenation of ketones to the corresponding secondary alcohols. The heterogeneous complex showed extremely high catalytic activity with 99% conversion rate under microwave heating condition. The complexes were regenerated by simple filtration and reused two times without significant loss of activity.

  9. Bane of Hydrogen-Bond Formation on the Photoinduced Charge-Transfer Process in Donor–Acceptor Systems

    KAUST Repository

    Alsam, Amani Abdu


    Controlling the ultrafast dynamical process of photoinduced charge transfer at donor acceptor interfaces remains a major challenge for physical chemistry and solar cell communities. The process is complicated by the involvement of other complex dynamical processes, including hydrogen bond formation, energy transfer, and solvation dynamics occurring on similar time scales. In this study, we explore the remarkable impact of hydrogen-bond formation on the interfacial charge transfer between a negatively charged electron donating anionic porphyrin and a positively charged electron accepting pi-conjugated polymer, as a model system in solvents with different polarities and capabilities for hydiogen bonding using femtosecond transient absorption spectroscopy. Unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our steadystate and time-resolved results reveal that the intervening hydrogen-bonding environment and, consequently, the probable longer spacing between the donor and acceptor molecules significantly hinders the charge-transfer process between them. These results show that site-specific hydrogen bonding and geometric considerations between donor and acceptor can be exploited to control both the charge-transfer dynamics and its efficiency not only at donor acceptor interfaces but also in complex biological systems.

  10. β-Cyclodextrins grafted with chiral amino acids: A promising supramolecular stabilizer of nanoparticles for asymmetric hydrogenation?


    Chau, Nguyet Trang Thanh; Guégan, Jean-Paul; Menuel, Stephane; Guerrero, Miguel; Hapiot, Frédéric; Monflier, Eric; Philippot, Karine; Denicourt-Nowicki, Audrey; Roucoux, Alain


    International audience; Water-soluble ruthenium nanoparticles stabilized by randomly methylated β-cyclodextrins (RaMeCDs) grafted with chiral amino-acid moieties like l-alanine (Ala) and l-leucine (Leu) were prepared in aqueous solution by two approaches: (i) a one-step hydrogen reduction of ruthenium trichloride as metal source in the presence of appropriate cyclodextrins (one-pot method) or (ii) a NaBH4 reduction of the metal salts, followed by the stabilization of ruthenium hydrosol by the...

  11. Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions. (United States)

    Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A


    Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important

  12. Theoretical and computational study of the energy dependence of the muon transfer rate from hydrogen to higher-Z gases

    Energy Technology Data Exchange (ETDEWEB)

    Bakalov, Dimitar, E-mail: [Institute for Nuclear Research and Nuclear Energy, Bulgarian Academy of Sciences, Tsarigradsko chaussée 72, Sofia 1784 (Bulgaria); Adamczak, Andrzej [Institute of Nuclear Physics, Polish Academy of Sciences, ul. Radzikowskiego 152, 31-342 Krakow (Poland); Stoilov, Mihail [Institute for Nuclear Research and Nuclear Energy, Bulgarian Academy of Sciences, Tsarigradsko chaussée 72, Sofia 1784 (Bulgaria); Vacchi, Andrea [Istituto Nazionale di Fisica Nucleare, Sezione di Trieste, Via A. Valerio 2, 34127 Trieste (Italy)


    The recent PSI Lamb shift experiment and the controversy about proton size revived the interest in measuring the hyperfine splitting in muonic hydrogen as an alternative possibility for comparing ordinary and muonic hydrogen spectroscopy data on proton electromagnetic structure. This measurement critically depends on the energy dependence of the muon transfer rate to heavier gases in the epithermal range. The available data provide only qualitative information, and the theoretical predictions have not been verified. We propose a new method by measurements of the transfer rate in thermalized target at different temperatures, estimate its accuracy and investigate the optimal experimental conditions. - Highlights: • Method for measuring the energy dependence of muon transfer rate to higher-Z gases. • Thermalization and depolarization of muonic hydrogen studied by Monte Carlo method. • Optimal experimental conditions determined by Monte Carlo simulations. • Mathematical model and for estimating the uncertainty of the experimental results.

  13. Efficient and Adaptive Methods for Computing Accurate Potential Surfaces for Quantum Nuclear Effects: Applications to Hydrogen-Transfer Reactions. (United States)

    DeGregorio, Nicole; Iyengar, Srinivasan S


    We present two sampling measures to gauge critical regions of potential energy surfaces. These sampling measures employ (a) the instantaneous quantum wavepacket density, an approximation to the (b) potential surface, its (c) gradients, and (d) a Shannon information theory based expression that estimates the local entropy associated with the quantum wavepacket. These four criteria together enable a directed sampling of potential surfaces that appears to correctly describe the local oscillation frequencies, or the local Nyquist frequency, of a potential surface. The sampling functions are then utilized to derive a tessellation scheme that discretizes the multidimensional space to enable efficient sampling of potential surfaces. The sampled potential surface is then combined with four different interpolation procedures, namely, (a) local Hermite curve interpolation, (b) low-pass filtered Lagrange interpolation, (c) the monomial symmetrization approximation (MSA) developed by Bowman and co-workers, and (d) a modified Shepard algorithm. The sampling procedure and the fitting schemes are used to compute (a) potential surfaces in highly anharmonic hydrogen-bonded systems and (b) study hydrogen-transfer reactions in biogenic volatile organic compounds (isoprene) where the transferring hydrogen atom is found to demonstrate critical quantum nuclear effects. In the case of isoprene, the algorithm discussed here is used to derive multidimensional potential surfaces along a hydrogen-transfer reaction path to gauge the effect of quantum-nuclear degrees of freedom on the hydrogen-transfer process. Based on the decreased computational effort, facilitated by the optimal sampling of the potential surfaces through the use of sampling functions discussed here, and the accuracy of the associated potential surfaces, we believe the method will find great utility in the study of quantum nuclear dynamics problems, of which application to hydrogen-transfer reactions and hydrogen

  14. Hydrogen atom transfer reactions of imido manganese(V) corrole: one reaction with two mechanistic pathways. (United States)

    Zdilla, Michael J; Dexheimer, Jennifer L; Abu-Omar, Mahdi M


    Hydrogen atom transfer (HAT) reactions of (tpfc)MnNTs have been investigated (tpfc = 5,10,15-tris(pentafluorophenyl)corrole and Ts = p-toluenesulfonate). 9,10-Dihydroanthracene and 1,4-dihydrobenzene reduce (tpfc)MnNTs via HAT with second-order rate constants 0.16 +/- 0.03 and 0.17 +/- 0.01 M(-1) s(-1), respectively, at 22 degrees C. The products are the respective arenes, TsNH(2) and (tpfc)Mn(III). Conversion of (tpfc)MnNTs to (tpfc)Mn by reaction with dihydroanthracene exhibits isosbestic behavior, and formation of 9,9',10,10'-tetrahydrobianthracene is not observed, suggesting that the intermediate anthracene radical rebounds in a second fast step without accumulation of a Mn(IV) intermediate. The imido complex (tpfc)Mn(V)NTs abstracts a hydrogen atom from phenols as well. For example, 2,6-di-tert-butyl phenol is oxidized to the corresponding phenoxyl radical with a second-order rate constant of 0.32 +/- 0.02 M(-1) s(-1) at 22 degrees C. The other products from imido manganese(V) are TsNH(2) and the trivalent manganese corrole. Unlike reaction with dihydroarenes, when phenols are used isosbestic behavior is not observed, and formation of (tpfc)Mn(IV)(NHTs) is confirmed by EPR spectroscopy. A Hammett plot for various p-substituted 2,6-di-tert-butyl phenols yields a V-shaped dependence on sigma, with electron-donating substituents exhibiting the expected negative rho while electron-withdrawing substituents fall above the linear fit (i.e., positive rho). Similarly, a bond dissociation enthalpy (BDE) correlation places electron-withdrawing substituents above the well-defined negative slope found for the electron-donating substituents. Thus two mechanisms are established for HAT reactions in this system, namely, concerted proton-electron transfer and proton-gated electron transfer in which proton transfer is followed by electron transfer.

  15. Hydrogen atom transfer reactions in thiophenol: photogeneration of two new thione isomers. (United States)

    Reva, Igor; Nowak, Maciej J; Lapinski, Leszek; Fausto, Rui


    Photoisomerization reactions of monomeric thiophenol have been investigated for the compound isolated in low-temperature argon matrices. The initial thiophenol population consists exclusively of the thermodynamically most stable thiol form. Phototransformations were induced by irradiation of the matrices with narrowband tunable UV light. Irradiation at λ > 290 nm did not induce any changes in isolated thiophenol molecules. Upon irradiation at 290-285 nm, the initial thiol form of thiophenol converted into its thione isomer, cyclohexa-2,4-diene-1-thione. This conversion occurs by transfer of an H atom from the SH group to a carbon atom at the ortho position of the ring. Subsequent irradiation at longer wavelengths (300-427 nm) demonstrated that this UV-induced hydrogen-atom transfer is photoreversible. Moreover, upon irradiation at 400-425 nm, the cyclohexa-2,4-diene-1-thione product converts, by transfer of a hydrogen atom from the ortho to para position, into another thione isomer, cyclohexa-2,5-diene-1-thione. The latter thione isomer is also photoreactive and is consumed if irradiated at λ atom-transfer isomerization reactions dominate the unimolecular photochemistry of thiophenol confined in a solid argon matrix. A set of low-intensity infrared bands, observed in the spectra of UV irradiated thiophenol, indicates the presence of a phenylthiyl radical with an H- atom detached from the SH group. Alongside the H-atom-transfer and H-atom-detachment processes, the ring-opening photoreaction occurred in cyclohexa-2,4-diene-1-thione by the cleavage of the C-C bond at the alpha position with respect to the thiocarbonyl C[double bond, length as m-dash]S group. The resulting open-ring conjugated thioketene adopts several isomeric forms, differing by orientations around single and double bonds. The species photogenerated upon UV irradiation of thiophenol were identified by comparison of their experimental infrared spectra with the spectra theoretically calculated for

  16. Concerted hydrogen atom and electron transfer mechanism for catalysis by lysine-specific demethylase. (United States)

    Yu, Tao; Higashi, Masahiro; Cembran, Alessandro; Gao, Jiali; Truhlar, Donald G


    We calculate the free energy profile for the postulated hydride transfer reaction mechanism for the catalysis of lysine demethylation by lysine-specific demethylase LSD1. The potential energy surface is obtained by using combined electrostatically embedded multiconfiguration molecular mechanics (EE-MCMM) and single-configuration molecular mechanics (MM). We employ a constant valence bond coupling term to obtain analytical energies and gradients of the EE-MCMM subsystem, which contains 45 quantum mechanics (QM) atoms and which is parametrized with density functional calculations employing specific reaction parameters obtained by matching high-level wave function calculations. In the MM region, we employ the Amber ff03 and TIP3P force fields. The free energy of activation at 300 K is calculated by molecular dynamics (MD) umbrella sampling on a system with 102,090 atoms as the maximum of the free energy profile along the reaction coordinate as obtained by the weighted histogram analysis method with 17 umbrella sampling windows. This yields a free energy of activation of only 10 kcal/mol, showing that the previously postulated direct hydride transfer reaction mechanism is plausible, although we find that it is better interpreted as a concerted transfer of a hydrogen atom and an electron.

  17. Palladium-Catalyzed Atom-Transfer Radical Cyclization at Remote Unactivated C(sp3)-H Sites: Hydrogen-Atom Transfer of Hybrid Vinyl Palladium Radical Intermediates. (United States)

    Ratushnyy, Maxim; Parasram, Marvin; Wang, Yang; Gevorgyan, Vladimir


    A novel mild, visible-light-induced palladium-catalyzed hydrogen atom translocation/atom-transfer radical cyclization (HAT/ATRC) cascade has been developed. This protocol involves a 1,5-HAT process of previously unknown hybrid vinyl palladium radical intermediates, thus leading to iodomethyl carbo- and heterocyclic structures. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Asymmetrical flow field-flow fractionation with on-line detection for drug transfer studies: a feasibility study

    DEFF Research Database (Denmark)

    Hinna, A.; Steiniger, F.; Hupfeld, S.


    Knowledge about drug retention within colloidal carriers is of uppermost importance particularly if drug targeting is anticipated. The aim of the present study was to evaluate asymmetrical flow field-flow fractionation (AF4) with on-line UV/VIS drug quantification for its suitability to determine...... was found repeatable and robust. The employed combination of AF4 with multi-angle laser light scattering furthermore provided detailed size information of the eluting sample and thus allowed to detect instabilities and/or interactions between the donor and acceptor liposomes. Drug quantification by on...

  19. Study of Thermodynamic Vent and Screen Baffle Integration for Orbital Storage and Transfer of Liquid Hydrogen (United States)

    Cady, E. C.


    A comprehensive analytical and experimental program was performed to determine the feasibility of integrating an internal thermodynamic vent system and a full wall-screen liner for the orbital storage and transfer of liquid hydrogen (LH2). Ten screens were selected from a comprehensive screen survey. The experimental study determined the screen bubble point, flow-through pressure loss, and pressure loss along rectangular channels lined with screen on one side, for the 10 screens using LH2 saturated at 34.5 N/cm2 (50 psia). The correlated experimental data were used in an analysis to determine the optimum system characteristics in terms of minimum weight for 6 tanks ranging from 141.6 m3 (5,000 ft3) to 1.416 m3 (50 ft3) for orbital storage times of 30 and 300 days.

  20. Evaluation of hydroconverted residues. Rationalization of analytical data through hydrogen transfer balance

    Energy Technology Data Exchange (ETDEWEB)

    Bacaud, Robert; Rouleau, Loiec [Institut de Recherches sur la Catalyse, CNRS, 2 Avenue Albert Einstein, 69626 Villeurbanne (France); Cebolla, Vicente L.; Membrado, Luis; Vela, Jesus [Departamento de Procesos Quimicos, Instituto de Carboquimica, CSIC, Calle Poeta Luciano Gracia 5, 50015 Zaragoza (Spain)


    Analytical evaluation of petroleum based materials and processed feeds is a complex task relying on a compromise between tedious in-depth characterizations and fast responding tools for process control. In the present paper, a large number of hydroprocessed vacuum residues, obtained either under catalytic or thermal conditions, have been submitted to the following analytical techniques: Simulated distillation, coupled Simdist/MS, UV spectroscopy, {sup 13}C NMR, quantitative thin-layer chromatography/FID, vapor phase osmometry. A confrontation of analytical data in the light of correlations with hydrogen transfer evaluation is proposed, which accounts for observed variations in aromatic content. Conradson carbon residue largely influences the results obtained with some of the examined techniques. Apparent discrepancies are rationalized and a strategy for a comprehensive analytical evaluation of hydroprocessed feeds is proposed

  1. Polyimides Based on Asymmetric Dianhydrides (II) (a-BPDA vs a-BTDA) for Resin Transfer Molding (RTM) (United States)

    Chuang, Kathy C.; Criss, Jim M.; Mintz, Eric A.


    A new series of low-melt viscosity imide resins (10-20 poise at 280 C) were formulated from asymmetric 2,3,3',4' -benzophenone dianhydride (a-BTDA) and 4-phenylethynylphthalic endcaps, along with 3,4' -oxydianiline, 3,3' -methylenedianiline and 3,3'- diaminobenzophenone, using a solvent-free melt process. a-BTDA RTM resins exhibited higher glass transition temperatures (Tg's = 330-400 C) compared to those prepared by asymmetric 2,3,3',4' -biphenyl dianhydride, (a-BPDA, Tg's = 320-370 C). These low-melt viscosity imide resins were fabricated into polyimide/T650-35 carbon fiber composites by a RTM process. Composites properties of a-BTDA resins, such as open-hole compression and short-beam shear strength, are compared to those of composites made from a-BPDA based resin at room temperature, 288 C and 315 C. These novel, high temperature RTM imide resins exhibit outstanding properties beyond the performance of conventional RTM resins, such as epoxy and BMI resins which have use-temperatures around 177 C and 232 C for aerospace applications.

  2. Barrier heights of hydrogen-transfer reactions with diffusion quantum monte carlo method. (United States)

    Zhou, Xiaojun; Wang, Fan


    Hydrogen-transfer reactions are an important class of reactions in many chemical and biological processes. Barrier heights of H-transfer reactions are underestimated significantly by popular exchange-correlation functional with density functional theory (DFT), while coupled-cluster (CC) method is quite expensive and can be applied only to rather small systems. Quantum Monte-Carlo method can usually provide reliable results for large systems. Performance of fixed-node diffusion quantum Monte-Carlo method (FN-DMC) on barrier heights of the 19 H-transfer reactions in the HTBH38/08 database is investigated in this study with the trial wavefunctions of the single-Slater-Jastrow form and orbitals from DFT using local density approximation. Our results show that barrier heights of these reactions can be calculated rather accurately using FN-DMC and the mean absolute error is 1.0 kcal/mol in all-electron calculations. Introduction of pseudopotentials (PP) in FN-DMC calculations improves efficiency pronouncedly. According to our results, error of the employed PPs is smaller than that of the present CCSD(T) and FN-DMC calculations. FN-DMC using PPs can thus be applied to investigate H-transfer reactions involving larger molecules reliably. In addition, bond dissociation energies of the involved molecules using FN-DMC are in excellent agreement with reference values and they are even better than results of the employed CCSD(T) calculations using the aug-cc-pVQZ basis set. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  3. Evaluation of industrially applied heat-transfer fluids as liquid organic hydrogen carrier systems. (United States)

    Brückner, Nicole; Obesser, Katharina; Bösmann, Andreas; Teichmann, Daniel; Arlt, Wolfgang; Dungs, Jennifer; Wasserscheid, Peter


    Liquid organic hydrogen carrier (LOHC) systems offer a very attractive method for the decentralized storage of renewable excess energy. In this contribution, industrially well-established heat-transfer oils (typically sold under trade names, e.g., Marlotherm) are proposed as a new class of LOHC systems. It is demonstrated that the liquid mixture of isomeric dibenzyltoluenes (m.p. -39 to -34 °C, b.p. 390 °C) can be readily hydrogenated to the corresponding mixture of perhydrogenated analogues by binding 6.2 wt% of H2. The liquid H2 -rich form can be stored and transported similarly to diesel fuel. It readily undergoes catalytic dehydrogenation at temperatures above 260 °C, which proves its applicability as a reversible H2 carrier. The presented LOHC systems are further characterized by their excellent technical availability at comparably low prices, full registration of the H2 -lean forms, and excellent thermal stabilities. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Hydrogen bonded charge transfer molecular salt (4-chloro anilinium-3-nitrophthalate) for photophysical and pharmacological applications (United States)

    Singaravelan, K.; Chandramohan, A.; Saravanabhavan, M.; Muthu Vijayan Enoch, I. V.; Suganthi, V. S.


    Radical scavenging activity against DPPH radical and binding properties of a hydrogen bonded charge transfer molecular salt 4-chloro anilinium-3-nitrophthalate(CANP) with calf thymus DNA has been studied by electronic absorption and emission spectroscopy. The molecular structure and crystallinity of the CANP salt have been established by carried out powder and single crystal X-ray diffraction analysis which indicated that cation and anion are linked through strong N+sbnd H…O- type of hydrogen bond. FTIR spectroscopic study was carried out to know the various functional groups present in the crystal. 1H and 13C NMR spectra were recorded to further confirm the molecular structure of the salt crystal. The thermal stability of the title salt was established by TG/DTA analyses simultaneously on the powdered sample of the title crystal. Further, the CANP salt was examined against various bacteria and fungi strains which showed a remarkable antimicrobial activity compared to that of the standards Ciproflaxin and Clotrimazole. The results showed that the CANP salt could interact with CT-DNA through intercalation. Antioxidant studies of the substrates alone and synthesized CANP salt showed that the latter has been better radical scavenging activity than that of the former against DPPH radical. The third order nonlinear susceptibility of the CANP salt was established by the Z-scan study.

  5. Asymmetric fluorination of α-branched cyclohexanones enabled by a combination of chiral anion phase-transfer catalysis and enamine catalysis using protected amino acids. (United States)

    Yang, Xiaoyu; Phipps, Robert J; Toste, F Dean


    We report a study involving the successful merger of two separate chiral catalytic cycles: a chiral anion phase-transfer catalysis cycle to activate Selectfluor and an enamine activation cycle, using a protected amino acid as organocatalyst. We have demonstrated the viability of this approach with the direct asymmetric fluorination of α-substituted cyclohexanones to generate quaternary fluorine-containing stereocenters. With these two chiral catalytic cycles operating together in a matched sense, high enantioselectivites can be achieved, and we envisage that this dual catalysis method has the potential to be more broadly applicable, given the breadth of enamine catalysis. It also represents a rare example of chiral enamine catalysis operating successfully on α-branched ketones, substrates commonly inert to this activation mode.

  6. NQR application to the study of hydrogen dynamics in hydrogen-bonded molecular dimers

    Energy Technology Data Exchange (ETDEWEB)

    Asaji, Tetsuo, E-mail: [Nihon University, Department of Chemistry, College of Humanities and Sciences (Japan)


    The temperature dependences of {sup 1}H NMR as well as {sup 35}Cl NQR spin-lattice relaxation times T{sub 1} were investigated in order to study the hydrogen transfer dynamics in carboxylic acid dimers in 3,5-dichloro- and 2,6-dichlorobenzoic acids. The asymmetry energy A/ k{sub B} and the activation energy V/ k{sub B} for the hydrogen transfer were estimated to be 240 K and 900 K, and 840 K and 2500 K, respectively, for these compounds. In spite of a large asymmetric potential the quantum nature of hydrogen transfer is recognized in the slope of the temperature dependence of T{sub 1} on the low-temperature side of the T{sub 1} minimum. The NQR T{sub 1} measurements was revealed to be a good probe for the hydrogen transfer dynamics.

  7. Theoretical investigation of the coupling between hydrogen-atom transfer and stacking interaction in adenine-thymine dimers. (United States)

    Villani, Giovanni


    Three different dimers of the adenine-thymine (A-T) base pair are studied to point out the changes of important properties (structure, atomic charge, energy and so on) induced by coupling between the movement of the atoms in the hydrogen bonds and the stacking interaction. The comparison of these results with those for the A-T monomer system explains the role of the stacking interaction in the hydrogen-atom transfer in this biologically important base pair. The results support the idea that this coupling depends on the exact dimer considered and is different for the N-N and N-O hydrogen bonds. In particular, the correlation between the hydrogen transfer and the stacking interaction is more relevant for the N-N bridge than for the N-O one. Also, the two different mechanisms of two-hydrogen transfer (step by step and concerted) can be modified by the stacking interaction between the base pairs. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Observation of the Marcus Inverted Region of Electron Transfer from Asymmetric Chemical Doping of Pristine (n,m) Single-Walled Carbon Nanotubes. (United States)

    Kunai, Yuichiro; Liu, Albert Tianxiang; Cottrill, Anton L; Koman, Volodymyr B; Liu, Pingwei; Kozawa, Daichi; Gong, Xun; Strano, Michael S


    The concept of electrical energy generation based on asymmetric chemical doping of single-walled carbon nanotube (SWNT) papers is presented. We explore 27 small, organic, electron-acceptor molecules that are shown to tune the output open-circuit voltage (VOC) across three types of pristine SWNT papers with varying (n,m) chirality distributions. A considerable enhancement in the observed VOC, from 80 to 440 mV, is observed for SWNT/molecule acceptor pairs that have molecular volume below 120 Å3 and lowest unoccupied molecular orbital (LUMO) energies centered around -0.8 eV. The electron transfer (ET) rate constants driving the VOC generation are shown to vary with the chirality-associated Marcus theory, suggesting that the energy gaps between SWNT and the LUMO of acceptor molecules dictate the ET process. When the ET rate constants and the maximum VOC are plotted versus the LUMO energy of the acceptor organic molecule, volcano-shaped dependencies, characteristic of the Marcus inverted region, are apparent for three distinct sources of SWNT papers with modes in diameter distributions of 0.95, 0.83, and 0.75 nm. This observation, where the ET driving force exceeds reorganization energies, allows for an estimation of the outer-sphere reorganization energies with values as low as 100 meV for the (8,7) SWNT, consistent with a proposed image-charge modified Born energy model. These results expand the fundamental understanding of ET transfer processes in SWNT and allow for an accurate calculation of energy generation through asymmetric doping for device applications.

  9. Homolytic N-H activation of ammonia: hydrogen transfer of parent iridium ammine, amide, imide, and nitride species

    NARCIS (Netherlands)

    Scheibel, M.G.; Abbenseth, J.; Kinauer, M.; Heinemann, F.W.; Würtele, C.; de Bruin, B.; Schneider, S.


    The redox series [Ir-n(NH(x))(PNP)] (n = II-IV, x = 3-0; PNP = N(CHCHPtBu(2))(2)) was examined with respect to electron, proton, and hydrogen atom transfer steps. The experimental and computational results suggest that the Ir-III imido species [Ir(NH) (PNP)] is not stable but undergoes to the

  10. Single crystal to single crystal transformation and hydrogen-atom transfer upon oxidation of a cerium coordination compound. (United States)

    Williams, Ursula J; Mahoney, Brian D; Lewis, Andrew J; DeGregorio, Patrick T; Carroll, Patrick J; Schelter, Eric J


    Trivalent and tetravalent cerium compounds of the octamethyltetraazaannulene (H2omtaa) ligand have been synthesized. Electrochemical analysis shows a strong thermodynamic preference for the formal cerium(IV) oxidation state. Oxidation of the cerium(III) congener Ce(Homtaa)(omtaa) occurs by hydrogen-atom transfer that includes a single crystal to single crystal transformation upon exposure to an ambient atmosphere.

  11. Hydrogen transfer on USY zeolites during gas oil cracking: Influence of the adsorption characteristics of the zeolite catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Corma, A.; Faraldos, M.; Martinez, A.; Mifsud, A. (CSIC, Madrid (Spain))


    In this work, the hydrogen transfer activity of two series of HY zeolites dealuminated by steam and by SiCl{sub 4} (24.47-24.24 {angstrom} unit cell) has been measured from the butene/butane ratio in the products obtained during the cracking of a vacuum gas oil at 756 K. With the steam-dealuminated zeolites, a sharp decrease in the ratio of hydrogen transfer to cracking is observed when the number of Al atoms per unit cell falls below 10. On the other hand, in samples dealuminated by SiCl{sub 4}, this ratio changes very little with dealumination. These results cannot be explained assuming the need for adjacent acid sites for the hydrogen transfer. The authors have found, by adsorption measurements of n-butane and 1-butene, that the changes in the relative rates of bimolecular (hydrogen transfer) to monomolecular (cracking) reactions, observed with dealuminated HY zeolites, can be explained by the changes in the adsorption capacity and adsorption selectivity which occur on zeolites dealuminated at different levels by different dealumination procedures, and which are due to changes in the electric fields inside the pores.

  12. Selective conversion of polyenes to monoenes by RuCl(3) -catalyzed transfer hydrogenation: the case of cashew nutshell liquid. (United States)

    Perdriau, Sébastien; Harder, Sjoerd; Heeres, Hero J; de Vries, Johannes G


    Cardanol, a constituent of cashew nutshell liquid (CNSL), was subjected to transfer hydrogenation catalyzed by RuCl(3) using isopropanol as a reductant. The side chain of cardanol, which is a mixture of a triene, a diene, and a monoene, was selectively reduced to the monoene. Surprisingly, it is the C8-C9 double bond that is retained with high selectivity. A similar transfer hydrogenation of linoleic acid derivatives succeeded only if the substrate contained an aromatic ring, such as a benzyl ester. TEM and a negative mercury test showed that the catalyst was homogeneous. By using ESI-MS, ruthenium complexes were identified that contained one, two, or even three molecules of substrate, most likely as allyl complexes. The interaction between ruthenium and the aromatic ring determines selectivity in the hydrogenation reaction. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Pier, M.


    A transcript is presented of a speech on the history of the development of hydrogenation of coal and tar. Apparently the talk had been accompanied by the showing of photographic slides, but none of the pictures were included with the report. In giving the history, Dr. Pier mentioned the dependence of much of the development of hydrogenation upon previous development in the related areas of ammonia and methanol syntheses, but he also pointed out several ways in which equipment appropriate for hydrogenation differed considerably from that used for ammonia and methanol. Dr. Pier discussed the difficulties encountered with residue processing, design of the reaction ovens, manufacture of ovens and preheaters, heating of reaction mixtures, development of steels, and development of compressor pumps. He described in some detail his own involvement in the development of the process. In addition, he discussed the development of methods of testing gasolines and other fuels. Also he listed some important byproducts of hydrogenation, such as phenols and polycyclic aromatics, and he discussed the formation of iso-octane fuel from the butanes arising from hydrogenation. In connection with several kinds of equipment used in hydrogenation (whose pictures were being shown), Dr. Pier gave some of the design and operating data.

  14. Mechanism of Action of Sulforaphane as a Superoxide Radical Anion and Hydrogen Peroxide Scavenger by Double Hydrogen Transfer: A Model for Iron Superoxide Dismutase. (United States)

    Prasad, Ajit Kumar; Mishra, P C


    The mechanism of action of sulforaphane as a scavenger of superoxide radical anion (O2(•-)) and hydrogen peroxide (H2O2) was investigated using density functional theory (DFT) in both gas phase and aqueous media. Iron superoxide dismutase (Fe-SOD) involved in scavenging superoxide radical anion from biological media was modeled by a complex consisting of the ferric ion (Fe(3+)) attached to three histidine rings. Reactions related to scavenging of superoxide radical anion by sulforaphane were studied using DFT in the presence and absence of Fe-SOD represented by this model in both gas phase and aqueous media. The scavenging action of sulforaphane toward both superoxide radical anion and hydrogen peroxide was found to involve the unusual mechanism of double hydrogen transfer. It was found that sulforaphane alone, without Fe-SOD, cannot scavenge superoxide radical anion in gas phase or aqueous media efficiently as the corresponding reaction barriers are very high. However, in the presence of Fe-SOD represented by the above-mentioned model, the scavenging reactions become barrierless, and so sulforaphane scavenges superoxide radical anion by converting it to hydrogen peroxide efficiently. Further, sulforaphane was found to scavenge hydrogen peroxide also very efficiently by converting it into water. Thus, the mechanism of action of sulforaphane as an excellent antioxidant has been unravelled.

  15. Hydrogen-Bond Strength of CC and GG Pairs Determined by Steric Repulsion: Electrostatics and Charge Transfer Overruled. (United States)

    van der Lubbe, Stephanie C C; Fonseca Guerra, Célia


    Theoretical and experimental studies have elucidated the bonding mechanism in hydrogen bonds as an electrostatic interaction, which also exhibits considerable stabilization by charge transfer, polarization, and dispersion interactions. Therefore, these components have been used to rationalize the differences in strength of hydrogen-bonded systems. A completely new viewpoint is presented, in which the Pauli (steric) repulsion controls the mechanism of hydrogen bonding. Quantum chemical computations on the mismatched DNA base pairs CC and GG (C=cytosine, G=guanine) show that the enhanced stabilization and shorter distance of GG is determined entirely by the difference in the Pauli repulsion, which is significantly less repulsive for GG than for CC. This is the first time that evidence is presented for the Pauli repulsion as decisive factor in relative hydrogen-bond strengths and lengths. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Improved performance in coprocessing through fundamental and mechanistic studies in hydrogen transfer and catalysis. Quarterly report, September 26, 1989--December 26, 1989

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W.


    To gain a fundamental understanding of the role and importance of hydrogen transfer reactions in thermal and catalytic coprocessing by examining possible hydrogen donation from cycloalkane/aromatic systems and by understanding the chemistry and enhanced reactivity of hydrotreated residuum, as well as by enriching petroleum solvent with potent new donors, nonaromatic hydroaromatics, thereby promoting hydrogen transfer reactions in coprocessing. The detailed results of experiments performed on several subtasks during the quarter are presented.

  17. Improved performance in coprocessing through fundamental and mechanistic studies in hydrogen transfer and catalysis. Quarterly report, December 26, 1989--March 26, 1990

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W.


    To gain a fundamental understanding of the role and importance of hydrogen transfer reactions in thermal and catalytic coprocessing by examining possible hydrogen donation from cycloalkane/aromatic systems and by understanding the chemistry and enhanced reactivity of hydrotreated residuum, as well as by enriching petroleum solvent with potent new donors, nonaromatic hydroaromatics, thereby promoting hydrogen transfer reactions in coprocessing. The detailed results of experiments performed on several subtasks during the quarter are presented.

  18. Proton-transfer in hydrogenated guanine-cytosine trimer neutral species, cations, and anions embedded in B-form DNA. (United States)

    Lin, Yuexia; Wang, Hongyan; Wu, Yingxi; Gao, Simin; Schaefer, Henry F


    The neutral DNA trimers with the hydrogen atom added to the C8 site of the middle guanine-cytosine (GC) base pair, the DNA trimers protonated at the N7 site of the middle GC base pair, and the anionic species resulting from hydride addition to the C6 site of the middle GC base pair are investigated using theoretical methods. The canonical Watson-Crick structures (WC), transition state structures (TS) and proton-transferred structures (PT) of each relevant system are optimized in the gas phase and in aqueous solution, in order to understand the processes of proton transfer. The proton transfer reactions of the DNA trimers are compared with the corresponding isolated hydrogenated GC base pairs to explore the influence of the surrounding molecules and the base sequence. The proton transfer reactions of the neutral species, cations, and anions are compared, aiming to clarify the effects of the system's total charge. The results reveal that the surrounding molecules decrease the reaction energies of proton-transfer in aqueous solution. The structures with the dATGCAT and dGCGCGC sequences facilitate proton H4a transfer, but hinder proton H1 transfer. The structures with the dCGGCCG and dTAGCTA sequences facilitate proton H1 transfer. The net charge on the system plays an important role in determining the single and double proton-transfer patterns. Anions are more likely to experience proton-transfer reactions than neutral species and cations, and all the proton-transfer reactions of the anions are exothermic.

  19. Nanoscale Layer Transfer by Hydrogen Ion-Cut Processing: A Brief Review Through Recent U.S. Patents. (United States)

    Lee, Benjamin T-H


    A hydrogen-based Ion-Cut layer-transfer technique, the so-called Ion-Cut or Smart-Cut processing, has been used in transferring a semiconductor membrane onto a desired substrate to reveal unique characteristics on a nanoscale size and to build functional electronic and photonic devices that are used for specific purposes. For example, the sub-100 nm thick silicon membrane transferred onto an insulator became a key substrate for fabricating nanoscale integrated circuit (IC) devices. Recent U.S. patents have exhibited integration of various thinning approaches requiring precision of a few nanometers in fabricating large-area semiconductor nanomembranes, especially for silicon. This paper reviews published patents and work on fabricating sub-100 nm silicon membranes with welldefined features without a chemical-mechanical polishing (CMP) thinning process. This included material analysis leads to ultraprecision thickness in the sub-100 nm region. This paper combines an analysis of peer-reviewed articles and issued patents using focused review keywords of hydrogen implantation, wafer bonding, and layer splitting. The quality of selected patents was appraised based on the authors' 20-year research experience in the field of ultrathin silicon layer-transfer technology. The paper covered more than 10 U.S. patents that have been filed on hydrogen-based Ion-Cut layer-transfer techniques. These patents described approaches for inserting hydrogen ions to split at a well-defined location and then transfer the as-split silicon membrane at the nanoscale thickness onto a desired substrate. Hydrogen-trap sites, implantation energy, and interface of the distinct doped regions could define the layer-split location. The insertion of high-dose hydrogen ions could be thoroughly achieved by ion implantation, plasma ion immersion implantation (PIII), plasma diffusion, and electrolysis. The article concludes with the discussion of the patent-orientated review of layer-transfer techniques

  20. Hydrogen. (United States)

    Bockris, John O'M


    The idea of a "Hydrogen Economy" is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO₂ in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H₂ from the electrolyzer. Methanol made with CO₂ from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan). Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs) by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech.

  1. Temperature-dependent kinetics of charge transfer, hydrogen-atom transfer, and hydrogen-atom expulsion in the reaction of CO+ with CH4 and CD4. (United States)

    Melko, Joshua J; Ard, Shaun G; Johnson, Ryan S; Shuman, Nicholas S; Guo, Hua; Viggiano, Albert A


    We have determined the rate constants and branching ratios for the reactions of CO(+) with CH4 and CD4 in a variable-temperature selected ion flow tube. We find that the rate constants are collisional for all temperatures measured (193-700 K for CH4 and 193-500 K for CD4). For the CH4 reaction, three product channels are identified, which include charge transfer (CH4(+) + CO), H-atom transfer (HCO(+) + CH3), and H-atom expulsion (CH3CO(+) + H). H-atom transfer is slightly preferred to charge transfer at low temperature, with the charge-transfer product increasing in contribution as the temperature is increased (H-atom expulsion is a minor product for all temperatures). Analogous products are identified for the CD4 reaction. Density functional calculations on the CO(+) + CH4 reaction were also conducted, revealing that the relative temperature dependences of the charge-transfer and H-atom transfer pathways are consistent with an initial charge transfer followed by proton transfer.

  2. Engineering design elements of a two-phase thermosyphon to transfer nuclear thermal energy to a hydrogen plant (United States)

    Sabharwall, Piyush

    Two hydrogen production processes, both powered by Next Generation Nuclear Plant (NGNP), are currently under investigation at the Idaho National Laboratory. The first is high-temperature steam electrolysis utilizing both heat and electricity and the second is thermo-chemical production through the sulfur-iodine process primarily utilizing heat. Both processes require high temperature (>850°C) for enhanced efficiency; temperatures indicative of NGNP. Safety and licensing mandates prudently dictate that the NGNP and the hydrogen production facility be physically isolated, perhaps requiring separation of over 100m. There are several options to transferring multi-megawatt thermal power over such a distance. One option is simply to produce only electricity, transfer by wire to the hydrogen plant, and then reconvert the electric energy to heat via Joule or induction heating. Electrical transport, however, suffers energy losses of 60-70% due to the thermal to electric conversion inherent in the Brayton cycle. A second option is thermal energy transport via a single-phase forced convection loop where a fluid is mechanically pumped between heat exchangers at the nuclear and hydrogen plants. High temperatures, however, present unique materials and pumping challenges. Single phase, low pressure helium is an attractive option for NGNP, but is not suitable for a single purpose facility dictated to hydrogen production because low pressure helium requires higher pumping power and makes the process very inefficient. A third option is two-phase heat transfer utilizing a high temperature thermosyphon. Heat transport occurs via evaporation and condensation, and the heat transport fluid is re-circulated by gravitational force. Thermosyphon has the capability to transport heat at high rates over appreciable distances, virtually isothermally and without any requirement for external pumping devices. For process heat, intermediate heat exchangers (IHX) are desired to transfer heat from

  3. Acid-Base Bifunctional Zirconium N-Alkyltriphosphate Nanohybrid for Hydrogen Transfer of Biomass-Derived Carboxides

    DEFF Research Database (Denmark)

    Li, Hu; He, Jian; Riisager, Anders


    Catalytic transfer hydrogenation (CTH) reactions are efficient transformation routes to upgrade biobased chemicals. Herein, we report a facile and template-free route to synthesize a series of heterogeneous nitrogen-containing alkyltriphosphonate-metal hybrids with enhancive Lewis acid and base...... of Lewis basic sites adjacent to acid sites with an appropriate base/acid site ratio (1:0.7) in ZrPN significantly improved the yield of FFA. Mechanistic studies for the transformation of FUR to FFA with ZrPN in 2-propanol-d(8) evidently indicate CTH reaction proceeding via a direct intermolecular hydrogen...

  4. Theoretical study on water-mediated excited-state multiple proton transfer in 7-azaindole: significance of hydrogen bond rearrangement. (United States)

    Yu, Xue-fang; Yamazaki, Shohei; Taketsugu, Tetsuya


    Excited-state multiple proton transfer (ESMPT) in the cluster of 7-azaindole with three water molecules [7-azaindole(H(2)O)(3)] is theoretically investigated by the TDDFT, CASPT2, and CC2 methods. Examination of the potential energy surface in the first excited state indicates that ESMPT in 7-azaindole(H(2)O)(3) proceeds initially with the rearrangement of hydrogen bond structure of water molecules from a bridged-planar isomer to a cyclic-nonplanar isomer, followed by triple proton transfer in the latter. This reaction is found to be energetically more favorable than quadruple proton transfer in the bridged-planar isomer without hydrogen bond reorganization. It is also shown that all proton-transfer processes follow a concerted mechanism rather than a stepwise mechanism. The computational results show good consistency with the unexpected experimental observations as to the electronic spectra and excited-state lifetime. In particular, the barrier of the hydrogen bond rearrangement is found to be less than 1 kcal/mol, consistent with the missing vibronic bands for 7-azaindole(H(2)O)(3) with an excess energy of more than 200 cm(-1) in the S(1) state.

  5. Research and development of asymmetrical heat transfer augmentation method in radial channels of blades for high temperature gas turbines (United States)

    Shevchenko, I. V.; Rogalev, A. N.; Garanin, I. V.; Vegera, A. N.; Kindra, V. O.


    The serpentine-like one and half-pass cooling channel systems are primarily used in blades fabricated by the lost-wax casting process. The heat transfer turbulators like cross-sectional or angled ribs used in channels of the midchord region failed to eliminate the temperature irregularity from the suction and pressure sides, which is reaching 200°C for a first stage blade of the high-pressure turbine for an aircraft engine. This paper presents the results of a numerical and experimental test of an advanced heat transfer augmentation system in radial channels developed for alignment of the temperature field from the suction and pressure sides. A numerical simulation of three-dimensional coolant flow for a wide range of Reynolds numbers was carried out using ANSYS CFX software. Effect of geometrical parameters on the heat removal asymmetry was determined. The test results of a blade with the proposed intensification system conducted in a liquid-metal thermostat confirmed the accuracy of calculations. Based on the experimental data, the dependencies for calculation of heat transfer coefficients to the cooling air in the blade studied were obtained.

  6. Non-typical fluorescence studies of excited and ground state proton and hydrogen transfer (United States)

    Gil, Michał; Kijak, Michał; Piwoński, Hubert; Herbich, Jerzy; Waluk, Jacek


    Fluorescence studies of tautomerization have been carried out for various systems that exhibit single and double proton or hydrogen translocation in various environments, such as liquid and solid condensed phases, ultracold supersonic jets, and finally, polymer matrices with single emitters. We focus on less explored areas of application of fluorescence for tautomerization studies, using porphycene, a porphyrin isomer, as an example. Fluorescence anisotropy techniques allow investigations of self-exchange reactions, where the reactant and product are formally identical. Excitation with polarized light makes it possible to monitor tautomerization in single molecules and to detect their three-dimensional orientation. Analysis of fluorescence from single vibronic levels of jet-isolated porphycene not only demonstrates coherent tunneling of two internal protons, but also indicates that the process is vibrational mode-specific. Next, we present bifunctional proton donor-acceptor systems, molecules that are able, depending on the environment, to undergo excited state single intramolecular or double intermolecular proton transfer. For molecules that have donor and acceptor groups located in separate moieties linked by a single bond, excited state tautomerization can be coupled to mutual twisting of the two subunits.

  7. Study of hydrogen implantation-induced blistering in GaSb for potential layer transfer applications (United States)

    Pathak, Ravi; Dadwal, U.; Singh, R.


    GaSb samples were implanted by 100 keV hydrogen ions (H+) at room temperature with fluence values of 1  ×  1017 and 2  ×  1017 ions cm-2. Post-implantation annealing studies revealed that the samples implanted with a fluence of 2  ×  1017 ions cm-2 did not show blistering/exfoliation. For the lower fluence, the samples showed the formation of surface blisters/craters along with the large area exfoliation of the top H-implanted surface. Topographical investigations of the samples were carried out using Nomarski optical microscopy, atomic force microscopy and stylus surface profilometry. The lateral sizes and heights of the blisters varied between 2-5 µm and 5-20 nm respectively. The root mean square roughness of the exfoliated region was about 12 nm while the exfoliation depth was found to be 730 nm. The exfoliation depth in the H-implanted GaSb is close to the damage concentration peak as found from SRIM calculations. The Föppl-von Karman theory of thin plates has been used to understand the effect of internal pressure and stress on the surface blistering. Using the above mentioned implantation and annealing parameters, potential layer transfer of GaSb could be enabled.

  8. Non-typical fluorescence studies of excited and ground state proton and hydrogen transfer

    KAUST Repository

    Gil, Michał


    Fluorescence studies of tautomerization have been carried out for various systems that exhibit single and double proton or hydrogen translocation in various environments, such as liquid and solid condensed phases, ultracold supersonic jets, and finally, polymer matrices with single emitters.We focus on less explored areas of application of fluorescence for tautomerization studies, using porphycene, a porphyrin isomer, as an example. Fluorescence anisotropy techniques allow investigations of self-exchange reactions, where the reactant and product are formally identical. Excitation with polarized light makes it possible to monitor tautomerization in single molecules and to detect their three-dimensional orientation. Analysis of fluorescence from single vibronic levels of jet-isolated porphycene not only demonstrates coherent tunneling of two internal protons, but also indicates that the process is vibrational mode-specific. Next, we present bifunctional proton donoracceptor systems, molecules that are able, depending on the environment, to undergo excited state single intramolecular or double intermolecular proton transfer. For molecules that have donor and acceptor groups located in separate moieties linked by a single bond, excited state tautomerization can be coupled to mutual twisting of the two subunits.

  9. Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

    KAUST Repository

    Dehury, Niranjan


    Herein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-arylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd compounds, the precursor PdCl2 and the phosphine based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit the tandem catalysis.

  10. Hydrogen permeation in asymmetric La28-xW4 + xO54 + 3x/2 membranes

    DEFF Research Database (Denmark)

    Gil, Vanesa; Gurauskis, Jonas; Kjølseth, Christian


    Asymmetric supported La28 - xW4 + xO 54 + 3x/2 (La/W ≈ 5.6) membranes were investigated for their hydrogen permeation properties as a function of temperature and feed gas conditions. Dense membranes of thickness 25-30 μm supported on substrates with 25 and 40 vol.% porosity were compared. Above 850.......14 NmL min-1 cm-2 was recorded at 1000 °C with 10 vol.% H2 (2.5 vol.% H2O) as feed gas....

  11. Hydrogen

    Directory of Open Access Journals (Sweden)

    John O’M. Bockris


    Full Text Available The idea of a “Hydrogen Economy” is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO2 in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H2 from the electrolyzer. Methanol made with CO2 from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan. Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech.

  12. Enantioselective Iridium Catalyzed Carbonyl Allylation from the Alcohol or Aldehyde Oxidation Level via Transfer Hydrogenative Coupling of Allyl Acetate: Departure from Chirally Modified Allyl Metal Reagents in Carbonyl Addition (United States)

    Kim, In Su; Ngai, Ming-Yu; Krische, Michael J.


    Under the conditions of transfer hydrogenation employing an iridium catalyst generated in situ from [Ir(cod)Cl]2, the chiral phosphine ligands (R)-BINAP or (R)-Cl,MeO-BIPHEP and m-nitrobenzoic acid, allyl acetate couples to allylic alcohols 1a-1c, aliphatic alcohols 1d-1l and benzylic alcohols 1m-1u to furnish products of carbonyl allylation 3a-3u with exceptional levels of asymmetric induction. The very same set of optically enriched carbonyl allylation products 3a-3u are accessible from enals 2a-2c, aliphatic aldehydes 2d-2l and aryl aldehydes 2m-2u, using iridium catalysts ligated by (-)-TMBTP or (R)-Cl,MeO-BIPHEP under identical conditions, but employing isopropanol as a hydrogen donor. As corroborated by single crystal X-ray diffraction, the active catalyst is the cyclometallated complex V, which arises upon ortho-C-H insertion of iridium onto m-nitrobenzoic acid. The results of isotopic labeling are consistent with intervention of symmetric iridium π-allylationl intermediates or rapid interconversion of σ-allyl haptomers through the agency of a symmetric π-allyl. Competition experiments demonstrate rapid and reversible hydrogenation-dehydrogenation of the carbonyl partner in advance of C-C coupling. The coupling products, which are homoallylic alcohols, experience very little erosion of optical purity by way of redox equilibration under the coupling conditions, although isopropanol, a secondary alcohol, may serve as terminal reductant. A plausible catalytic mechanism accounting for these observations is proposed, along with a stereochemical model that accounts for the observed sense of absolute stereoinduction. This protocol for asymmetric carbonyl allylation transcends the barriers imposed by oxidation level and the use of preformed allyl-metal reagents. PMID:18841896

  13. Enantioselective iridium-catalyzed carbonyl allylation from the alcohol or aldehyde oxidation level via transfer hydrogenative coupling of allyl acetate: departure from chirally modified allyl metal reagents in carbonyl addition. (United States)

    Kim, In Su; Ngai, Ming-Yu; Krische, Michael J


    Under the conditions of transfer hydrogenation employing an iridium catalyst generated in situ from [Ir(cod)Cl]2, chiral phosphine ligand (R)-BINAP or (R)-Cl,MeO-BIPHEP, and m-nitrobenzoic acid, allyl acetate couples to allylic alcohols 1a-c, aliphatic alcohols 1d-l, and benzylic alcohols 1m-u to furnish products of carbonyl allylation 3a-u with exceptional levels of asymmetric induction. The very same set of optically enriched carbonyl allylation products 3a-u are accessible from enals 2a-c, aliphatic aldehydes 2d-l, and aryl aldehydes 2m-u, using iridium catalysts ligated by (-)-TMBTP or (R)-Cl,MeO-BIPHEP under identical conditions, but employing isopropanol as a hydrogen donor. A catalytically active cyclometallated complex V, which arises upon ortho-C-H insertion of iridium onto m-nitrobenzoic acid, was characterized by single-crystal X-ray diffraction. The results of isotopic labeling are consistent with intervention of symmetric iridium pi-allyl intermediates or rapid interconversion of sigma-allyl haptomers through the agency of a symmetric pi-allyl. Competition experiments demonstrate rapid and reversible hydrogenation-dehydrogenation of the carbonyl partner in advance of C-C coupling. However, the coupling products, which are homoallylic alcohols, experience very little erosion of optical purity by way of redox equilibration under the coupling conditions, although isopropanol, a secondary alcohol, may serve as terminal reductant. A plausible catalytic mechanism accounting for these observations is proposed, along with a stereochemical model that accounts for the observed sense of absolute stereoinduction. This protocol for asymmetric carbonyl allylation transcends the barriers imposed by oxidation level and the use of preformed allyl metal reagents.

  14. Experiments of time elapse comparison of two hydrogen clocks based on two-way satellite time and frequency transfer (United States)

    Shen, Ziyu; Cai, Chenghui; Shen, Wen-Bin


    Since optical atomic clocks in laboratory have achieved a stability and accuracy of 10E-18 level, scientists expect near-future potential applications of precise clocks in geoscience, including for instance the geopotential measurement and world height system unification. Here we provide time ticks comparison between a fixed hydrogen clock and a portable hydrogen clock using the two-way satellite time and frequency transfer (TWSTFT) technique. After comparing the time ticks of two hydrogen clocks at the positions at the same height level for a period, they were separated for a height difference and compared again for a period. Experimental results are expected to confirm the general relativity theory and may provide technical details for future actual applications of precise clocks in geodesy. This study is supported by National 973 Project China (grant No. 2013CB733301 and 2013CB733305) and NSFCs (grant Nos. 41174011, 41429401, 41210006, 41128003, 41021061).

  15. Stepwise vs concerted excited state tautomerization of 2-hydroxypyridine: Ammonia dimer wire mediated hydrogen/proton transfer

    Energy Technology Data Exchange (ETDEWEB)

    Esboui, Mounir, E-mail: [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications, Département de Physique, Faculté des Sciences de Tunis, 2092 Tunis (Tunisia); Technical and Vocational Training Corporation, Hail College of Technology, P.O. Box 1960, Hail 81441 (Saudi Arabia)


    The stepwise and concerted excited state intermolecular proton transfer (PT) and hydrogen transfer (HT) reactions in 2-hydroxypyridine-(NH{sub 3}){sub 2} complex in the gas phase under Cs symmetry constraint and without any symmetry constraints were performed using quantum chemical calculations. It shows that upon excitation, the hydrogen bonded in 2HP-(NH{sub 3}){sub 2} cluster facilitates the releasing of both hydrogen and proton transfer reactions along ammonia wire leading to the formation of the 2-pyridone tautomer. For the stepwise mechanism, it has been found that the proton and the hydrogen may transfer consecutively. These processes are distinguished from each other through charge translocation analysis and the coupling between the motion of the proton and the electron density distribution along ammonia wire. For the complex under Cs symmetry, the excited state HT occurs on the A″({sup 1}πσ{sup ∗}) and A′({sup 1}nσ{sup ∗}) states over two accessible energy barriers along reaction coordinates, and excited state PT proceeds mainly through the A′({sup 1}ππ{sup ∗}) and A″({sup 1}nπ{sup ∗}) potential energy surfaces. For the unconstrained complex, potential energy profiles show two {sup 1}ππ{sup ∗}-{sup 1}πσ{sup ∗} conical intersections along enol → keto reaction path indicating that proton and H atom are localized, respectively, on the first and second ammonia of the wire. Moreover, the concerted excited state PT is competitive to take place with the stepwise process, because it proceeds over low barriers of 0.14 eV and 0.11 eV with respect to the Franck-Condon excitation of enol tautomer, respectively, under Cs symmetry and without any symmetry constraints. These barriers can be probably overcome through tunneling effect.

  16. [Two-dimensional model of a double-well potential: proton transfer when a hydrogen bond is deformed]. (United States)

    Krasilnikov, P M


    The potential energy cross-section profile along a hydrogen bond may contain two minima in certain conditions; it is so-called a double well potential. The H-bond double well potential is essential for proton transfer along this hydrogen bond. We have considered the two-dimensional model of such double well potential in harmonic approximation, and we have also investigated the proton tunneling in it. In real environments thermal motion of atoms or conformational changes may cause reorientation and relative shift of molecule fragment forming the hydrogen bond and, as a result, the hydrogen bond isdeformed. This deformation is liable to change the double well potential form and, hence, the probability of the proton tunneling is changed too. As it is shown the characteristic time of proton tunneling is essentially increased by even small relative shift of heavy atoms forming the H-bond and also rotational displacement of covalent bond generated by one of heavy atoms and the proton (hydrogen atom). However, it is also shown, at the certain geometry of the H-bond deformation the opposite effect occurred, i.e., the characteristic time is not increased and even decreased. Notice that such its behavior arises from two-dimensionality of potential wells; this and other properties of our model are discussed in detail.

  17. Structural and medium effects on the reactions of the cumyloxyl radical with intramolecular hydrogen bonded phenols. The interplay between hydrogen-bonding and acid-base interactions on the hydrogen atom transfer reactivity and selectivity. (United States)

    Salamone, Michela; Amorati, Riccardo; Menichetti, Stefano; Viglianisi, Caterina; Bietti, Massimo


    A time-resolved kinetic study on the reactions of the cumyloxyl radical (CumO(•)) with intramolecularly hydrogen bonded 2-(1-piperidinylmethyl)phenol (1) and 4-methoxy-2-(1-piperidinylmethyl)phenol (2) and with 4-methoxy-3-(1-piperidinylmethyl)phenol (3) has been carried out. In acetonitrile, intramolecular hydrogen bonding protects the phenolic O-H of 1 and 2 from attack by CumO(•) and hydrogen atom transfer (HAT) exclusively occurs from the C-H bonds that are α to the piperidine nitrogen (α-C-H bonds). With 3 HAT from both the phenolic O-H and the α-C-H bonds is observed. In the presence of TFA or Mg(ClO4)2, protonation or Mg(2+) complexation of the piperidine nitrogen removes the intramolecular hydrogen bond in 1 and 2 and strongly deactivates the α-C-H bonds of the three substrates. Under these conditions, HAT to CumO(•) exclusively occurs from the phenolic O-H group of 1-3. These results clearly show that in these systems the interplay between intramolecular hydrogen bonding and Brønsted and Lewis acid-base interactions can drastically influence both the HAT reactivity and selectivity. The possible implications of these findings are discussed in the framework of the important role played by tyrosyl radicals in biological systems.

  18. Asymmetrical transfer effects of cognitive bias modification: Modifying attention to threat influences interpretation of emotional ambiguity, but not vice versa. (United States)

    Bowler, J O; Hoppitt, L; Illingworth, J; Dalgleish, T; Ononaiye, M; Perez-Olivas, G; Mackintosh, B


    It is well established that attention bias and interpretation bias each have a key role in the development and continuation of anxiety. How the biases may interact with one another in anxiety is, however, poorly understood. Using cognitive bias modification techniques, the present study examined whether training a more positive interpretation bias or attention bias resulted in transfer of effects to the untrained cognitive domain. Differences in anxiety reactivity to a real-world stressor were also assessed. Ninety-seven first year undergraduates who had self-reported anxiety were allocated to one of four groups: attention bias training (n = 24), interpretation bias training (n = 26), control task training (n = 25) and no training (n = 22). Training was computer-based and comprised eight sessions over four weeks. Baseline and follow-up measures of attention and interpretation bias, anxiety and depression were taken. A significant reduction in threat-related attention bias and an increase in positive interpretation bias occurred in the attention bias training group. The interpretation bias training group did not exhibit a significant change in attention bias, only interpretation bias. The effect of attention bias training on interpretation bias was significant as compared with the two control groups. There were no effects on self-report measures. The extent to which interpretive training can modify attentional processing remains unclear. Findings support the idea that attentional training might have broad cognitive consequences, impacting downstream on interpretive bias. However, they do not fully support a common mechanism hypothesis, as interpretive training did not impact on attentional bias. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

  19. Hydrogen Bonding to Alkanes: Computational Evidence

    DEFF Research Database (Denmark)

    Hammerum, Steen; Olesen, Solveig Gaarn


    The structural, vibrational, and energetic properties of adducts of alkanes and strong cationic proton donors were studied with composite ab initio calculations. Hydrogen bonding in [D-H+ H-alkyl] adducts contributes to a significant degree to the interactions between the two components, which...... is substantiated by NBO and AIM results. The hydrogen bonds manifest themselves in the same manner as conventional hydrogen bonds, D-H bond elongation, D-H vibrational stretching frequency red shift and intensity increase, and adduct stabilization. The alkane adducts also exhibit elongation of the C-H bonds...... involved and a concurrent red shift, which is rationalized in terms of charge-transfer interactions that cause simultaneous weakening of both the O-H and C-H bonds. Like other dihydrogen-bonded adducts, the adducts possess a bent structure and asymmetric bifurcated hydrogen bonds. The hydrogen bonds...

  20. Solvent-dependent excited-state hydrogen transfer and intersystem crossing in 2-(2′-hydroxyphenyl)-benzothiazole

    KAUST Repository

    Aly, Shawkat Mohammede


    The excited-state intramolecular hydrogen transfer (ESIHT) of 2-(2′-hydroxyphenyl) benzothiazole (HBT) has been investigated in a series of nonpolar, polar aprotic, and polar protic solvents. A variety of state-of-the-art experimental methods were employed, including femto- and nanosecond transient absorption and fluorescence upconversion spectroscopy with broadband capabilities. We show that the dynamics and mechanism of ESIHT of the singlet excited HBT are strongly solvent-dependent. In nonpolar solvents, the data demonstrate that HBT molecules adopt a closed form stabilized by O-H⋯N chelated hydrogen bonds with no twisting angle, and the photoinduced H transfer occurs within 120 fs, leading to the formation of a keto tautomer. In polar solvents, owing to dipole-dipole cross talk and hydrogen bonding interactions, the H transfer process is followed by ultrafast nonradiative deactivation channels, including ultrafast internal conversion (IC) and intersystem crossing (ISC). This is likely to be driven by the twisting motion around the C-C bond between the hydroxyphenyl and thiazole moieties, facilitating the IC back to the enol ground state or to the keto triplet state. In addition, our femtosecond time-resolved fluorescence experiments indicate, for the first time, that the lifetime of the enol form in ACN is approximately 280 fs. This observation indicates that the solvent plays a crucial role in breaking the H bond and deactivating the excited state of the HBT. Interestingly, the broadband transient absorption and fluorescence up-conversion data clearly demonstrate that the intermolecular proton transfer from the excited HBT to the DMSO solvent is about 190 fs, forming the HBT anion excited state.

  1. Ground state isomerism in betacarboline hydrogen bond complexes: The charge transfer nature of its large Stokes shifted emission (United States)

    Sánchez-Coronilla, Antonio; Balón, Manuel; Muñoz, María A.; Hidalgo, José; Carmona, Carmen


    The hydrogen bonding and excited state proton transfer reactions between betacarboline, 9 H-pyrido[3,4- b]indole, BC, and 1,1,1,3,3,3-hexafluoropropan-2-ol, HFIP, have been studied in the aprotic solvents cyclohexane and toluene by absorption, steady state and time resolved fluorescence measurements. On the basis of these results and those of previous works (Refs. [A. Sánchez-Coronilla, C. Carmona, M.A. Muñoz, M. Balón, Chem. Phys., 327 (2006) 70] and [A. Sánchez-Coronilla, M. Balón, M.A. Muñoz, C. Carmona, Chem. Phys. 344 (2008) 72]) two main fundamental conclusions can be drawn on the photophysical behaviour of BC. Thus, it is shown, for the first time, that the non-cyclic double hydrogen bond complexes formed through both nitrogen atoms of BC, DHB, can suffer, in their ground state, an isomerisation process. These adducts acquire a quinoid structure in cyclohexane, but maintain a dipolar zwitterionic structure in toluene. Moreover, it is concluded that the observed large Stokes shifted emission, around 520 nm, is not due, as it has been so far generally accepted, to the emission of a BC zwitterionic phototautomer, but to the intramolecular charge transfer, ICT, excited state emissions of the DHB hydrogen bond adducts.

  2. Hydrogen bond strengthening induces fluorescence quenching of PRODAN derivative by turning on twisted intramolecular charge transfer (United States)

    Yang, Yonggang; Li, Donglin; Li, Chaozheng; Liu, YuFang; Jiang, Kai


    Researchers have proposed different effective mechanisms of hydrogen bonding (HB) on the fluorescence of 6-propionyl-2-dimethylaminonaphthalene (PRODAN) and its derivatives. Herein, excited state transition and dynamics analysis confirm that the fluorescence of PD (a derivative of PRODAN with ethyl replaced by 3-hydroxy-2,2-dimethylpropan) emits from the planar intramolecular charge transfer (PICT) state rather than twist ICT (TICT) state, because the fluorescence emission and surface hopping from the TICT state to the twist ground (T-S0) state is energy forbidden. Nevertheless, the strengthening of intramolecular-HB (intra-HB) and intermolecular-HB (inter-HB) of PD-(methanol)2 smooth the pathway of surface hopping from TICT to T-S0 state and the external conversion going to planar ground state by decreasing the energy difference of the two states. This smoothing changes the fluorescence state of PD-(methanol)2 to the TICT state in which fluorescence emission does not occur but surface hopping, leading to the partial fluorescence quenching of PD in methanol solvent. This conclusion is different from previous related reports. Moreover, the inter-HB strengthening of PD-methanol in PICT state induces the cleavage of intra-HB and a fluorescence red-shift of 54 nm compared to PD. This red-shift increases to 66 nm for PD-(methanol)2 for the strengthening of the one intra-HB and two inter-HBs. The dipole moments of PD-methanol and PD-(methanol)2 respectively increase about 10.3D and 8.1D in PICT state compared to PD. The synergistic effect of intra-HB and inter-HB induces partial quenching of PD in methanol solvent by turning on the TICT state and fluorescence red-shift. This work gives a reasonable description on the fluorescence red-shift and partial quenching of PD in methanol solvent, which will bring insight into the study of spectroscopic properties of molecules owning better spectral characteristics.

  3. Deactivation of 6-Aminocoumarin Intramolecular Charge Transfer Excited State through Hydrogen Bonding (United States)

    Krystkowiak, Ewa; Dobek, Krzysztof; Maciejewski, Andrzej


    This paper presents results of the spectral (absorption and emission) and photophysical study of 6-aminocoumarin (6AC) in various aprotic hydrogen-bond forming solvents. It was established that solvent polarity as well as hydrogen-bonding ability influence solute properties. The hydrogen-bonding interactions between S1-electronic excited solute and solvent molecules were found to facilitate the nonradiative deactivation processes. The energy-gap dependence on radiationless deactivation in aprotic solvents was found to be similar to that in protic solvents. PMID:25244014

  4. Phonon driven proton transfer in crystals with short strong hydrogen bonds

    NARCIS (Netherlands)

    Fontaine-Vive, F.; Johnson, M.R.; Kearley, G.J.; Cowan, J.A.; Howard, J.A.K.; Parker, S.F.


    Recent work on understanding why protons migrate with increasing temperature in short, strong hydrogen bonds is extended here to three more organic, crystalline systems. Inelastic neutron scattering and density functional theory based simulations are used to investigate structure, vibrations, and

  5. Technology Development for Hydrogen Propellant Storage and Transfer at the Kennedy Space Center (KSC) (United States)

    Youngquist, Robert; Starr, Stanley; Krenn, Angela; Captain, Janine; Williams, Martha


    The National Aeronautics and Space Administration (NASA) is a major user of liquid hydrogen. In particular, NASA's John F. Kennedy (KSC) Space Center has operated facilities for handling and storing very large quantities of liquid hydrogen (LH2) since the early 1960s. Safe operations pose unique challenges and as a result NASA has invested in technology development to improve operational efficiency and safety. This paper reviews recent innovations including methods of leak and fire detection and aspects of large storage tank health and integrity. We also discuss the use of liquid hydrogen in space and issues we are addressing to ensure safe and efficient operations should hydrogen be used as a propellant derived from in-situ volatiles.

  6. Production of hydrogen by electron transfer catalysis using conventional and photochemical means (United States)

    Rillema, D. P.


    Alternate methods of generating hydrogen from the sulfuric acid thermal or electrochemical cycles are presented. A number of processes requiring chemical, electrochemical or photochemical methods are also presented. These include the design of potential photoelectrodes and photocatalytic membranes using Ru impregnated nafion tubing, and the design of experiments to study the catalyzed electrolytic formation of hydrogen and sulfuric acid from sulfur dioxide and water using quinones as catalysts. Experiments are carried out to determine the value of these approaches to energy conversion.

  7. Ultrasound assisted selective catalytic transfer hydrogenation of soybean oil using 5% Pd/C as catalyst under ambient conditions in water. (United States)

    Sancheti, Sonam V; Gogate, Parag R


    Catalytic transfer hydrogenation (CTH) is an alternative approach that does not require the use of potentially dangerous hydrogen gas. Pd/C is the most favoured catalyst for the selective hydrogenation of soybean oil yielding lower extent of formation of stearic acid and trans-isomer, which have adverse health effects. The present work deals with intensification of catalytic transfer hydrogenation of soybean oil in the presence of 5wt.% Pd/C using ultrasound under ambient reaction conditions. The effect of important operating parameters such as ultrasound power, temperature, type of hydrogen donor, catalyst loading and donor concentration on the progress of reaction has been investigated. It was established that the maximum extent of hydrogenation as indicated by reduction in iodine value from 135 to 95 was observed under optimized conditions of irradiation power as 100W, 22kHz frequency, 90% duty cycle, ammonium formate concentration of 0.32mol/50ml water and 2% (w/w) Pd/C loading at ambient temperature and pressure in the presence of water as solvent. The approach also offered excellent selectivity with much lower trans-isomer formation as compared to the conventional approach of high pressure hydrogenation. Overall, the work has successfully demonstrated process intensification benefits due to the use of ultrasound for the Pd/C catalyzed transfer hydrogenation of soybean oil. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction. Quarterly technical progress report, March 1, 1991--May 31, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Eisch, J.J.


    The ultimate objective of this research is to uncover new catalytic processes for the liquefaction of coal and for upgrading coal-derived fuels by removing undesirable organosulfur, organonitrogen and organooxygen constituents. Basic to both the liquefaction of coal and the purification of coal liquids is the transfer of hydrogen from such sources as dihydrogen, metal hydrides or partially reduced aromatic hydrocarbons to the extensive aromatic rings in coal itself or to aromatic sulfides, amines or ethers. Accordingly, this study is exploring how such crucial hydrogen-transfer processes might be catalyzed by soluble, low-valent transition metal complexes and/or Lewis acids under moderate conditions of temperature and pressure. By learning the mechanism whereby H{sub 2}, metal hydrides or partially hydrogenated aromatics do transfer hydrogen to model aromatic compounds, with the aid of homogeneous, bimetallic catalysts, we hope to identify new methods for producing superior fuels from coal.

  9. Development of Novel Electrode Materials for the Electrocatalysis of Oxygen-Transfer and Hydrogen-Transfer Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Simpson, Brett Kimball [Iowa State Univ., Ames, IA (United States)


    Throughout this thesis, the fundamental aspects involved in the electrocatalysis of anodic O-transfer reactions and cathodic H-transfer reactions have been studied. The investigation into anodic O-transfer reactions at undoped and Fe(III)[doped MnO2 films] revealed that MnO2 film electrodes prepared by a cycling voltammetry deposition show improved response for DMSO oxidation at the film electrodes vs. the Au substrate. Doping of the MnO2 films with Fe(III) further enhanced electrode activity. Reasons for this increase are believed to involve the adsorption of DMSO by the Fe(III) sites. The investigation into anodic O-transfer reactions at undoped and Fe(III)-doped RuO2 films showed that the Fe(III)-doped RuO2-film electrodes are applicable for anodic detection of sulfur compounds. The Fe(III) sites in the Fe-RuO2 films are speculated to act as adsorption sites for the sulfur species while the Ru(IV) sites function for anodic discharge of H2O to generate the adsorbed OH species. The investigation into cathodic H-transfer reactions, specifically nitrate reduction, at various pure metals and their alloys demonstrated that the incorporation of metals into alloy materials can create a material that exhibits bifunctional properties for the various steps involved in the overall nitrate reduction reaction. The Sb10Sn20Ti70, Cu63Ni37 and Cu25Ni75 alloy electrodes exhibited improved activity for nitrate reduction as compared to their pure component metals. The Cu63Ni37 alloy displayed the highest activity for nitrate reduction. The final investigation was a detailed study of the electrocatalytic activity of cathodic H-transfer reactions (nitrate reduction) at various compositions of Cu-Ni alloy electrodes. Voltammetric response for NO3- at the Cu-Ni alloy electrode is superior to

  10. Hydrogen-bond-dynamics-based switching of conductivity and magnetism: a phase transition caused by deuterium and electron transfer in a hydrogen-bonded purely organic conductor crystal. (United States)

    Ueda, Akira; Yamada, Shota; Isono, Takayuki; Kamo, Hiromichi; Nakao, Akiko; Kumai, Reiji; Nakao, Hironori; Murakami, Youichi; Yamamoto, Kaoru; Nishio, Yutaka; Mori, Hatsumi


    A hydrogen bond (H-bond) is one of the most fundamental and important noncovalent interactions in chemistry, biology, physics, and all other molecular sciences. Especially, the dynamics of a proton or a hydrogen atom in the H-bond has attracted increasing attention, because it plays a crucial role in (bio)chemical reactions and some physical properties, such as dielectricity and proton conductivity. Here we report unprecedented H-bond-dynamics-based switching of electrical conductivity and magnetism in a H-bonded purely organic conductor crystal, κ-D3(Cat-EDT-TTF)2 (abbreviated as κ-D). This novel crystal κ-D, a deuterated analogue of κ-H3(Cat-EDT-TTF)2 (abbreviated as κ-H), is composed only of a H-bonded molecular unit, in which two crystallographically equivalent catechol-fused ethylenedithiotetrathiafulvalene (Cat-EDT-TTF) skeletons with a +0.5 charge are linked by a symmetric anionic [O···D···O](-1)-type strong H-bond. Although the deuterated and parent hydrogen systems, κ-D and κ-H, are isostructural paramagnetic semiconductors with a dimer-Mott-type electronic structure at room temperature (space group: C2/c), only κ-D undergoes a phase transition at 185 K, to change to a nonmagnetic insulator with a charge-ordered electronic structure (space group: P1). The X-ray crystal structure analysis demonstrates that this dramatic switching of the electronic structure and physical properties originates from deuterium transfer or displacement within the H-bond accompanied by electron transfer between the Cat-EDT-TTF π-systems, proving that the H-bonded deuterium dynamics and the conducting TTF π-electron are cooperatively coupled. Furthermore, the reason why this unique phase transition occurs only in κ-D is qualitatively discussed in terms of the H/D isotope effect on the H-bond geometry and potential energy curve.

  11. Hydrogen atom vs electron transfer in catecholase-mimetic oxidations by superoxometal complexes. Deuterium kinetic isotope effects. (United States)

    Simándi, Tatiana M; May, Zoltán; Szigyártó, Imola Cs; Simándi, László I


    Dioximato-cobalt(II), -iron(II) and -manganese(II) complexes (1)-(6), acting as functional catecholase and phenoxazinone synthase models, exhibit a deuterium kinetic isotope effect predicted by theory (k4H/k4D < or = 3) in the catalytic oxidative dehydrogenation of 3,5-di-tert-butylcatechol and 2-aminophenol by O2. KIEs in the range of (k4H/k4D approximately 1.79-3.51) are observed with (1) and (2) as catalysts, pointing to hydrogen atom transfer in the rate-determining step from the substrate hydroxy group to the metal-bound superoxo ligand. Less significant KIEs (1.06-1.20) are exhibited by catalysts systems (3)-(6), indicating that proton-coupled electron transfer is the preferred route in those cases.

  12. Control of interspecies electron transfer flow during anaerobic digestion: dynamic diffusion reaction models for hydrogen gas transfer in microbial flocs. (United States)

    Ozturk, S S; Palsson, B O; Thiele, J H


    Dynamic reaction diffusion models were used to analyze the consequences of aggregation for syntrophic reactions in methanogenic ecosystems. Flocs from a whey digestor were used to measure all model parameters under the in situ conditions of a particular defined biological system. Fermentation simulations without adjustable parameters could precisely predict the kinetics of H(2) gas production of digestor flocs during syntrophic methanogenesis from ethanol. The results demonstrated a kinetic compartmentalization of H(2) metabolism inside the flocs. The interspecies electron transfer reaction was mildly diffusion controlled. The H(2) gas profiles across the flocs showed high H (2) concentrations inside the flocs at any time. Simulations of the syntrophic metabolism at low substrate concentrations such as in digestors or sediments showed that it is impossible to achieve high H(2) gas turnovers at simultaneously low steady-state H(2) concentrations. This showed a mechanistic contradiction in the concept of postulated low H(2) microenvironments for the anaerobic digestion process. The results of the computer experiments support the conclusion that syntrophic H(2) production may only be a side reaction of H(2) independent interspecies electron transfer in methanogenic ecosystems.

  13. External Mass Transfer Model for Hydrogen Peroxide Decomposition by Terminox Ultra Catalase in a Packed-Bed Reactor

    Directory of Open Access Journals (Sweden)

    Grubecki Ireneusz


    Full Text Available It is known that external diffusional resistances are significant in immobilized enzyme packed-bed reactors, especially at large scales. Thus, the external mass transfer effects were analyzed for hydrogen peroxide decomposition by immobilized Terminox Ultra catalase in a packed-bed bioreactor. For this purpose the apparent reaction rate constants, kP, were determined by conducting experimental works at different superficial velocities, U, and temperatures. To develop an external mass transfer model the correlation between the Colburn factor, JD, and the Reynolds number, Re, of the type JD = K Re(n-1 was assessed and related to the mass transfer coefficient, kmL. The values of K and n were calculated from the dependence (am kp-1 - kR-1 vs. Re-1 making use of the intrinsic reaction rate constants, kR, determined before. Based on statistical analysis it was found that the mass transfer correlation JD = 0.972 Re-0.368 predicts experimental data accurately. The proposed model would be useful for the design and optimization of industrial-scale reactors.

  14. Monodisperse Ag/Pd core/shell nanoparticles assembled on reduced graphene oxide as highly efficient catalysts for the transfer hydrogenation of nitroarenes. (United States)

    Metin, Önder; Can, Hasan; Şendil, Kıvılcım; Gültekin, Mehmet Serdar


    Addressed herein is a facile seed-mediated synthesis of Ag/Pd core/shell nanoparticles (NPs) and their assembly on reduced graphene oxide (rGO) to catalyze the transfer hydrogenation of nitroarenes to anilines using ammonia borane (AB) as a hydrogen donor under ambient conditions. Monodisperse Ag/Pd core/shell NPs with controllable Pd shell-thickness were synthesized by the means of thermal decomposition of palladium(II) bromide over as-prepared Ag NPs in the mixture of oleylamine and oleic acid at 220°C. As-synthesized Ag/Pd core/shell NPs were characterized by TEM, HR-TEM, XRD, XPS, UV-Vis spectroscopy and ICP-MS and then they were assembled on reduced graphene oxide (rGO). Next, rGO@Ag/Pd catalysts were tested in the transfer hydrogenation of nitroarenes in which ammonia borane (AB) was used as a hydrogen donor at room temperature. It was demonstrated that the thickness of the Pd shell has a significant effect on the catalytic activity of rGO@Ag/Pd catalysts and the 1.75nm Pd shell provided the highest performance in the transfer hydrogenation reactions. The rGO@Ag/Pd catalyzed transfer hydrogenation reactions were tested over a variety of nitroarenes (total 16 examples) and they were all converted to the corresponding aniline derivatives with high yields in 5-15min under ambient conditions. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. In-situ diagnostic tools for hydrogen transfer leak characterization in PEM fuel cell stacks part II: Operational applications (United States)

    Niroumand, Amir M.; Homayouni, Hooman; DeVaal, Jake; Golnaraghi, Farid; Kjeang, Erik


    This paper describes a diagnostic tool for in-situ characterization of the rate and distribution of hydrogen transfer leaks in Polymer Electrolyte Membrane (PEM) fuel cell stacks. The method is based on reducing the air flow rate from a high to low value at a fixed current, while maintaining an anode overpressure. At high air flow rates, the reduction in air flow results in lower oxygen concentration in the cathode and therefore reduction in cell voltages. Once the air flow rate in each cell reaches a low value at which the cell oxygen-starves, the voltage of the corresponding cell drops to zero. However, oxygen starvation results from two processes: 1) the electrochemical oxygen reduction reaction which produces current; and 2) the chemical reaction between oxygen and the crossed over hydrogen. In this work, a diagnostic technique has been developed that accounts for the effect of the electrochemical reaction on cell voltage to identify the hydrogen leak rate and number of leaky cells in a fuel cell stack. This technique is suitable for leak characterization during fuel cell operation, as it only requires stack air flow and voltage measurements, which are readily available in an operational fuel cell system.

  16. New phosphine-diamine and phosphine-amino-alcohol tridentate ligands for ruthenium catalysed enantioselective hydrogenation of ketones and a concise lactone synthesis enabled by asymmetric reduction of cyano-ketones

    Directory of Open Access Journals (Sweden)

    Fuentes José A


    Full Text Available Abstract Enantioselective hydrogenation of ketones is a key reaction in organic chemistry. In the past, we have attempted to deal with some unsolved challenges in this arena by introducing chiral tridentate phosphine-diamine/Ru catalysts. New catalysts and new applications are presented here, including the synthesis of phosphine-amino-alcohol P,N,OH ligands derived from (R,S-1-amino-2-indanol, (S,S-1-amino-2-indanol and a new chiral P,N,N ligand derived from (R,R-1,2-diphenylethylenediamine. Ruthenium pre-catalysts of type [RuCl2(L(DMSO] were isolated and then examined in the hydrogenation of ketones. While the new P,N,OH ligand based catalysts are poor, the new P,N,N system gives up to 98% e.e. on substrates that do not react at all with most catalysts. A preliminary attempt at realising a new delta lactone synthesis by organocatalytic Michael addition between acetophenone and acrylonitrile, followed by asymmetric hydrogenation of the nitrile functionalised ketone is challenging in part due to the Michael addition chemistry, but also since Noyori pressure hydrogenation catalysts gave massively reduced reactivity relative to their performance for other acetophenone derivatives. The Ru phosphine-diamine system allowed quantitative conversion and around 50% e.e. The product can be converted into a delta lactone by treatment with KOH with complete retention of enantiomeric excess. This approach potentially offers access to this class of chiral molecules in three steps from the extremely cheap building blocks acrylonitrile and methyl-ketones; we encourage researchers to improve on our efforts in this potentially useful but currently flawed process.

  17. Theoretical investigation of hydrogen atom transfer in the cytosine-guanine base pair and its coupling with electronic rearrangement. Concerted vs stepwise mechanism. (United States)

    Villani, Giovanni


    The transformation of the DNA base pairs from the Watson-Crick (WC) structures to its tautomers having imino-enol form can be achieved via two types of hydrogen atom transfer processes: (i) concerted, and/or (ii) stepwise (step by step). Here, we have studied and compared these two mechanisms in the cytosine-guanine (C-G) system. In the first mechanism there is the concerted movement of two hydrogen atoms along two of the three H-bridges that bond the bases, one from the cytosine to guanine and the other in the opposite direction. This movement must be coupled to an electronic reorganization, with some bond orders that pass from single to double and vice versa, in order to preserve the neutrality of these new structures. In the stepwise mechanism the movement of the hydrogen atoms and the electronic reorganization are not concerted, and it implicates the movement of a hydrogen atom at a time with the identification of two or more steps in this reaction. There are two possible neutral imino-enol structures in the C-G system, and both have been considered here. The principal result from this paper is that a different behavior is observed if the hydrogen transfer begins with a H of the guanine or of the cytosine and that a concerted (synchronic in the N-N and asynchronic in the N-O) double-hydrogen transfer can be activated only when the first H atom to move is that of the guanine, in particular. This is different from the A-T system(1) studied previously where the movement in a N-N bridge produces a zwitterionic structure and that in the N-O the concerted double-hydrogen transfer. In both cases a general conclusion can be given: the concerted double-hydrogen process begins with a hydrogen atom of a purinic base.

  18. Improved performance in coprocessing through fundamental and mechanistic studies in hydrogen transfer and catalysis. Final report, September 26, 1989--March 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W.


    The key results obtained from this research project are given: (1) Hydrogen transfer from naphthenes to aromatics, coal and resid occurred at coprocessing temperatures and in a N{sub 2} atmosphere; (2) Hydrogen donors ranked in reactivity as cyclic olefins (nonaromatic hydroaromatic compounds) > hydroaromatic compounds > naphthenes. This ranking held regardless of the type of atmosphere, hydrogen or nitrogen, used; (3) Resids reduced by the Birch method transferred substantially more hydrogen to the aromatic acceptor than did the parent resids under coprocessing conditions; (4) Hydropretreatment of resids resulted in enhanced coal conversion compared to the parent resid; (5) Addition of hydrogen donors such as cyclic olefins or hydroaromatic donors increased the amount of coal conversion during coprocessing. Cyclic olefins and the active hydroaromatic donor, dihydroanthracene, showed the highest level of hydrogen donability. Tetralin and octahydroanthracene showed low reactivity; (6) Reduced resids were more effective in coprocessing than the parent resids, in terms of enhanced coal conversion; (7) Thermal and catalytic reactivity of cyclic olefins under nitrogen and hydrogen atmospheres was much higher than conventional hydroaromatic donors when no aromatic acceptor was present; (8) Reactivity of hydrogen donors was dependent upon the reactivity of the acceptor as well as that of the donors; (9) Three-ring hydrogen donors, dihydroanthracene and hexahydroanthracene, were most effective for transferring hydrogen to the Argonne coals while octahydroanthracene was the least reactive; (10) The kinetics data obtained for thermal and catalytic reactions involving cyclic olefins and hydroaromatic donors were adequately modeled by pseudo-first order kinetics; and (11) {Delta}G values calculated for cyclic olefins and hydroaromatic donors based on kinetics data adequately represented the reactivity observed experimentally.

  19. Termolecular proton transfer reactions assisted by ionic hydrogen bond formation: Reactions of aromatic cations with polar molecules (United States)

    Daly, G. M.; Meot-Ner, M.; Pithawalla, Y. B.; El-Shall, M. S.


    We present a new method that applies resonant-two-photon ionization to generate reactant ions selectively in the source of a high-pressure mass spectrometer (R2PI-HPMS) for kinetic and equilibrium studies. Applications to reactions that would be obscured otherwise in a complex system are illustrated in mixtures of benzene with polar solvent molecules (S). We observe a novel type of proton transfer reactions from C6H6+• to two S molecules where S=CH3CN, CH3OH, C2H5OH and CH3COOC2H5, and from C6H5CH3+• to two S molecules where S=CH3OH and C2H5OH to form protonated solvent S2H+ dimers. The reactions are driven by the strong hydrogen bonds in the S2H+ dimers and therefore require the formation of the hydrogen bond concertedly with proton transfer, to make the process energetically feasible. The adducts (C6H6+•)S are observed with blocked solvent molecules where the subsequent switching reaction to yield S2H+ is slow, but not with alcohol reactants that can form hydrogen-bonded chains that facilitate fast subsequent proton extraction. Correspondingly, kinetic simulations suggest that the mechanism proceeds through (C6H6+•)S+S→S2H++C6H5• and C6H6+•+2S→S2H++C6H5• reactions, respectively. The rate coefficients of these reactions are in the range 10-13-10-12 cm3 s-1 for the reaction through a bimolecular switching channel and in the range 10-26-10-28 cm6 s-1 for reaction through a direct termolecular proton extraction mechanism. The relation to energetics and reactant structure is examined.

  20. Control of Interspecies Electron Flow during Anaerobic Digestion: Significance of Formate Transfer versus Hydrogen Transfer during Syntrophic Methanogenesis in Flocs. (United States)

    Thiele, Jurgen H; Zeikus, J Gregory


    Microbial formate production and consumption during syntrophic conversion of ethanol or lactate to methane was examined in purified flocs and digestor contents obtained from a whey-processing digestor. Formate production by digestor contents or purified digestor flocs was dependent on CO(2) and either ethanol or lactate but not H(2) gas as an electron donor. During syntrophic methanogenesis, flocs were the primary site for formate production via ethanol-dependent CO(2) reduction, with a formate production rate and methanogenic turnover constant of 660 muM/h and 0.044/min, respectively. Floc preparations accumulated fourfold-higher levels of formate (40 muM) than digestor contents, and the free flora was the primary site for formate cleavage to CO(2) and H(2) (90 muM formate per h). Inhibition of methanogenesis by CHCl(3) resulted in formate accumulation and suppression of syntrophic ethanol oxidation. H(2) gas was an insignificant intermediary metabolite of syntrophic ethanol conversion by flocs, and its exogenous addition neither stimulated methanogenesis nor inhibited the initial rate of ethanol oxidation. These results demonstrated that >90% of the syntrophic ethanol conversion to methane by mixed cultures containing primarily Desulfovibrio vulgaris and Methanobacterium formicicum was mediated via interspecies formate transfer and that <10% was mediated via interspecies H(2) transfer. The results are discussed in relation to biochemical thermodynamics. A model is presented which describes the dynamics of a bicarbonate-formate electron shuttle mechanism for control of carbon and electron flow during syntrophic methanogenesis and provides a novel mechanism for energy conservation by syntrophic acetogens.

  1. Proton transfer reactions and hydrogen-bond networks in protein environments. (United States)

    Ishikita, Hiroshi; Saito, Keisuke


    In protein environments, proton transfer reactions occur along polar or charged residues and isolated water molecules. These species consist of H-bond networks that serve as proton transfer pathways; therefore, thorough understanding of H-bond energetics is essential when investigating proton transfer reactions in protein environments. When the pKa values (or proton affinity) of the H-bond donor and acceptor moieties are equal, significantly short, symmetric H-bonds can be formed between the two, and proton transfer reactions can occur in an efficient manner. However, such short, symmetric H-bonds are not necessarily stable when they are situated near the protein bulk surface, because the condition of matching pKa values is opposite to that required for the formation of strong salt bridges, which play a key role in protein-protein interactions. To satisfy the pKa matching condition and allow for proton transfer reactions, proteins often adjust the pKa via electron transfer reactions or H-bond pattern changes. In particular, when a symmetric H-bond is formed near the protein bulk surface as a result of one of these phenomena, its instability often results in breakage, leading to large changes in protein conformation.

  2. Influence of heat transfer rates on pressurization of liquid/slush hydrogen propellant tanks (United States)

    Sasmal, G. P.; Hochstein, J. I.; Hardy, T. L.


    A multi-dimensional computational model of the pressurization process in liquid/slush hydrogen tank is developed and used to study the influence of heat flux rates at the ullage boundaries on the process. The new model computes these rates and performs an energy balance for the tank wall whereas previous multi-dimensional models required a priori specification of the boundary heat flux rates. Analyses of both liquid hydrogen and slush hydrogen pressurization were performed to expose differences between the two processes. Graphical displays are presented to establish the dependence of pressurization time, pressurant mass required, and other parameters of interest on ullage boundary heat flux rates and pressurant mass flow rate. Detailed velocity fields and temperature distributions are presented for selected cases to further illuminate the details of the pressurization process. It is demonstrated that ullage boundary heat flux rates do significantly effect the pressurization process and that minimizing heat loss from the ullage and maximizing pressurant flow rate minimizes the mass of pressurant gas required to pressurize the tank. It is further demonstrated that proper dimensionless scaling of pressure and time permit all the pressure histories examined during this study to be displayed as a single curve.

  3. Manipulating the Energetics and Rates of Electron Transfer in Rhodobacter capsulatus Reaction Centers with Asymmetric Pigment Content

    Energy Technology Data Exchange (ETDEWEB)

    Faries, Kaitlyn M. [Department; Dylla, Nicholas P. [Biosciences Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Hanson, Deborah K. [Biosciences Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Holten, Dewey [Department; Laible, Philip D. [Biosciences Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Kirmaier, Christine [Department


    Seemingly redundant parallel pathways for electron transfer (ET), composed of identical sets of cofactors, are a cornerstone feature of photosynthetic reaction centers (RCs) involved in light-energy conversion. In native bacterial RCs, both A and B branches house one bacteriochlorophyll (BChl) and one bacteriopheophytin (BPh), but the A branch is used exclusively. Described herein are the results-obtained for two Rhodobacter capsulatus RCs with an unnaturally high degree of cofactor asymmetry, two BPh on the RC's B side and two BChl on the A side. These pigment changes derive, respectively, from the His(M180)Leu mutation [a BPh ((Phi(B)) replaces the B-side BChl (BB)], and the Leu(M212)His mutation [a BChl (beta(A))) replaces the A-side BPh (H-A)]. Additionally, Tyr(M208)Phe was employed to disfavor ET to the A branch; in one mutant, Val(M131)Glu creates a hydrogen bond to H-B to enhance ET to H-B. In both Phi(B) mutants, the decay kinetics of the excited primary ET donor (P*) resolve three populations with lifetimes of similar to 9 ps (50-60%), similar to 40 ps (10-20%), and similar to 200 ps (20-30%), with P+Phi(-)(B) formed predominantly from the 9 ps fraction. The 50-60% yield of P+Phi(B)- is the highest yet observed for a Phi(B)-containing RC. The results provide insight into factors needed for efficient multistep ET.

  4. Role of intramolecular hydrogen bonding in the excited-state intramolecular double proton transfer (ESIDPT of calix[4]arene: A TDDFT study

    Directory of Open Access Journals (Sweden)

    Wang Se


    Full Text Available The time-dependent density functional theory (TDDFT method was performed to investigate the excited-state intramolecular double proton transfer (ESIDPT reaction of calix[4]arene (C4A and the role of the intramolecular hydrogen bonds in the ESIDPT process. The geometries of C4A in the ground state and excited states (S1, S2 and T1 were optimized. Four intramolecular hydrogen bonds formed in the C4A are strengthened or weakened in the S2 and T1 states compared to those in the ground state. Interestingly, upon excitation to the S1 state of C4A, two protons H1 and H2 transfer along the two intramolecular hydrogen bonds O1-H1···O2 and O2-H2···O3, while the other two protons do not transfer. The ESIDPT reaction breaks the primary symmetry of C4A in the ground state. The potential energy curves of proton transfer demonstrate that the ESIDPT process follows the stepwise mechanism but not the concerted mechanism. Findings indicate that intramolecular hydrogen bonding is critical to the ESIDPT reactions in intramolecular hydrogen-bonded systems.

  5. Theoretical study of excited-state proton transfer of 2,7-diazaindole·(H2O)2 cluster via hydrogen bonding dynamics (United States)

    Liu, Yuan; Tang, Zhe; Wang, Yi; Tian, Jing; Fei, Xu; Cao, Fang; Li, GuangYue


    A new chromophore, 2,7-diazaindole (2,7-DAI), has been designed to surpass the limitation of 7-azaindole (7AI). It exhibits remarkable water catalyzed proton-transfer properties. Excited-state proton transfer (ESPT) has been investigated based on the time-dependent density functional theory method. The calculated vertical excitation energies in the S0 and S1 states agree well with the experimental values. Proton transfer couples with hydrogen-bonding dynamics between the 2,7-diazaindole and the surrounding water molecules. Hydrogen bond strengthening has been testified in the S1 state based on a comparison of primary bond lengths and hydrogen bond energy that is involved in the intermolecular hydrogen bond between the S0 and S1 states. Frontier molecular further suggest that the electron density changes between the ground and excited states serve as basic driving forces for proton transfer. We determined the potential-energy curves of the S0 and S1 states to characterize the ESPT process. This work explains that the ESPT process for 2,7-DAI·(H2O)2 clusters at the molecular level, and highlights the importance of hydrogen bonding in ESPT.

  6. Hirshfeld atom refinement for modelling strong hydrogen bonds. (United States)

    Woińska, Magdalena; Jayatilaka, Dylan; Spackman, Mark A; Edwards, Alison J; Dominiak, Paulina M; Woźniak, Krzysztof; Nishibori, Eiji; Sugimoto, Kunihisa; Grabowsky, Simon


    High-resolution low-temperature synchrotron X-ray diffraction data of the salt L-phenylalaninium hydrogen maleate are used to test the new automated iterative Hirshfeld atom refinement (HAR) procedure for the modelling of strong hydrogen bonds. The HAR models used present the first examples of Z' > 1 treatments in the framework of wavefunction-based refinement methods. L-Phenylalaninium hydrogen maleate exhibits several hydrogen bonds in its crystal structure, of which the shortest and the most challenging to model is the O-H...O intramolecular hydrogen bond present in the hydrogen maleate anion (O...O distance is about 2.41 Å). In particular, the reconstruction of the electron density in the hydrogen maleate moiety and the determination of hydrogen-atom properties [positions, bond distances and anisotropic displacement parameters (ADPs)] are the focus of the study. For comparison to the HAR results, different spherical (independent atom model, IAM) and aspherical (free multipole model, MM; transferable aspherical atom model, TAAM) X-ray refinement techniques as well as results from a low-temperature neutron-diffraction experiment are employed. Hydrogen-atom ADPs are furthermore compared to those derived from a TLS/rigid-body (SHADE) treatment of the X-ray structures. The reference neutron-diffraction experiment reveals a truly symmetric hydrogen bond in the hydrogen maleate anion. Only with HAR is it possible to freely refine hydrogen-atom positions and ADPs from the X-ray data, which leads to the best electron-density model and the closest agreement with the structural parameters derived from the neutron-diffraction experiment, e.g. the symmetric hydrogen position can be reproduced. The multipole-based refinement techniques (MM and TAAM) yield slightly asymmetric positions, whereas the IAM yields a significantly asymmetric position.

  7. Efficient transfer hydrogenation reaction Catalyzed by a dearomatized PN 3P ruthenium pincer complex under base-free Conditions

    KAUST Repository

    He, Lipeng


    A dearomatized complex [RuH(PN 3P)(CO)] (PN 3PN, N′-bis(di-tert-butylphosphino)-2,6-diaminopyridine) (3) was prepared by reaction of the aromatic complex [RuH(Cl)(PN 3P)(CO)] (2) with t-BuOK in THF. Further treatment of 3 with formic acid led to the formation of a rearomatized complex (4). These new complexes were fully characterized and the molecular structure of complex 4 was further confirmed by X-ray crystallography. In complex 4, a distorted square-pyramidal geometry around the ruthenium center was observed, with the CO ligand trans to the pyridinic nitrogen atom and the hydride located in the apical position. The dearomatized complex 3 displays efficient catalytic activity for hydrogen transfer of ketones in isopropanol. © 2011 Elsevier B.V. All rights reserved.

  8. Hydrogen transfer hydrocracking of C. procera latex under ambient pressure conditions to get value added chemicals and fuels

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, D.K.; Behera, B.K.; Arora, M. (Indian Institute of Technology, New Delhi (India). Fuels and Biofuels Engineering Lab.)


    Biomass is renewable source of energy while the reserves of petroleum are being depleted. The latex of a potential petrocrop, Calotropis procera, a laticifer, arid-plant which is rich in hydrocarbon type triterpene compounds etc. was found to be a better feed stock for thermal hydrocracking as compared to whole plant biomass in terms of liquid product yield. Studies of chemical reaction dynamics of the thermal cracking of latex at 200-400[degree]C showed that the process should be termed as hydrogen-transfer (H-T) hydrocracking of latex under ambient pressure conditions. The hydrogen rich cracked triterpenoids act as the H-donors in this process, where nascent hydrogen atoms and free radicals chemically plug the cracked moieties to stabilise these. Latex was also coagulated and the H-T hydrocracking of the feedstock coagulum gave a higher yield of cracked oil in comparison to that from the dried latex. The temperature for hydrocracking of latex has been optimized to 350[degree]C and molecular sieve was found to catalyse the H-T hydrocracking process to yield more liquid product. The distillation range of cracked latex oil (CLO) obtained from H-T hydrocracking of C. procera latex indicated that it can be used as fuel oil or substitute for diesel fuel. Moreover, CLO resembled diesel fuels and was predominantly paraffinic in nature as characterised by NMR and FTIR spectral analysis. A process has been recommended for getting value added fuels and chemicals from C. procera latex. 29 refs., 5 figs., 3 tabs.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  10. The role of interspecies hydrogen transfer on thermophilic protein and amino acid metabolism

    Energy Technology Data Exchange (ETDEWEB)

    Oerlygsson, J.


    The dynamics of thermophilic protein (peptone) degradation to fatty acids was followed in small-scale, semi-continuous, steady state, thermophilic enrichment cultures under methanogenic conditions. Although only 4-9% of the carbon was recovered in methane, methanogenesis was crucial both for the complete hydrolysis of peptone and the degradation of the amino acids released. Under non-methanogenic conditions, the degradation of the branched-chain amino acids alanine, methionine and phenylalanine, all known to be deaminated oxidatively, was partly inhibited. The degradation under these conditions was probably due to the Stickland reaction. During the degradation of several different amino acids with these peptone enrichment cultures, large differences were found in both deamination rates and in amounts degraded between methanogenic and non-methanogenic conditions. Leucine, valine and alanine were completely degraded only under methanogenic conditions and at relatively low rates. Serine, threonine, cysteine and methionine were degraded under both methanogenic and non-methanogenic conditions. However, deamination rates were 1.3 to 2.2 times higher during methanogenesis. A Clostridium sp. strain P2, was isolated from one of the semi-continuously peptone-fed enrichment cultures. Like in mixed cultures, the degradation of the branched-chain amino acids by this isolate was dependent on hydrogen removal. During growth on glucose, fructose and mannose, strain P2 produced substantial amounts of L-alanine as a fermentation product. Pyruvate was the source of alanine, and the formation of the latter was strongly influenced by ammonium. The partial pressure of hydrogen was of less importance for the formation of alanine than was the concentration of ammonia. 101 refs, 4 figs, 1 tab

  11. Hydrogen Atom Transfer (HAT) Processes Promoted by the Quinolinimide-N-oxyl Radical. A Kinetic and Theoretical Study. (United States)

    DiLabio, Gino A; Franchi, Paola; Lanzalunga, Osvaldo; Lapi, Andrea; Lucarini, Fiorella; Lucarini, Marco; Mazzonna, Marco; Prasad, Viki Kumar; Ticconi, Barbara


    A kinetic study of the hydrogen atom transfer (HAT) reactions from a series of organic compounds to the quinolinimide-N-oxyl radical (QINO) was performed in CH3CN. The HAT rate constants are significantly higher than those observed with the phthalimide-N-oxyl radical (PINO) as a result of enthalpic and polar effects due to the presence of the N-heteroaromatic ring in QINO. The relevance of polar effects is supported by theoretical calculations conducted for the reactions of the two N-oxyl radicals with toluene, which indicate that the HAT process is characterized by a significant degree of charge transfer permitted by the π-stacking that occurs between the toluene and the N-oxyl aromatic rings in the transition state structures. An increase in the HAT reactivity of QINO was observed in the presence of 0.15 M HClO4 and 0.15 M Mg(ClO4)2 due to the protonation or complexation with the Lewis acid of the pyridine nitrogen that leads to a further decrease in the electron density in the N-oxyl radical. These results fully support the use of N-hydroxyquinolinimide as a convenient substitute for N-hydroxyphthalimide in the catalytic aerobic oxidations of aliphatic hydrocarbons characterized by relatively high C-H bond dissociation energies.

  12. Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes

    KAUST Repository

    Li, Yang


    © 2014 AIP Publishing LLC. The atomic structure and the electron transfer properties of hydrogen bonds formed between two carboxylated alkanethiol molecules connected to gold electrodes are investigated by employing the non-equilibrium Green\\'s function formalism combined with density functional theory. Three types of molecular junctions are constructed, in which one carboxyl alkanethiol molecule contains two methylene, -CH2, groups and the other one is composed of one, two, or three -CH2 groups. Our calculations show that, similarly to the cases of isolated carboxylic acid dimers, in these molecular junctions the two carboxyl, -COOH, groups form two H-bonds resulting in a cyclic structure. When self-interaction corrections are explicitly considered, the calculated transmission coefficients of these three H-bonded molecular junctions at the Fermi level are in good agreement with the experimental values. The analysis of the projected density of states confirms that the covalent Au-S bonds localized at the molecule-electrode interfaces and the electronic coupling between -COOH and S dominate the low-bias junction conductance. Following the increase of the number of the -CH2 groups, the coupling between -COOH and S decreases deeply. As a result, the junction conductance decays rapidly as the length of the H-bonded molecules increases. These findings not only provide an explanation to the observed distance dependence of the electron transfer properties of H-bonds, but also help the design of molecular devices constructed through H-bonds.

  13. Measurement of muon transfer from proton to triton and {ital pp}{mu} molecular formation in solid hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Mulhauser, F.; Beveridge, J.L.; Marshall, G.M. [TRIUMF, 4004 Wesbrook Mall, Vancouver, British Columbia, V6T 2A3 (CANADA); Bailey, J.M. [Chester Technology, Chester (England); Beer, G.A.; Knowles, P.E.; Mason, G.R.; Olin, A. [University of Victoria, Victoria, British Columbia, V8W 2Y2 (CANADA); Fujiwara, M.C. [University of British Columbia, Vancouver, British Columbia, V6T 2A6 (CANADA); Huber, T.M. [Gustavus Adolphus College, St. Peter, Minnesota 56082 (United States); Jacot-Guillarmod, R. [Institut de Physique, Universite de Fribourg, CH-1700 Fribourg (Switzerland); Kammel, P.; Zmeskal, J. [Austrian Academy of Sciences, A-1090 Vienna (Austria); Kim, S.K. [Jeonbuk National University, Jeonju City 560-756, South (Korea); Kunselman, A.R. [University of Wyoming, Laramie, Wyoming 82071 (United States); Markushin, V.E. [Russian Research Center, Kurchatov Institute, Moscow 123182 (Russia); Martoff, C.J. [Temple University, Philadelphia, Pennsylvania 19122 (United States); Petitjean, C. [Paul Scherrer Institute, PSI, CH-5232 Villigen (Switzerland)


    An alternate approach was used to study the reactions of muonic atoms and molecules in solid layers of hydrogen isotopes. Muons stopped in a protium layer with a small admixture of tritium producing {mu}{ital p} atoms. Muon transfer from a proton to a triton generated {mu}{ital t} atoms, which were emitted into a deuterium layer. Subsequent epithermal {ital dt}{mu} molecular formation followed by {ital dt} fusion gave a prompt signal for the {mu}{ital t} emission. Fusion time spectra at various tritium concentrations were measured by detecting neutrons and {alpha} particles and the {mu}{ital p} disappearance rates were determined. The rates of {mu}{ital p}{r_arrow}{mu}{ital t} transfer and {ital pp}{mu} formation were measured to be {lambda}{sub {ital pt}}=[5.86{plus_minus}(0.10){sub {ital stat}}{plus_minus}(0.15){sub {ital syst}}({sub {minus}0}{sup +0.30}){sub {ital model}}]{times}10{sup 9} s{sup {minus}1} and {lambda}{sub {ital pp}}{sub {mu}}=[3.21 {plus_minus}(0.10){sub {ital stat}}{plus_minus}(0.14){sub {ital syst}}({sub {minus}0.06}{sup +0}){sub {ital model}(}]{times}10{sup 6} s{sup {minus}1}, respectively. Comparisons are made with the most recent theoretical values. {copyright} {ital 1996 The American Physical Society.}

  14. Sites involved in intra- and interdomain allostery associated with the activation of factor VIIa pinpointed by hydrogen-deuterium exchange and electron transfer dissociation mass spectrometry

    DEFF Research Database (Denmark)

    Song, Hongjian; Olsen, Ole H; Persson, Egon


    enhancement remain elusive. Here we have applied hydrogen/deuterium exchange mass spectrometry coupled to electron transfer dissociation to pinpoint individual residues in the heavy chain of FVIIa whose conformation and/or local interaction pattern changes when the enzyme transitions to the active form...

  15. Proton Transfer and Low-Barrier Hydrogen Bonding: a Shifting Vibrational Landscape Dictated by Large Amplitude Tunneling (United States)

    Vealey, Zachary; Foguel, Lidor; Vaccaro, Patrick


    Our fundamental understanding of synergistic hydrogen-bonding and proton-transfer phenomena has been advanced immensely by studies of model systems in which the coherent transduction of hydrons is mediated by two degenerate equilibrium configurations that are isolated from one another by a potential barrier of substantial height. This topography advantageously affords unambiguous signatures for the underlying state-resolved dynamics in the form of tunneling-induced spectral bifurcations, the magnitudes of which encode both the overall efficacy and the detailed mechanism of the unimolecular transformation. As a prototypical member of this class of compounds, 6-hydroxy-2-formylfulvene (HFF) supports an unusual quasi-linear O-H...O \\leftrightarrow O...H-O reaction coordinate that presents a minimal impediment to proton migration - a situation commensurate with the concepts of low-barrier hydrogen bonding (which are characterized by great strength, short distance, and a vanishingly small barrier for hydron migration). A variety of fluorescence-based, laser-spectroscopic probes have been deployed in a cold supersonic free-jet expansion to explore the vibrational landscape and anomalously large tunneling-induced shifts that dominate the ˜{X}^{1}A_{1} potential-energy surface of HFF, thus revealing the most rapid proton tunneling ever reported for a molecular ground state (τ_{pt}≤120fs). The surprising efficiency of such tunneling-mediated processes stems from proximity of the zero-point level to the barrier crest and produces a dramatic alteration in the canonical pattern of vibrational features that reflects, in part, the subtle transition from quantum-mechanical barrier penetration to classical over-the-barrier dynamics. The ultrafast proton-transfer regime that characterizes the ˜{X}^{1}A_{1} manifold will be juxtaposed against analogous findings for the lowest-lying singlet excited state ˜{A}^{1}B_{2} (π*←π), where a marked change in the nature of the

  16. Handshake electron transfer from hydrogen Rydberg atoms incident at a series of metallic thin films. (United States)

    Gibbard, J A; Softley, T P


    Thin metallic films have a 1D quantum well along the surface normal direction, which yields particle-in-a-box style electronic quantum states. However the quantum well is not infinitely deep and the wavefunctions of these states penetrate outside the surface where the electron is bound by its own image-charge attraction. Therefore a series of discrete, vacant states reach out from the thin film into the vacuum increasing the probability of electron transfer from an external atom or molecule to the thin film, especially for the resonant case where the quantum well energy matches that of the atom. We show that "handshake" electron transfer from a highly excited Rydberg atom to these thin-film states is experimentally measurable. Thicker films have a wider 1D box, changing the energetic distribution and image-state contribution to the thin film wavefunctions, resulting in more resonances. Calculations successfully predict the number of resonances and the nature of the thin-film wavefunctions for a given film thickness.

  17. Measurement of muon transfer rate {lambda}{sub pt} and molecular formation rate {lambda}{sub pp{mu}} in solid hydrogen targets

    Energy Technology Data Exchange (ETDEWEB)

    Mulhauser, F.; Beveridge, J.L.; Douglas, J.L.; Maier, M.; Marshall, G.M. [British Columbia Univ., Vancouver, BC (Canada). TRIUMF Facility; Bailey, J.M. [EA Technology, Capenhurst (United Kingdom); Beer, G.A.; Knowles, P.E.; Mason, G.R.; Olin, A.; Porcelli, T.A. [Victoria Univ., BC (Canada); Fujiwara, M.C. [British Columbia Univ., Vancouver, BC (Canada); Huber, T.M. [Gustavus Adolphus Coll., St. Peter, MN (United States); Jacot-Guillarmod, R. [Fribourg Univ. (Switzerland); Kammel, P. [Lawrence Berkeley Lab., CA (United States); Kim, S.K. [Jeonbuk National Univ., Jeonju (Korea, Republic of); Kunselman, A.R. [Wyoming Univ., Laramie, WY (United States); Markushin, V.E. [Gosudarstvennyj Komitet po Ispol`zovaniyu Atomnoj Ehnergii SSSR, Moscow (Russian Federation). Inst. Atomnoj Ehnergii; Martoff, C.J. [Temple Univ., Philadelphia, PA (United States); Petitjean, C. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Zmeskal, J. [Oesterreichische Akademie der Wissenschaften, Vienna (Austria)


    The knowledge of muon transfer from protium to tritium is essentially theoretical and the different theoretical values disagree partially. Using solid hydrogen-tritium targets, with different tritium concentrations, we obtained precise experimental results for the transfer rate to tritium and the HH{mu} molecular formation rate. The time spectra of neutrons and alpha particles produced after DT{mu} fusion are used to determine the transfer rate {lambda}{sub pt} and the molecule formation rate {lambda}{sub pp{mu}}. (orig.). 27 refs.

  18. Electrochemical studies of a reconstituted photosynthetic electron-transfer chain or towards a biomimetic photoproduction of hydrogen; Etudes electrochimiques de chaines de transfert d'electrons photosynthetiques ou vers une photoproduction biomimetique d'hydrogene

    Energy Technology Data Exchange (ETDEWEB)

    Fourmond, V


    The aim of this work is to find an efficient process to convert solar energy into hydrogen. The electrons transfers in reconstituted photosynthetic chains have been particularly studied with the aims 1)in one hand, to better understand the interactions of the different molecules of the photosynthetic chain in order to optimize the changes of the entire organisms for hydrogen production 2)in another hand, to insert the hydrogenases in a photosynthetic chain and then to photo reduce them in order to obtain kinetic data to better understand how it works. (O.M.)

  19. Hydrogen transfer in the formation and destruction of retrograde products in coal conversion

    Energy Technology Data Exchange (ETDEWEB)

    McMillen, D.F.; Malhotra, R. [SRI International, Menlo Park, CA (United States)


    The conversion of coals to volatiles or liquids during pyrolysis and liquefaction is notoriously limited by the formation of retrograde products. Analysis of literature data for coals with grafted structures and for polymeric coal models demonstrates that the formation of volatile products from these materials does not correlate primarily with the weakness of the original bonding but correlates with the facility for retrogressive reaction. This analysis suggests further that simple recombination of resonance-stabilized radicals does not tend to yield true retrograde products, except in the case of aryloxy radicals. For pure hydrocarbon structural elements, radical addition to aromatic systems appears to be a key class of retrograde reactions, where the key factor is the kinetics of radical or H-atom loss from a cyclohexadienyl intermediate. We have used a mechanistic numerical model with a detailed set of radical reactions and thermochemically based kinetic parameters operating on a limited set of hydrocarbon structures to delineate important factors in mitigating retrograde processes. This showed that, not only the cleavage of critical bonds in the original coal structures but also the net prevention of retrogression may be due to the H-transfer-induced cleavage of strong bonds.

  20. The π-Tetrel Bond and its Influence on Hydrogen Bonding and Proton Transfer. (United States)

    Wei, Yuanxin; Li, Qingzhong; Scheiner, Steve


    The positive region that lies above the plane of F 2 TO (T=C and Si) interacts with malondialdehyde (MDA), which contains an intramolecular H-bond. The T atom of F 2 TO can lie either in the MDA molecular plane, forming a T⋅⋅⋅O tetrel bond, or F 2 TO can stack directly above MDA in a parallel arrangement. The former structure is more stable than the latter, and in either case, F 2 SiO engages in a much stronger interaction than does F 2 CO, reaching nearly 200 kJ mol -1 . The π-tetrel bond strengthens/weakens the MDA H-bond when the bond is formed to the hydroxyl/carbonyl group of MDA, and causes an accompanying inhibition/promotion of proton transfer within this H-bond; this effect is stronger for F 2 SiO. These same aspects can be tuned by substituents placed on any of the C atoms of MDA, although their effects are not fully correlated with the electron-withdrawing or electron-releasing properties of the substituent. A new type of π-π tetrel bond occurs when the π-hole on the T atom of F 2 TO approaches the middle carbon atom of MDA from above, and a similar configuration is also found between F 2 TO and benzene. Evidence for extensive C⋅⋅⋅C π-π tetrel bonding in crystal materials is presented. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. TDDFT study on the excited-state proton transfer of 8-hydroxyquinoline: key role of the excited-state hydrogen-bond strengthening. (United States)

    Lan, Sheng-Cheng; Liu, Yu-Hui


    Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations have been employed to study the excited-state intramolecular proton transfer (ESIPT) reaction of 8-hydroxyquinoline (8HQ). Infrared spectra of 8HQ in both the ground and the lowest singlet excited states have been calculated, revealing a red-shift of the hydroxyl group (-OH) stretching band in the excited state. Hence, the intramolecular hydrogen bond (O-H···N) in 8HQ would be significantly strengthened upon photo-excitation to the S1 state. As the intramolecular proton-transfer reaction occurs through hydrogen bonding, the ESIPT reaction of 8HQ is effectively facilitated by strengthening of the electronic excited-state hydrogen bond (O-H···N). As a result, the intramolecular proton-transfer reaction would occur on an ultrafast timescale with a negligible barrier in the calculated potential energy curve for the ESIPT reaction. Therefore, although the intramolecular proton-transfer reaction is not favorable in the ground state, the ESIPT process is feasible in the excited state. Finally, we have identified that radiationless deactivation via internal conversion (IC) becomes the main dissipative channel for 8HQ by analyzing the energy gaps between the S1 and S0 states for the enol and keto forms. Copyright © 2014 Elsevier B.V. All rights reserved.


    African Journals Online (AJOL)

    Abstract. Quenching of curcumine fluorescence by thionine, both immobilised in cellulose acetate occurs in accordance with the Forster mechanism of energy transfer. The rate constant of energy transfer for this donor - acceptor pair is found to be 9.4 x 109 L ' mol S1 with R0 = 37±1 Б. When this donor - acceptor pair is ...

  3. Asymmetric Ashes (United States)


    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

  4. Photoinduced electron transfer in hydrogen bonded donor--acceptor systems. Free energy and distance dependence studies and an analysis of the role of diffusion. (United States)

    Smitha, M A; Prasad, E; Gopidas, K R


    The free energy dependence of electron transfer in a few small-molecule donor--acceptor systems having hydrogen-bonding appendages was studied to evaluate the role of diffusion in masking the inverted region in bimolecular PET reactions. A small fraction of the probe molecules associate and this led to the simultaneous observation of unimolecular and diffusion-mediated quenching of the probe fluorescence. Free energy dependence studies showed that the unimolecular electron transfer obeys Marcus behavior and the diffusion-mediated electron transfer obeys Rehm--Weller behavior. The absence of an inverted region in bimolecular PET reactions is thus attributed to diffusion. The results of the free energy dependence studies suggest that distance dependence of electron transfer plays a role in masking the inverted region. To ascertain this aspect we have carried out a study of the distance dependence of electron transfer in the hydrogen-bonded donor--acceptor systems. For a system in the normal region an exponential rate decrease was observed. For a system in the inverted region it was observed that the rate depends very feebly on distance. Thus distance dependence studies did not confirm the prediction of enhanced rates at larger distances in the inverted region.

  5. Development of Asymmetric Hydrogenation Catalysts via High Throughput Experimentation Développement de catalyseurs d’hydrogénation asymétrique par criblage haut débit

    Directory of Open Access Journals (Sweden)

    de Vries J. G.


    Full Text Available The dynamics of drugs discovery imposes severe time constraints on the development chemist in charge of implementing the large scale production of a new Active Pharmaceutical Ingredient (API. This results in the use of well-established and robust transformations at the expense of the cost-efficiency and the sustainability of the process. In order to cope with the short development time and allow the implementation of new more efficient production technologies such as asymmetric hydrogenation, we have turned towards the use of high throughput experimentation for the discovery of new catalysts. The protocol for the preparation of a library of chiral ligands and its application to real-life pharmaceutical molecules is described in this article. La découverte de nouvelles molécules pharmaceutiques a sa propre dynamique qui impose des contraintes temporelles très strictes au chimiste en charge de développer la production du principe actif à large échelle. En conséquence, ce dernier va se tourner vers l’utilisation de technologies éprouvées et robustes quitte à rendre le procédé plus coûteux ou plus polluant. Afin de pouvoir faire face à des temps de développement très courts et d’introduire en production des technologies modernes et non polluantes comme l’hydrogénation asymétrique, nous avons développé une plateforme de criblage haut débit pour la découverte de nouveaux catalyseurs. Dans cet article, nous décrivons une des facettes de cette plateforme qui est la synthèse de librairies de ligands chiraux et leur application au cas réel d’une molécule pharmaceutique.

  6. Coumarin or benzoxazinone bearing benzimidazolium and bis(benzimidazolium) salts; involvement in transfer hydrogenation of acetophenone derivatives and hCA inhibition


    Mert Olgun Karataş; Serkan Dayan; Nilgün Kayacı; Çiğdem Bilen; Emre Yavuz; Nahit Gencer; Bülent Alıcı; Nilgün Ozpozan Kalaycıoğlu; Oktay Arslan


    Four new salts of benzimidazolium and bis(benzimidazolium) which include coumarin or benzoxazinone moieties were synthesized and the structures of the newly synthesized compounds were elucidated on the basis of spectral analyses such as 1H-NMR, 13C-NMR, HSQC, IR, LC-MS and elemental analysis. Benzimidazolium salts were used intensively as N-heterocyclic carbene (NHC) precursors in the various catalytic reactions such as transfer hydrogenation (TH), C-H bond activation, Heck, Suzuki reaction e...

  7. Peristaltic transport of MHD flow and heat transfer in an asymmetric channel: Effects of variable viscosity, velocity-slip and temperature jump

    Directory of Open Access Journals (Sweden)

    A. Sinha


    Full Text Available In this article, a theoretical study is presented for peristaltic flow of a MHD fluid in an asymmetric channel. Effects of viscosity variation, velocity-slip as well as thermal-slip have been duly taken care of in the present study. The energy equation is formulated by including a heat source term which simulates either absorption or generation. The governing equations of motion and energy are simplified using long wave length and low Reynolds number approximation. The coupled non-linear differential equations are solved analytically by means of the perturbation method for small values of Reynolds model viscosity parameter. The salient features of pumping and trapping are discussed with particular focus on the effects of velocity-slip parameter, Grashof number and magnetic parameter. The study reveals that the velocity at the central region diminishes with increasing values of the velocity-slip parameter. The size of trapped bolus decreases and finally vanishes for large values of magnetic parameter.

  8. Investigation of the Mechanism of Electron Capture and Electron Transfer Dissociation of Peptides with a Covalently Attached Free Radical Hydrogen Atom Scavenger. (United States)

    Sohn, Chang Ho; Yin, Sheng; Peng, Ivory; Loo, Joseph A; Beauchamp, J L


    The mechanisms of electron capture and electron transfer dissociation (ECD and ETD) are investigated by covalently attaching a free-radical hydrogen atom scavenger to a peptide. The 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO) radical was chosen as the scavenger due to its high hydrogen atom affinity (ca. 280 kJ/mol) and low electron affinity (ca. 0.45 ev), and was derivatized to the model peptide, FQX TEMPO EEQQQTEDELQDK. The X TEMPO residue represents a cysteinyl residue derivatized with an acetamido-TEMPO group. The acetamide group without TEMPO was also examined as a control. The gas phase proton affinity (882 kJ/mol) of TEMPO is similar to backbone amide carbonyls (889 kJ/mol), minimizing perturbation to internal solvation and sites of protonation of the derivatized peptides. Collision induced dissociation (CID) of the TEMPO tagged peptide dication generated stable odd-electron b and y type ions without indication of any TEMPO radical induced fragmentation initiated by hydrogen abstraction. The type and abundance of fragment ions observed in the CID spectra of the TEMPO and acetamide tagged peptides are very similar. However, ECD of the TEMPO labeled peptide dication yielded no backbone cleavage. We propose that a labile hydrogen atom in the charge reduced radical ions is scavenged by the TEMPO radical moiety, resulting in inhibition of N-C α backbone cleavage processes. Supplemental activation after electron attachment (ETcaD) and CID of the charge-reduced precursor ion generated by electron transfer of the TEMPO tagged peptide dication produced a series of b + H (b H ) and y + H (y H ) ions along with some c ions having suppressed intensities, consistent with stable O-H bond formation at the TEMPO group. In summary, the results indicate that ECD and ETD backbone cleavage processes are inhibited by scavenging of a labile hydrogen atom by the localized TEMPO radical moiety. This observation supports the conjecture that ECD and ETD processes involve long

  9. Asymmetric bifurcated halogen bonds. (United States)

    Novák, Martin; Foroutan-Nejad, Cina; Marek, Radek


    Halogen bonding (XB) is being extensively explored for its potential use in advanced materials and drug design. Despite significant progress in describing this interaction by theoretical and experimental methods, the chemical nature remains somewhat elusive, and it seems to vary with the selected system. In this work we present a detailed DFT analysis of three-center asymmetric halogen bond (XB) formed between dihalogen molecules and variously 4-substituted 1,2-dimethoxybenzene. The energy decomposition, orbital, and electron density analyses suggest that the contribution of electrostatic stabilization is comparable with that of non-electrostatic factors. Both terms increase parallel with increasing negative charge of the electron donor molecule in our model systems. Depending on the orientation of the dihalogen molecules, this bifurcated interaction may be classified as 'σ-hole - lone pair' or 'σ-hole - π' halogen bonds. Arrangement of the XB investigated here deviates significantly from a recent IUPAC definition of XB and, in analogy to the hydrogen bonding, the term bifurcated halogen bond (BXB) seems to be appropriate for this type of interaction.

  10. Two Closely Related Organic Charge-Transfer Complexes Based on Tetrathiafulvalene and 9H-fluorenone Derivatives. Competition between Hydrogen Bonding and Stacking Interactions

    Directory of Open Access Journals (Sweden)

    Amparo Salmerón-Valverde


    Full Text Available Two 1:1 charge-transfer organic complexes were formed using tetrathiafulvalene as a donor and a 9H-fluorenone derivative as acceptor: 4,5,7-trinitro-9H-fluoren-9-one-2-carboxylic acid (complex 1 or 4,5,7-trinitro-9H-fluoren-9-one-2-carboxylic acid methyl ester (complex 2. Both systems crystallize with alternated donor and acceptor stacks. However, the crystal structure of 1 is influenced by classical hydrogen bonds involving carboxylic acid groups, which force to arrange acceptors as centrosymmetric dimers in the crystal, via R2 2(8 ring motifs, while such a restriction is no longer present in the case of 2, affording thus a different crystal structure. This main difference is reflected in stacking interactions, and, in turn, in the degree of charge transfer observed in the complexes. The degree of charge transfer, estimated using Raman spectroscopy, is δ1 = 0.07 for 1 and δ2 = 0.14 for 2. It thus seems that, at least for the studied complexes, hydrogen bonding is an unfavorable factor for charge transfer.

  11. Magnetic Co@g-C3N4 Core-Shells on rGO Sheets for Momentum Transfer with Catalytic Activity toward Continuous-Flow Hydrogen Generation. (United States)

    Duan, Shasha; Han, Guosheng; Su, Yongheng; Zhang, Xiaoyu; Liu, Yanyan; Wu, Xianli; Li, Baojun


    Magnetic core-shell structures provide abundant opportunities for the construction of multifunctional composites. In this article, magnetic core-shells were fabricated with Co nanoparticles (NPs) as cores and g-C3N4 as shells. In the fabrication process, the Co@g-C3N4 core-shells were anchored onto the rGO nanosheets to form a Co@g-C3N4-rGO composite (CNG-I). For hydrogen generation from the hydrolysis of NaBH4 or NH3BH3, the Co NP cores act as catalytic active sites. The g-C3N4 shells protect Co NPs cores from aggregating or growing. The connection between Co NPs and rGO was strengthened by the g-C3N4 shells to prevent them from leaching or flowing away. The g-C3N4 shells also work as a cocatalyst for hydrogen generation. The magnetism of Co NPs and the shape of rGO nanosheets achieve effective momentum transfer in the external magnetic field. In the batch reactor, a higher catalytic activity was obtained for CNG-I in self-stirring mode than in magneton stirring mode. In the continuous-flow process, stable hydrogen generation was carried out with CNG-I being fixed and propelled by the external magnetic field. The separation film is unnecessary because of magnetic momentum transfer. This idea of the composite design and magnetic momentum transfer will be useful for the development of both hydrogen generation and multifunctional composite materials.

  12. Synthesis of alpha-amino acids via asymmetric phase transfer-catalyzed alkylation of achiral nickel(II) complexes of glycine-derived Schiff bases. (United States)

    Belokon, Yuri N; Bespalova, Natalia B; Churkina, Tatiana D; Císarová, Ivana; Ezernitskaya, Marina G; Harutyunyan, Syuzanna R; Hrdina, Radim; Kagan, Henri B; Kocovský, Pavel; Kochetkov, Konstantin A; Larionov, Oleg V; Lyssenko, Konstantin A; North, Michael; Polásek, Miroslav; Peregudov, Alexander S; Prisyazhnyuk, Vladimir V; Vyskocil, Stepán


    Achiral, diamagnetic Ni(II) complexes 1 and 3 have been synthesized from Ni(II) salts and the Schiff bases, generated from glycine and PBP (7) and PBA (11), respectively, in MeONa/MeOH solutions. The requisite carbonyl-derivatizing agents pyridine-2-carboxylic acid(2-benzoyl-phenyl)-amide 7 (PBP) and pyridine-2-carboxylic acid(2-formyl-phenyl)-amide 11 (PBA) were readily prepared from picolinic acid and o-aminobenzophenone or picolinic acid and methyl o-anthranilate, respectively. The structure of 1 was established by X-ray crystallography. Complexes 1 and 3 were found to undergo C-alkylation with alkyl halides under PTC conditions in the presence of beta-naphthol or benzyltriethylammonium bromide as catalysts to give mono- and bis-alkylated products, respectively. Decomposition of the complexes with aqueous HCl under mild conditions gave the required amino acids, and PBP and PBA were recovered. Alkylation of 1 with highly reactive alkyl halides, carried out under the PTC conditions in the presence of 10% mol of (S)- or (R)-2-hydroxy-2'-amino-1,1'-binaphthyl 31a (NOBIN) and/or its N-acyl derivatives and by (S)- or (R)-2-hydroxy-8'-amino-1,1'-binaphthyl 32a (iso-NOBIN) and its N-acyl derivatives, respectively, gave rise to alpha-amino acids with high enantioselectivities (90-98.5% ee) in good-to-excellent chemical yields at room temperature within several minutes. An unusually large positive nonlinear effect was observed in these reactions. The Michael addition of acrylic derivatives 37 to 1 was conducted under similar conditions with up to 96% ee. The (1)H NMR and IR spectra of a mixture of the sodium salt of NOBIN and 1 indicated formation of a complex between the two components. Implications of the association and self-association of NOBIN for the observed sense of asymmetric induction and nonlinear effects are discussed.

  13. Heat transfer and critical heat flux in a spiral flow in an asymmetrical heated tube; Transfert thermique et flux critique dans un ecoulement helicoidal en tube chauffe asymetriquement

    Energy Technology Data Exchange (ETDEWEB)

    Boscary, J. [CEA Centre d`Etudes de Cadarache, 13 - Saint-Paul-lez-Durance (France). Direction des Sciences de la Matiere]|[Association Euratom-CEA, Centre d`Etudes Nucleaires de Cadarache, 13 - Saint-Paul-lez-Durance (France). Dept. de Recherches sur la Fusion Controlee


    The design of plasma facing components is crucial for plasma performance in next fusion reactors. These elements will be submitted to very high heat flux. They will be actively water-cooled by swirl tubes in the subcooled boiling regime. High heat flux experiments were conducted in order to analyse the heat transfer and to evaluate the critical heat flux. Water-cooled mock-ups were one-side heated by an electron beam gun for different thermal-hydraulic conditions. The critical heat flux was detected by an original method based on the isotherm modification on the heated surface. The wall heat transfer law including forced convection and subcooled boiling regimes was established. Numerical calculations of the material heat transfer conduction allowed the non-homogeneous distribution of the wall temperature and of the wall heat flux to be evaluated. The critical heat flux value was defined as the wall maximum heat flux. A critical heat flux model based on the liquid sublayer dryout under a vapor blanket was established. A good agreement with test results was found. (author) 197 refs.

  14. Heat transfer and critical heat flux in a asymmetrically heated tube helicoidal flow; Transfert thermique et flux critique dans un ecoulement helicoidal en tube chauffe asymetriquement

    Energy Technology Data Exchange (ETDEWEB)

    Boscary, J.


    The design of plasma facing components is crucial for plasma performance in next fusion reactors. These elements will be submitted to very high heat flux. They will be actively water-cooled by swirl tubes in the subcooled boiling regime. High heat flux experiments were conducted in order to analyse the heat transfer and to evaluate the critical heat flux. Water-cooled mock-ups were one-side heated by an electron beam gun for different thermal-hydraulic conditions. The critical heat flux was detected by an original method based on the isotherm modification on the heated surface. The wall heat transfer law including forced convection and subcooled boiling regimes was established. Numerical calculations of the material heat transfer conduction allowed the non-homogeneous distribution of the wall temperature and of the wall heat flux to be evaluated. The critical heat flux value was defined as the wall maximum heat flux. A critical heat flux model based on the liquid sublayer dryout under a vapor blanket was established. A good agreement with test results was found. (author). 198 refs., 126 figs., 21 tabs.

  15. Analysis of the effects of explosion of a hydrogen cylinder on the transfer of radioactive liquid wastes at nuclear power stations

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, Karina B., E-mail: [Industrias Nucleares do Brasil (INB), Rio de Janeiro, RJ (Brazil); Melo, Paulo Fernando F.F. e, E-mail: frutoso@nuclear.ufrj.b [Universidade Federal do Rio de Janeiro (PEN/COPPE/UFRJ), RJ (Brazil). Coordenacao dos Programas de Pos-Graduacao de Engenharia. Programa de Engenharia Nuclear


    This work presents a study of explosion effects of a stored hydrogen cylinder on the transfer of radioactive liquid wastes at nuclear power plants. The peak overpressure is calculated, as well as the strength of resulting fragments, thus confirming the main harmful effect of an explosion of flammable vapor cloud, based on the TNT equivalent method. The scenarios identified are calculated and compared with the overpressure ranges of 1%, 50% and 99% of structural damages, which were determined by the Eisenberg's vulnerability model. The results show that the overpressure and the resulting fragments from the explosion of a hydrogen gas cylinder are not able to cause the overturning of the tanker under study, and also show that a minimum distance of 30 meters between the hydrogen cylinder and the tanker can be considered a safe distance to the passage of this tanker during the transfer of radioactive liquid waste, in which the likelihood of occurrence of structural damages is less than 1%. (author)

  16. Nanotube Adsorption for the Capture and Re-liquefaction of Hydrogen Biol-Off During Tanker Transfer Operations Project (United States)

    National Aeronautics and Space Administration — This proposal discloses an innovative, economically feasible technique to capture and re-liquefy the hydrogen boil-off by using carbon nanotube adsorption prior to...

  17. Excited-state intramolecular hydrogen transfer (ESIHT) of 1,8-Dihydroxy-9,10-anthraquinone (DHAQ) characterized by ultrafast electronic and vibrational spectroscopy and computational modeling

    KAUST Repository

    Mohammed, Omar F.


    We combine ultrafast electronic and vibrational spectroscopy and computational modeling to investigate the photoinduced excited-state intramolecular hydrogen-transfer dynamics in 1,8-dihydroxy-9,10-anthraquinone (DHAQ) in tetrachloroethene, acetonitrile, dimethyl sulfoxide, and methanol. We analyze the electronic excited states of DHAQ with various possible hydrogen-bonding schemes and provide a general description of the electronic excited-state dynamics based on a systematic analysis of femtosecond UV/vis and UV/IR pump-probe spectroscopic data. Upon photoabsorption at 400 nm, the S 2 electronic excited state is initially populated, followed by a rapid equilibration within 150 fs through population transfer to the S 1 state where DHAQ exhibits ESIHT dynamics. In this equilibration process, the excited-state population is distributed between the 9,10-quinone (S2) and 1,10-quinone (S1) states while undergoing vibrational energy redistribution, vibrational cooling, and solvation dynamics on the 0.1-50 ps time scale. Transient UV/vis pump-probe data in methanol also suggest additional relaxation dynamics on the subnanosecond time scale, which we tentatively ascribe to hydrogen bond dynamics of DHAQ with the protic solvent, affecting the equilibrium population dynamics within the S2 and S1 electronic excited states. Ultimately, the two excited singlet states decay with a solvent-dependent time constant ranging from 139 to 210 ps. The concomitant electronic ground-state recovery is, however, only partial because a large fraction of the population relaxes to the first triplet state. From the similarity of the time scales involved, we conjecture that the solvent plays a crucial role in breaking the intramolecular hydrogen bond of DHAQ during the S2/S1 relaxation to either the ground or triplet state. © 2014 American Chemical Society.

  18. Computing modal dispersion characteristics of radially Asymmetric ...

    African Journals Online (AJOL)

    determine how the modal characteristics change as circular Bragg fiber is changed to asymmetric Bragg fiber. The key to this transfer matrix method (TMM) is the accurate calculation of the propagation constants of modes. And validity of this method is verified by FDTD method. We compare these results with obtained from ...

  19. Heat and Mass Transfer during Hydrogen Generation in an Array of Fuel Bars of a BWR Using a Periodic Unit Cell

    Directory of Open Access Journals (Sweden)

    H. Romero-Paredes


    Full Text Available This paper presents, the numerical analysis of heat and mass transfer during hydrogen generation in an array of fuel cylinder bars, each coated with a cladding and a steam current flowing outside the cylinders. The analysis considers the fuel element without mitigation effects. The system consists of a representative periodic unit cell where the initial and boundary-value problems for heat and mass transfer were solved. In this unit cell, we considered that a fuel element is coated by a cladding with steam surrounding it as a coolant. The numerical simulations allow describing the evolution of the temperature and concentration profiles inside the nuclear reactor and could be used as a basis for hybrid upscaling simulations.

  20. Hydride, hydrogen atom, proton, and electron transfer driving forces of various five-membered heterocyclic organic hydrides and their reaction intermediates in acetonitrile. (United States)

    Zhu, Xiao-Qing; Zhang, Ming-Tian; Yu, Ao; Wang, Chun-Hua; Cheng, Jin-Pei


    weak one-electron oxidation agents. The energies of the intramolecular hydrogen bond in 3H, 3H+*, and 3* with a hydroxyl group at ortho-position on the 2-phenyl ring were estimated by using experimental method, the results disclose that the hydrogen bond energy is 3.2, 2.8-3.0, and 3.9-4.0 kcal/mol for 3H, 3H+*, and 3* in acetonitrile, respectively, which is favorable for hydrogen atom transfer but unfavorable for hydride transfer from 3H. The relative effective charges on the active center in ZH, ZH+*, Z*, and Z+, which is an efficient measurement of electrophilicity or nucleophilicity as well as dimerizing ability of a chemical species, were estimated by using experimental method; the results indicate that 1*-5* belong to electron-sufficient carbon-radicals, 6*-7* belong to electron-deficient carbon radicals, they are all difficult to dimerize, and that 1+-5+ belong to weak electrophilic agents, 6+-7+ belong to strong electrophilic agents. All these information disclosed in this work could not only supply a gap of the chemical thermodynamics of the five-membered heterocyclic compounds as organic hydride donors, but also strongly promote the fast development of the chemistry and applications of the five-membered heterocyclic organic hydrides.

  1. Energy of Intramolecular Hydrogen Bonding in ortho-Hydroxybenzaldehydes, Phenones and Quinones. Transfer of Aromaticity from ipso-Benzene Ring to the Enol System(s). (United States)

    Rusinska-Roszak, Danuta


    Intramolecular hydrogen bonding (HB) is one of the most studied noncovalent interactions of molecules. Many physical, spectral, and topological properties of compounds are under the influence of HB, and there are many parameters used to notice and to describe these changes. Hitherto, no general method of measurement of the energy of intramolecular hydrogen bond (EHB) has been put into effect. We propose the molecular tailoring approach (MTA) for EHB calculation, modified to apply it to Ar-O-H∙∙∙O=C systems. The method, based on quantum calculations, was checked earlier for hydroxycarbonyl-saturated compounds, and for structures with resonance-assisted hydrogen bonding (RAHB). For phenolic compounds, the accuracy, repeatability, and applicability of the method is now confirmed for nearly 140 structures. For each structure its aromaticity HOMA indices were calculated for the central (ipso) ring and for the quasiaromatic rings given by intramolecular HB. The comparison of calculated HB energies and values of estimated aromaticity indices allowed us to observe, in some substituted phenols and quinones, the phenomenon of transfer of aromaticity from the ipso-ring to the H-bonded ring via the effect of electron delocalization.

  2. Energy of Intramolecular Hydrogen Bonding in ortho-Hydroxybenzaldehydes, Phenones and Quinones. Transfer of Aromaticity from ipso-Benzene Ring to the Enol System(s

    Directory of Open Access Journals (Sweden)

    Danuta Rusinska-Roszak


    Full Text Available Intramolecular hydrogen bonding (HB is one of the most studied noncovalent interactions of molecules. Many physical, spectral, and topological properties of compounds are under the influence of HB, and there are many parameters used to notice and to describe these changes. Hitherto, no general method of measurement of the energy of intramolecular hydrogen bond (EHB has been put into effect. We propose the molecular tailoring approach (MTA for EHB calculation, modified to apply it to Ar-O-H∙∙∙O=C systems. The method, based on quantum calculations, was checked earlier for hydroxycarbonyl-saturated compounds, and for structures with resonance-assisted hydrogen bonding (RAHB. For phenolic compounds, the accuracy, repeatability, and applicability of the method is now confirmed for nearly 140 structures. For each structure its aromaticity HOMA indices were calculated for the central (ipso ring and for the quasiaromatic rings given by intramolecular HB. The comparison of calculated HB energies and values of estimated aromaticity indices allowed us to observe, in some substituted phenols and quinones, the phenomenon of transfer of aromaticity from the ipso-ring to the H-bonded ring via the effect of electron delocalization.

  3. Mechanistic elucidation of the stepwise formation of a tetranuclear manganese pinned butterfly cluster via N-N bond cleavage, hydrogen atom transfer, and cluster rearrangement. (United States)

    Hamilton, Clifton R; Gau, Michael R; Baglia, Regina A; McWilliams, Sean F; Zdilla, Michael J


    A mechanistic pathway for the formation of the structurally characterized manganese-amide-hydrazide pinned butterfly complex, Mn4(μ3-PhN-NPh-κ(3)N,N')2(μ-PhN-NPh-κ(2)-N,N')(μ-NHPh)2L4 (L = THF, py), is proposed and supported by the use of labeling studies, kinetic measurements, kinetic competition experiments, kinetic isotope effects, and hydrogen atom transfer reagent substitution, and via the isolation and characterization of intermediates using X-ray diffraction and electron paramagnetic resonance spectroscopy. The data support a formation mechanism whereby bis[bis(trimethylsilyl)amido]manganese(II) (Mn(NR2)2, where R = SiMe3) reacts with N,N'-diphenylhydrazine (PhNHNHPh) via initial proton transfer, followed by reductive N-N bond cleavage to form a long-lived Mn(IV) imido multinuclear complex. Coordinating solvents activate this cluster for abstraction of hydrogen atoms from an additional equivalent of PhNHNHPh resulting in a Mn(II)phenylamido dimer, Mn2(μ-NHPh)2(NR2)2L2. This dimeric complex further assembles in fast steps with two additional equivalents of PhNHNHPh replacing the terminal silylamido ligands with η(1)-hydrazine ligands to give a dimeric Mn2(μ-NHPh)2(PhN-NHPh)2L4 intermediate, and finally, the addition of two additional equivalents of Mn(NR2)2 and PhNHNHPh gives the pinned butterfly cluster.

  4. Field-controlled electron transfer and reaction kinetics of the biological catalytic system of microperoxidase-11 and hydrogen peroxide

    Directory of Open Access Journals (Sweden)

    Yongki Choi


    Full Text Available Controlled reaction kinetics of the bio-catalytic system of microperoxidase-11 and hydrogen peroxide has been achieved using an electrostatic technique. The technique allowed independent control of 1 the thermodynamics of the system using electrochemical setup and 2 the quantum mechanical tunneling at the interface between microperoxidase-11 and the working electrode by applying a gating voltage to the electrode. The cathodic currents of electrodes immobilized with microperoxidase-11 showed a dependence on the gating voltage in the presence of hydrogen peroxide, indicating a controllable reduction reaction. The measured kinetic parameters of the bio-catalytic reduction showed nonlinear dependences on the gating voltage as the result of modified interfacial electron tunnel due to the field induced at the microperoxidase-11-electrode interface. Our results indicate that the kinetics of the reduction of hydrogen peroxide can be controlled by a gating voltage and illustrate the operation of a field-effect bio-catalytic transistor, whose current-generating mechanism is the conversion of hydrogen peroxide to water with the current being controlled by the gating voltage.

  5. Hydroperoxyl Radicals (HOO(.) ): Vitamin E Regeneration and H-Bond Effects on the Hydrogen Atom Transfer. (United States)

    Cedrowski, Jakub; Litwinienko, Grzegorz; Baschieri, Andrea; Amorati, Riccardo


    Hydroperoxyl (HOO(.) ) and alkylperoxyl (ROO(.) ) radicals show a different behavior in H-atom-transfer processes. Both radicals react with an analogue of α-tocopherol (TOH), but HOO(.) , unlike ROO(.) , is able to regenerate TOH by a fast H-atom transfer: TO(.) +HOO(.) →TOH+O2 . The kinetic solvent effect on the H-atom transfer from TOH to HOO(.) is much stronger than that observed for ROO(.) because noncovalent interactions with polar solvents (Solv⋅⋅⋅HOO(.) ) destabilize the transition state. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Asymmetric Divisions in Oogenesis. (United States)

    Bilinski, Szczepan M; Kubiak, Jacek Z; Kloc, Malgorzata

    In the majority of animals, the oocyte/egg is structurally, molecularly, and functionally asymmetric. Such asymmetry is a prerequisite for a flawless fertilization and faithful segregation of maternal determinants during subsequent embryonic development. The oocyte asymmetry develops during oogenesis and must be maintained during consecutive and obligatorily asymmetric oogonial divisions, which depending on the species lead to the formation of either oocyte alone or oocyte and nurse cell complex. In the following chapter, we summarize current knowledge on the asymmetric oogonial divisions in invertebrate (insects) and vertebrate (Xenopus) species.

  7. Study of the transfer of electrons and hydrogen atoms between substituted p-benzoquinone triplets and diphenylamine by flash-photolysis methods

    Energy Technology Data Exchange (ETDEWEB)

    Levin, P.P.; Kokrashvili, T.A.


    The primary and secondary aromatic amines quench the triplet states of carbonyl compounds through processes involving the transfer of charges and hydrogen atoms. The interaction of the benzophenone triplet with primary and secondary aromatic amines involves a one-step transfer of H atoms, and leads to the formation of ketyl and aminyl radicals in both polar and nonpolar solvents. The triplet state of 2,6-diphenyl-1,4-benzoquinone can be quenched through diphenylamine (DPA), a secondary aromatic amine, the quenching mechanism involving a diffusion-limited transfer of both charges and H atoms. The processes of electron and H atom transfer are in competition here, proceeding independently in the collision complex. Neutral radicals and short-lived radical-ion pairs (t approx. 100 nsec) are formed as the result of quenching in low-polarity solvents. Both neutral and charged radicals are formed through quenching in acetonitrile, but only radical-ions are formed through quenching in alcoholic solution. Only charged radicals are formed through quenching of duroquinone by DPA in ethanol-water mixtures. An understanding of the factors determining the mechanism of carbonyl compound triplet state quenching by electron and H atom donors can be obtained through a study of the effect of the structures of the reacting molecules, and the solvent, on the kinetics of the transfer processes. The present work has used flash photolysis methods to study the intermediates formed during the quenching of the triplet states of the p-benzoquinones by DFA in solvents of various polarities.

  8. Dichotomous Hydrogen Atom Transfer vs. Proton Coupled Electron Transfer During Activation of X-H Bonds (X = C, N, O) by Nonheme Iron-Oxo Complexes of Variable Basicity (United States)

    Usharani, Dandamudi; Lacy, David C.; Borovik, A. S.; Shaik, Sason


    We describe herein the hydrogen-atom transfer (HAT)/ proton-coupled electron-transfer (PCET) reactivity for FeIV-oxo and FeIII-oxo complexes (1–4) that activate C-H, N-H, and O-H bonds in 9,10 dihydroanthracene (S1), dimethylformamide (S2), 1,2 diphenylhydrazine (S3), p-methoxyphenol (S4), and 1,4-cyclohexadiene (S5). In 1–3, the iron is pentacoordinated by tris[N'-tert-butylureaylato)-N-ethylene]aminato ([H3buea]3−) or its derivatives. These complexes are basic, in the order 3 >> 1 > 2. Oxidant 4, [FeIVN4Py(O)]2+ (N4Py: N,N-bis(2-pyridylmethyl)-bis(2-pyridyl) methylamine), is the least basic oxidant. The DFT results match experimental trends and exhibit a mechanistic spectrum ranging from concerted HAT and PCET reactions to concerted-asynchronous proton transfer (PT) / electron transfer (ET) mechanisms, all the way to PT. The singly occupied orbital along the O---H---X (X= C, N, O) moiety in the TS shows clearly that in the PCET cases, the electron is transferred separately from the proton. The Bell-Evans-Polanyi principle does not account for the observed reactivity pattern, as evidenced by the scatter in the plot of calculated barrier vs. reactions driving forces. However, a plot of the deformation energy in the TS vs. the respective barrier provides a clear signature of the HAT/PCET dichotomy. Thus, in all C-H bond activations, the barrier derives from the deformation energy required to create the TS, whereas in N-H/O-H bond activations, the deformation energy is much larger than the corresponding barrier, indicating the presence of stabilizing interaction between the TS fragments. A valence bond model is used to link the observed results with the basicity/acidity of the reactants. PMID:24124906

  9. Interlimb Transfer of Grasp Orientation is Asymmetrical

    Directory of Open Access Journals (Sweden)

    Victor Frak


    Full Text Available One the most fundamental aspects of the human motor system is the hemispheric asymmetry seen in behavioral specialization. Hemispheric dominance can be inferred by a contralateral hand preference in grasping. Few studies have considered grasp orientation in the context of manual lateralization and none has looked at grasp orientation with natural prehension. Thirty right-handed adults performed precision grasps of a cylinder using the thumb and index fingers, and the opposition axis (OA was defined as the line connecting these two contact points on the cylinder. Subjects made ten consecutive grasps with one hand (primary hand movements followed by ten grasps with the other hand (trailing movements. Differences between primary and trailing grasps revealed that each hemisphere is capable of programming the orientation of the OA and that primary movements with the right hand significantly influenced OA orientation of the trailing left hand. These results extend the hemispheric dominance of the left hemisphere to the final positions of fingers during prehension.

  10. Hydrogen Bond Switching among Flavin and Amino Acids Determines the Nature of Proton-Coupled Electron Transfer in BLUF Photoreceptors

    NARCIS (Netherlands)

    Mathes, T.; Zhu, J.; van Stokkum, I.H.M.; Groot, M.L.; Hegemann, P.; Kennis, J.T.M.


    BLUF domains are flavin-binding photoreceptors that can be reversibly switched from a dark-adapted state to a light-adapted state. Proton-coupled electron transfer (PCET) from a conserved tyrosine to the flavin that results in a neutral flavin semiquinone/tyrosyl radical pair constitutes the

  11. Kinetic isotope effect of proton-coupled electron transfer in a hydrogen bonded phenol-pyrrolidino[60]fullerene

    NARCIS (Netherlands)

    Ravensbergen, J.; Brown, C.L.; Moore, G.F.; Frese, R.N.; van Grondelle, R.; Gust, D.; Moore, T.A.; Moore, A.L.; Kennis, J.T.M.


    Proton-coupled electron transfer (PCET) plays a central role in photosynthesis and potentially in solar-to-fuel systems. We report a spectroscopy study on a phenol-pyrrolidino[60]fullerene. Quenching of the singlet excited state from 1 ns to 250 ps is assigned to PCET. A H/D exchange study reveals a

  12. Vinylimidazole-Based Asymmetric Ion Pair Comonomers: Synthesis, Polymerization Studies and Formation of Ionically Crosslinked PMMA

    NARCIS (Netherlands)

    Jana, S.; Vasantha, V.A.; Stubbs, L.P.; Parthiban, A.; Vancso, Gyula J.


    Vinylimidazole-based asymmetric ion pair comonomers (IPCs) which are free from nonpolymerizable counter ions have been synthesized, characterized and polymerized by free radical polymerization (FRP), atom transfer radical polymerization (ATRP), and reversible addition-fragmentation chain transfer

  13. Crystal structure of acetanilide at 15 and 295 K by neutron diffraction. Lack of evidence for proton transfer along the N-H...O hydrogen bond

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, S.W.; Eckert, J. [Los Alamos National Lab., NM (United States); Barthes, M. [Universite Montpellier II (France); McMullan, R.K. [Brookhaven National Lab., Upton, NY (United States); Muller, M. [Universite Lille I, Villeneuve d`Ascq (France)


    The crystal structure of acetanilide C{sub 8}H{sub 9}NO, M{sub r} = 135.17, orthorhombic, space group Pbca, Z=8, has been determined from neutron diffraction data at 15 and 295 K. The crystal data obtained are presented. This new investigation of the structure of acetanilide has been undertaken in order to assess a recent suggestion that confirmational substates in the amide proton position may be responsible for the vibrational anomalies. We found no evidence for multiple conformations or transfer along the N-H...O hydrogen bond of the amide proton at either temperature. However the intramolecular O...H6 distance from O to the nearest phenyl ring proton is unusually short and the amide proton has relatively close contacts with one of the phenyl and one of the methyl protons, which may well affect the vibrational parameters of the respective molecular groups. 44 refs., 6 figs., 5 tabs.

  14. Rapid crystallization of a-Si:H films with various silicon-to-hydrogen bonding configurations using rapid energy transfer annealing

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Y.-L. [Department of Electrical Engineering, National Chung Hsing University, Taichung 402, Taiwan (China)]. E-mail:; Chang, Y.-C. [Department of Electrical Engineering, National Chung Hsing University, Taichung 402, Taiwan (China)


    Hydrogenated amorphous silicon (a-Si:H) films were prepared by changing substrate temperature of plasma-enhanced chemical vapor deposition to induce different contents of monohydride and polyhydride bonds, which were then crystallized into polysilicon (poly-Si) films by rapid energy transfer annealing. Fourier transform infrared and transmission spectra show that the formation of numerous polyhydride bonds increases the hydrogen content and reduces the refractive index of a-Si:H films. The rise in the concentration of polyhydride bonds in as-deposited a-Si:H films can result in the increase of ultraviolet reflectance, small peak shift, and change in full width at half maximum of Raman scattering and X-ray diffraction peaks of the obtained poly-Si films after annealing. These results demonstrate that high-concentration polyhydride bonds can promote the rapid crystallization of a-Si:H and obtain high-crystallinity poly-Si films. Transmission electron microscopy identifies that the poly-Si films have the typical dendrite-like grain structure.

  15. Comparative study of Green's function matrix elements and charge transfers obtained from different partitioning schemes of molecular charge in hydrogen-bonded complexes

    Directory of Open Access Journals (Sweden)

    Parnaíba-da Silva Antenor J.


    Full Text Available RHF and MP2 ab initio molecular orbital calculations using the 4-31G**, 6-311G** and cc-pVTZ basis sets have revealed that the Green's function matrix element (G D,A values show a good correlation with the amount of intermolecular transferred charges obtained from different charge partitioning schemes for the CNH?CNH, NCH?CNH, CNH?NCH and NCH?NCH hydrogen bonded complexes. This is evident specially when the hydrogen bond distance is progressively increased from the equilibrium position until 4.5 Å. However, G D,A values show a better linear correlation with deltaQ values using corrected Mülliken charges, which are obtained from the charge-charge flux-overlap (CCFO model for infrared intensities. In this case, both G D,A and deltaQcorr form two practically superposed exponential curves. On the other hand, G D,A values show a smaller agreement with deltaQ values obtained from atomic charges derived from natural bonding orbitals. This is clearly verified when considering the first order exponential decay rate of G D,A versus deltaQ obtained from different charge partitioning schemes.

  16. Ultralow charge-transfer resistance with ultralow Pt loading for hydrogen evolution and oxidation using Ru@Pt core-shell nanocatalysts (United States)

    Wang, Jia X.; Zhang, Yu; Capuano, Christopher B.; Ayers, Katherine E.


    We evaluated the activities of well-defined Ru@Pt core-shell nanocatalysts for hydrogen evolution and oxidation reactions (HER-HOR) using hanging strips of gas diffusion electrode (GDE) in solution cells. With gas transport limitation alleviated by micro-porous channels in the GDEs, the charge transfer resistances (CTRs) at the hydrogen reversible potential were conveniently determined from linear fit of ohmic-loss-corrected polarization curves. In 1 M HClO4 at 23 °C, a CTR as low as 0.04 Ω cm-2 was obtained with only 20 μg cm-2 Pt and 11 μg cm-2 Ru using the carbon-supported Ru@Pt with 1:1 Ru:Pt atomic ratio. Derived from temperature-dependent CTRs, the activation barrier of the Ru@Pt catalyst for the HER-HOR in acids is 0.2 eV or 19 kJ mol-1. Using the Ru@Pt catalyst with total metal loadings <50 μg cm-2 for the HER in proton-exchange-membrane water electrolyzers, we recorded uncompromised activity and durability compared to the baseline established with 3 mg cm-2 Pt black.

  17. A luminescent lanthanide coordination polymer based on energy transfer from metal to metal for hydrogen peroxide detection. (United States)

    Zeng, Hui-Hui; Zhang, Li; Rong, Lian-Qing; Liang, Ru-Ping; Qiu, Jian-Ding


    A bimetal lanthanide coordination polymer nanoparticle (ATP-Ce/Tb-Tris CPNs) with good biocompatibility was synthesized in Tris-HCl buffer using adenosine triphosphate (ATP) molecules as the bridge ligands. The large absorption cross section and suitable emission energy of Ce3+ matching to the adsorption energy of Tb3+(4fn) results in the efficient energy transfer from Ce3+ to Tb3+, thus the synthesized ATP-Ce/Tb-Tris CPNs exhibit the characteristic green emission of Tb3+. Such energy transfer from metal to metal in fluorescent lanthanide coordination polymer nanoparticles (Ln-CPNs) has been demonstrated. It is found that the oxidation of Ce3+ in ATP-Ce/Tb-Tris CNPs to Ce4+ would interrupt the energy transfer from Ce3+ to Tb3+, leading to fluorescence quenching of Tb3+. On the basis of this quenching mechanism, ATP-Ce/Tb-Tris CPNs has been successfully used to detect reactive oxygen H2O2 with detection limit as low as 2nM. If glucose oxidase is present in the system, glucose can be determined using the ATP-Ce/Tb-Tris CNPs nanosensor. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Worldwide clean energy system technology using hydrogen (WE-NET). Subtask 5. Development of hydrogen transfer and storage technology (development of various common equipment); Suiso riyo kokusai clean energy system gijutsu (WE-NET). subtask 5. Suiso yuso chozo gijutsu no kaihatsu (kakushu kyotsu kikirui no kaihatsu)

    Energy Technology Data Exchange (ETDEWEB)



    This report describes large pumps for liquid hydrogen, large-size vacuum-insulated tubes, valves for liquid hydrogen, and instrumentation equipment. In the WE-NET Project, large pumps for liquid hydrogen are to be used for feeding pressurized liquid hydrogen to the combustors in power generative facilities as well as transferring large amounts of liquid hydrogen in liquefying facilities, and to or from tankers, etc. As a result of the examination, axial flow pump and mixed flow pump are to be applied to the large pumps, and centrifugal pump is to be applied to the pressurized pump. A vertical shaft wet motor pump which is directly connected to wound-rotor induction motor has been adopted as a basic specification. For the large-size vacuum-insulated tubes, examination has been conducted with the emphasis on method of relaxing the thermal stress from the viewpoint of transferring the liquid hydrogen at large flow-rate and cryogenic temperature in a stable and safe manner over long distances. It has been shown that the development of marine loading arm is indispensable. For the valves for liquid hydrogen, a ball valve and a butterfly valve, which are operated pneumatically, have been investigated. For the instrumentation equipment, level sensor for tanks, flow meter, and method of leakage detection have been examined. 315 refs., 50 figs., 16 tabs.

  19. Influence of geometrical non-uniformities of LaNi5 metal hydride bed on its structure and heat and mass transfer at hydrogen absorption (United States)

    Blinov, D. V.; Dunikov, D. O.; Kazakov, A. N.; Romanov, I. A.


    We perform cycling of a 500 g bed of La0.9Ce0.1Ni5 intermetallic compound in vertical and horizontal orientations with measurements of PCT isotherms, and further XRD and SEM investigation of bed structure. Significant decrease in equilibrium absorption pressure is observed in vertical orientation of the bed from 1.58 to 1.36 MPa at 333K, and from 2.68 to 2.51 MPa at 353K, accompanied by evident particle segregation by the bed height and densification at a bottom with formation of a robust agglomerate of small particles (mass transfer inside a vertical metal hydride reactor RSP-8 with 1 kg of La0.9Ce0.1Ni5 also show considerable non-uniformity of pressure inside the bed. If the reactor is charged from the top the hydrogen pressure at the bottom is lower on 0.2-0.3 MPa, which results in earlier occurrence of heat and mass transfer crisis.

  20. Asymmetrical field emitter (United States)

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


    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.

  1. Effect of Basic Site Substituents on Concerted Proton-Electron Transfer in Hydrogen Bonded-Pyridyl Phenols (United States)

    Markle, Todd F.; Tronic, Tristan A.; DiPasquale, Antonio G.; Kaminsky, Werner


    Separated concerted proton-electron transfer (sCPET) reactions of two series of phenols with pendent substituted pyridyl moieties are described. The pyridine is either attached directly to the phenol (HOAr-pyX) or connected through a methylene linker (HOArCH2pyX) (X = 4-NO2, 5-CF3, 4-CH3, 4-NMe2). Electron-donating and -withdrawing substituents also have a substantial effect on the chemical environment of the transferring proton, as indicated by IR and 1H NMR spectra, X-ray structures and computational studies. One-electron oxidation of the phenols occurs concomitantly with proton transfer from the phenolic oxygen to the pyridyl nitrogen. The oxidation potentials vary linearly with the pKa of the free pyridine (pyX), with slopes slightly below the Nerstian value of 59 mV/pKa. For the HOArCH2pyX series, the rate constants ksCPET for oxidation by NAr3•+ or [Fe(diimine)3]3+ vary primarily with the thermodynamic driving force (ΔG°sCPET), whether ΔG° is changed by varying the potential of the oxidant or the substituent on the pyridine, indicating a constant intrinsic barrier λ. In contrast, the substituents in the HOAr-pyX series affect λ as well as ΔG°sCPET, and compounds with electron-withdrawing substituents have significantly lower reactivity. The relationship between the structural and spectroscopic properties of the phenols and their CPET reactivity is discussed. PMID:23176252

  2. Effect of basic site substituents on concerted proton-electron transfer in hydrogen-bonded pyridyl-phenols. (United States)

    Markle, Todd F; Tronic, Tristan A; DiPasquale, Antonio G; Kaminsky, Werner; Mayer, James M


    Separated concerted proton-electron transfer (sCPET) reactions of two series of phenols with pendent substituted pyridyl moieties are described. The pyridine is either attached directly to the phenol (HOAr-pyX) or connected through a methylene linker (HOArCH(2)pyX) (X = 4-NO(2), 5-CF(3), 4-CH(3), and 4-NMe(2)). Electron-donating and -withdrawing substituents have a substantial effect on the chemical environment of the transferring proton, as indicated by IR and (1)H NMR spectra, X-ray structures, and computational studies. One-electron oxidation of the phenols occurs concomitantly with proton transfer from the phenolic oxygen to the pyridyl nitrogen. The oxidation potentials vary linearly with the pK(a) of the free pyridine (pyX), with slopes slightly below the Nerstian value of 59 mV/pK(a). For the HOArCH(2)pyX series, the rate constants k(sCPET) for oxidation by NAr(3)(•+) or [Fe(diimine)(3)](3+) vary primarily with the thermodynamic driving force (ΔG°(sCPET)), whether ΔG° is changed by varying the potential of the oxidant or the substituent on the pyridine, indicating a constant intrinsic barrier λ. In contrast, the substituents in the HOAr-pyX series affect λ as well as ΔG°(sCPET), and compounds with electron-withdrawing substituents have significantly lower reactivity. The relationship between the structural and spectroscopic properties of the phenols and their CPET reactivity is discussed.

  3. In-situ biogas upgrading in thermophilic granular UASB reactor: key factors affecting the hydrogen mass transfer rate

    DEFF Research Database (Denmark)

    Bassani, Ilaria; Kougias, Panagiotis; Angelidaki, Irini


    in the biogas into CH4, via hydrogenotrophic methanogenesis. The setup consisted of a granular reactor connected to a separate chamber, where H2 was injected. Different packing materials (rashig rings and alumina ceramic sponge) were tested to increase gas-liquid mass transfer. This aspect was optimized...... by liquid and gas recirculation and chamber configuration. It was shown that by distributing H2 through a metallic diffuser followed by ceramic sponge in a separate chamber, having a volume of 25% of the reactor, and by applying a mild gas recirculation, CO2 content in the biogas dropped from 42 to 10...

  4. In-situ biogas upgrading in thermophilic granular UASB reactor: key factors affecting the hydrogen mass transfer rate. (United States)

    Bassani, Ilaria; Kougias, Panagiotis G; Angelidaki, Irini


    Biological biogas upgrading coupling CO 2 with external H 2 to form biomethane opens new avenues for sustainable biofuel production. For developing this technology, efficient H 2 to liquid transfer is fundamental. This study proposes an innovative setup for in-situ biogas upgrading converting the CO 2 in the biogas into CH 4 , via hydrogenotrophic methanogenesis. The setup consisted of a granular reactor connected to a separate chamber, where H 2 was injected. Different packing materials (rashig rings and alumina ceramic sponge) were tested to increase gas-liquid mass transfer. This aspect was optimized by liquid and gas recirculation and chamber configuration. It was shown that by distributing H 2 through a metallic diffuser followed by ceramic sponge in a separate chamber, having a volume of 25% of the reactor, and by applying a mild gas recirculation, CO 2 content in the biogas dropped from 42 to 10% and the final biogas was upgraded from 58 to 82% CH 4 content. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Asymmetrical international attitudes

    NARCIS (Netherlands)

    Van Oudenhoven, JP; Askevis-Leherpeux, F; Hannover, B; Jaarsma, R; Dardenne, B


    In general, attitudes towards nations have a fair amount of reciprocity: nations either like each other are relatively indifferent to each other or dislike each other Sometimes, however international attitudes are asymmetrical. In this study, we use social identity theory in order to explain

  6. How Is Nature Asymmetric?

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 7; Issue 6. How Is Nature Asymmetric? - Discrete Symmetries in Particle Physics and their Violation ... Indian Institute of Technology, Chennai. Aligarh Muslim University. University of Rajasthan, Jaipur. Indian Institute of Science, Bangalore 560012, India.

  7. Hydrogen maser clocks in space for solid-Earth research and time-transfer applications: Experiment overview and evaluation of Russian miniature sapphire loaded cavity (United States)

    Busca, G.; Bernier, L. G.; Silvestrin, P.; Feltham, S.; Gaygerov, B. A.; Tatarenkov, V. M.


    The Observatoire Cantonal de Neuchatel (ON) is developing for ESTEC a compact H-maser for space use based upon a miniature sapphire loaded microwave cavity, a technique pioneered at VNIIFTRI. Various contacts between West-European parties, headed by ESA, and the Russian parties, headed by ESA, led to the proposal for flying two H-masers on Meteor 3M, a Russian meteorology satellite in low polar orbit. The experiment will include two masers, one provided by ON and the other by VNIIFTRI. T/F transfer and precise positioning will be performed by both a microwave link, using PRARE equipment, and an optical link, using LASSO-like equipment. The main objectives of the experiment are precise orbit determination and point positioning for geodetic/geophysical research, ultra-accurate time comparison and dissemination as well as in-orbit demonstration of operation and performance of H-masers. Within the scope of a preliminary space H-maser development phase performed for ESTEC at ON in preparation to the joint experiment, a Russian miniature sapphire loaded microwave cavity, on loan from VNIIFTRI, was evaluated in a full-size EFOS hydrogen maser built by ON. The experimental evaluation confirmed the theoretical expectation that with a hydrogen storage volume of only 0.65 liter an atomic quality factor of 1.5 x 10(exp 9) can be obtained for a -105 dBm output power. This represents a theoretical Allan deviation of 1.7 x 10(exp -15) averaged on a 1000 s time interval. From a full-size design to a compact one, therefore, the sacrifice in performance due to the reduction of the storage volume is very small.

  8. Photoelectron spectroscopy investigation of the temperature-induced deprotonation and substrate-mediated hydrogen transfer in a hydroxyphenyl-substituted porphyrin

    Energy Technology Data Exchange (ETDEWEB)

    Smykalla, Lars, E-mail: [Technische Universität Chemnitz, Institute of Physics, Solid Surfaces Analysis Group, D-09107 Chemnitz (Germany); Shukrynau, Pavel [Technische Universität Chemnitz, Institute of Physics, Solid Surfaces Analysis Group, D-09107 Chemnitz (Germany); Mende, Carola; Lang, Heinrich [Technische Universität Chemnitz, Institute of Chemistry, Inorganic Chemistry, D-09107 Chemnitz (Germany); Knupfer, Martin [Electronic and Optical Properties Department, IFW Dresden, D-01171 Dresden (Germany); Hietschold, Michael [Technische Universität Chemnitz, Institute of Physics, Solid Surfaces Analysis Group, D-09107 Chemnitz (Germany)


    Highlights: • Photoelectron spectroscopy of tetra(p-hydroxyphenyl)porphyrin on Au(1 1 1) and Ag(1 1 0). • Ratio of amount of −NH− to −N= in the molecule on Au(1 1 1) decreases after annealing. • Dissociation of −OH groups and transfer of hydrogen atoms to −N= on Ag(1 1 0). • Cleavage of C−H bonds of porphyrin macro-cycle at high temperature. • Changes of the valence band of the molecule in dependance of annealing temperature. - Abstract: The temperature dependent stepwise deprotonation of 5,10,15,20-tetra(p-hydroxyphenyl)-porphyrin is investigated using photoelectron spectroscopy. An abundance of pyrrolic relative to iminic nitrogen and a decrease in the ratio of the amount of −NH− to −N= with increasing annealing temperature is found. In contrast to the molecules adsorbed on Au(1 1 1), on the more reactive Ag(1 1 0) surface, partial dissociation of the hydroxyl groups and subsequent diffusion and rebonding of hydrogen to the central nitrogen atoms resulting in a zwitterionic molecule was clearly observed. Moreover, partial C−H bond cleavage and the formation of new covalent bonds with adjacent molecules or the surface starts at a relatively high annealing temperature of 300 °C. This reaction is identified to occur at the carbon atoms of the pyrrole rings, which leads also to a shift in the N 1s signal and changes in the valence band of the molecules. Our results show that annealing can significantly alter the molecules which were deposited depending on the maximum temperature and the catalytic properties of the specific substrate. The thermal stability should be considered if a molecular monolayer is prepared from a multilayer by desorption, or if annealing is applied to enhance the self-assembly of molecular structures.

  9. Direct electron transfer of glucose oxidase and dual hydrogen peroxide and glucose detection based on water-dispersible carbon nanotubes derivative

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Hsiao-Chien [Department of Biochemistry and Molecular Cell Biology, School of Medicine, College of Medicine, Taipei Medical University, 250, Wuxing St., Taipei 11031, Taiwan (China); Tu, Yi-Ming; Hou, Chung-Che [Department of Chemical and Materials Engineering, Chang Gung University, 259 Wen-Hwa 1st Rd., Tao-Yuan 33302, Taiwan (China); Lin, Yu-Chen [Wah Hong industrial Co. Ltd., 6 Lixing St., Guantian Dist., Tainan City 72046,Taiwan (China); Chen, Ching-Hsiang [Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, 43 Keelung Rd., Sec. 4, Taipei 10607, Taiwan (China); Yang, Kuang-Hsuan, E-mail: [Department of Food and Beverage Management, Vanung University, 1, Van Nung Rd., Shuei-Wei Li, Chung-Li City 32061, Taiwan (China)


    Highlights: • Dual hydrogen peroxide and glucose sensor. • Direct electrochemistry of glucose oxidase used MWCNT-Py/GC electrode. • Change sensing function by adjusting pH value. - Abstract: A water-dispersible multi-walled carbon nanotubes (MWCNTs) derivative, MWCNTs-1-one-dihydroxypyridine (MWCNTs-Py) was synthesis via Friedel–Crafts chemical acylation. Raman spectra demonstrated the conjugated level of MWCNTs-Py was retained after this chemical modification. MWCNTs-Py showed dual hydrogen peroxide (H{sub 2}O{sub 2}) and glucose detections without mutual interference by adjusting pH value. It was sensitive to H{sub 2}O{sub 2} in acidic solution and displayed the high performances of sensitivity, linear range, response time and stability; meanwhile it did not respond to H{sub 2}O{sub 2} in neutral solution. In addition, this positively charged MWCNTs-Py could adsorb glucose oxidase (GOD) by electrostatic attraction. MWCNTs-Py-GOD/GC electrode showed the direct electron transfer (DET) of GOD with a pair of well-defined redox peaks, attesting the bioactivity of GOD was retained due to the non-destroyed immobilization. The high surface coverage of active GOD (3.5 × 10{sup −9} mol cm{sup −2}) resulted in exhibiting a good electrocatalytic activity toward glucose. This glucose sensor showed high sensitivity (68.1 μA mM{sup −1} cm{sup −2}) in a linear range from 3 μM to 7 mM in neutral buffer solution. The proposed sensor could distinguish H{sub 2}O{sub 2} and glucose, thus owning high selectivity and reliability.

  10. Total syntheses of (–)-Borrelidin and (–)-Doliculide and the development of the catalytic asymmetric addition of Grignard reagents to ketones

    NARCIS (Netherlands)

    Madduri Venkata, Ashoka Vardhan Reddy


    This thesis describes the application of copper-catalyzed asymmetric conjugate addition and ruthenium-catalyzed asymmetric hydrogenation in novel total syntheses of the macrocyclic polyketides Borrelidin and Doliculide. A second topic in the thesis comprizes the development of a novel asymmetric

  11. Highly asymmetric rice genomes

    Directory of Open Access Journals (Sweden)

    Chen Jian-Qun


    Full Text Available Abstract Background Individuals in the same species are assumed to share the same genomic set. However, it is not unusual to find an orthologous gene only in small subset of the species, and recent genomic studies suggest that structural rearrangements are very frequent between genomes in the same species. Two recently sequenced rice genomes Oryza sativa L. var. Nipponbare and O. sativa L. var. 93-11 provide an opportunity to systematically investigate the extent of the gene repertoire polymorphism, even though the genomic data of 93-11 derived from whole-short-gun sequencing is not yet as complete as that of Nipponbare. Results We compared gene contents and the genomic locations between two rice genomes. Our conservative estimates suggest that at least 10% of the genes in the genomes were either under presence/absence polymorphism (5.2% or asymmetrically located between genomes (4.7%. The proportion of these "asymmetric genes" varied largely among gene groups, in which disease resistance (R genes and the RLK kinase gene group had 11.6 and 7.8 times higher proportion of asymmetric genes than housekeeping genes (Myb and MADS. The significant difference in the proportion of asymmetric genes among gene groups suggests that natural selection is responsible for maintaining genomic asymmetry. On the other hand, the nucleotide diversity in 17 R genes under presence/absence polymorphism was generally low (average nucleotide diversity = 0.0051. Conclusion The genomic symmetry was disrupted by 10% of asymmetric genes, which could cause genetic variation through more unequal crossing over, because these genes had no allelic counterparts to pair and then they were free to pair with homologues at non-allelic loci, during meiosis in heterozygotes. It might be a consequence of diversifying selection that increased the structural divergence among genomes, and of purifying selection that decreased nucleotide divergence in each R gene locus.

  12. Copper-catalyzed asymmetric oxidation of sulfides. (United States)

    O'Mahony, Graham E; Ford, Alan; Maguire, Anita R


    Copper-catalyzed asymmetric sulfoxidation of aryl benzyl and aryl alkyl sulfides, using aqueous hydrogen peroxide as the oxidant, has been investigated. A relationship between the steric effects of the sulfide substituents and the enantioselectivity of the oxidation has been observed, with up to 93% ee for 2-naphthylmethyl phenyl sulfoxide, in modest yield in this instance (up to 30%). The influence of variation of solvent and ligand structure was examined, and the optimized conditions were then used to oxidize a number of aryl alkyl and aryl benzyl sulfides, producing sulfoxides in excellent yields in most cases (up to 92%), and good enantiopurities in certain cases (up to 84% ee).

  13. Kinetic study of the 7-endo selective radical cyclization of N-tert-butyl-o-bromobenzylmethacryl amides: kinetic investigation of the cyclization and 1,7-hydrogen transfer of aromatic radicals. (United States)

    Kamimura, Akio; Kotake, Tomoko; Ishihara, Yuriko; So, Masahiro; Hayashi, Takahiro


    A kinetic investigation of the radical cyclization of N-tert-butyl-o-bromobenzylmethacryl amides to give 2-benzazepines via 7-endo selective cyclization was undertaken. The aryl radical generated from the amide precursor by treatment with Bu3SnH gave the three compounds, which are a 7-endo cyclized adduct, a 6-exocyclized adduct, and a reduced product. The cyclization reactions under various Bu3SnH concentrations were traced by GC analysis. The 7-endo/6-exo selectivity was constant irrespective of variation in Bu3SnH concentration. These results revealed that regioselectivity is controlled in a kinetic manner and that there is no possibility of a neophyl rearrangement. The use of Bu3SnD revealed that 1,7-hydrogen transfer, in which an aryl radical abstracts a hydrogen atom from the methallylic methyl group, occurs during the reaction. Hydrogen abstraction from toluene, the reaction solvent, was also observed. The 1,7-transfer rate depended on the Bu3SnX (X = H or D), and the reaction kinetics was examined. The k(H)/k(D) value for the hydrogen abstraction of aryl radical from Bu3SnX (X = H or D) was estimated using 4-bromoanisol. The utilization of these values revealed the overall reaction kinetics and relative rates for the cyclization and reduction by Bu3SnX (X = H or D). Kinetic parameters for hydrogen abstraction from toluene by aryl radicals were also estimated.

  14. The Role of Symmetric-Stretch Vibration in Asymmetric-Stretch Vibrational Frequency Shift: the Case of 2CH Excitation Infrared Spectra of Acetylene-Hydrogen Van Der Waals Complex (United States)

    Hou, Dan; Ma, Yong-Tao; Zhang, Xiao-Long; Zhai, Yu; Li, Hui


    Direct infrared spectra predictions for van der Waals (vdW) complexes rely on accurate intra-molecular vibrationally excited inter-molecular potential. Due to computational cost increasing with number of freedom, constructing an effective reduced-dimension potential energy surface, which only includes direct relevant intra- molecular modes, is the most feasible way and widely used in the recent potential studies. However, because of strong intra-molecular vibrational coupling, some indirect relevant modes are also play important roles in simulating infrared spectra of vdW complexes. The questions are how many intra-molecular modes are needed, and which modes are most important in determining the effective potential and direct infrared spectra simulations. Here, we explore these issues using a simple, flexible and efficient vibration-averaged approach, and apply the method to vdW complex C_2H_2-H_2. With initial examination of the intra-molecular vibrational coupling, an effective seven-dimensional ab initio potential energy surface(PES) for C_2H_2-H_2, which explicitly takes into account the Q_1,Q_2 symmetric-stretch and Q_3 asymmetric-stretch normal modes of the C_2H_2 monomer, has been generated. Analytic four-dimensional PESs are obtained by least-squares fitting vibrationally averaged interaction energies for νb{3}(C_2H_2)=0 and 1 to the Morse/long-range(MLR) potential function form. We provide the first prediction of the infrared spectra and band origin shifts for C_2H_2-H_2 dimer. We particularly examine the dependence of the symmetric-stretch normal mode on asymmetric-stretch frequency shift for the complex.

  15. Coumarin or benzoxazinone bearing benzimidazolium and bis(benzimidazolium salts; involvement in transfer hydrogenation of acetophenone derivatives and hCA inhibition

    Directory of Open Access Journals (Sweden)

    Mert Olgun Karataş


    Full Text Available Four new salts of benzimidazolium and bis(benzimidazolium which include coumarin or benzoxazinone moieties were synthesized and the structures of the newly synthesized compounds were elucidated on the basis of spectral analyses such as 1H-NMR, 13C-NMR, HSQC, IR, LC-MS and elemental analysis. Benzimidazolium salts were used intensively as N-heterocyclic carbene (NHC precursors in the various catalytic reactions such as transfer hydrogenation (TH, C-H bond activation, Heck, Suzuki reaction etc. With the prospect of potential NHC precursor properties of the synthesized compounds, they were employed in the (TH reaction of p-substitute acetophenones (acetophenone, p-methyl acetophenone, p-chloro acetophenone and good yields were observed. Coumarin compounds are known as inhibitor of carbonic anhydrase and inhibition effects of the synthesized compounds on human carbonic anhydrases (hCA were investigated as in vitro. The in vitro results demonstrated that all compounds inhibited hCA I and hCA II activity. Among the synthesized compounds 1,4-bis(1-((6,8-dimethyl-2H-chromen-2-one-4-ylmethylbenzimidazolium-3-ylbutane dichloride was found to be the most active IC50= 5.55 mM and 6.06 mM for hCA I and hCA II, respectively.

  16. The excited-state intramolecular proton transfer in Nsbnd H-type dye molecules with a seven-membered-ring intramolecular hydrogen bond: A theoretical insight (United States)

    Yuan, Huijuan; Feng, Songyan; Wen, Keke; Guo, Xugeng; Zhang, Jinglai


    Excited-state intramolecular proton transfer (ESIPT) reactions of a series of N(R)sbnd H ⋯ N-type seven-membered-ring hydrogen-bonding compounds were explored by employing density functional theory/time-dependent density functional theory calculations with the PBE0 functional. Our results indicate that the absorption and emission spectra predicted theoretically match very well the experimental findings. Additionally, as the electron-withdrawing strength of R increases, the intramolecular H-bond of the Nsbnd S1 form gradually enhances, and the forward energy barrier along the ESIPT reaction gradually decreases. For compound 4, its ESIPT reaction is found to be a barrierless process due to the involvement of a strong electron-withdrawing COCF3 group. It is therefore a reasonable presumption that the ESIPT efficiency of these N(R)sbnd H ⋯ N-type seven-membered-ring H-bonding systems can be improved when a strong electron-withdrawing group in R is introduced.

  17. Deformed transition-state theory: Deviation from Arrhenius behavior and application to bimolecular hydrogen transfer reaction rates in the tunneling regime. (United States)

    Carvalho-Silva, Valter H; Aquilanti, Vincenzo; de Oliveira, Heibbe C B; Mundim, Kleber C


    A formulation is presented for the application of tools from quantum chemistry and transition-state theory to phenomenologically cover cases where reaction rates deviate from Arrhenius law at low temperatures. A parameter d is introduced to describe the deviation for the systems from reaching the thermodynamic limit and is identified as the linearizing coefficient in the dependence of the inverse activation energy with inverse temperature. Its physical meaning is given and when deviation can be ascribed to quantum mechanical tunneling its value is calculated explicitly. Here, a new derivation is given of the previously established relationship of the parameter d with features of the barrier in the potential energy surface. The proposed variant of transition state theory permits comparison with experiments and tests against alternative formulations. Prescriptions are provided and implemented to three hydrogen transfer reactions: CH 4  + OH → CH 3  + H 2 O, CH 3 Cl + OH → CH 2 Cl + H 2 O and H 2  + CN → H + HCN, widely investigated both experimentally and theoretically. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  18. Asymmetric extractions in orthodontics

    Directory of Open Access Journals (Sweden)

    Camilo Aquino Melgaço


    Full Text Available INTRODUCTION: Extraction decisions are extremely important in during treatment planning. In addition to the extraction decision orthodontists have to choose what tooth should be extracted for the best solution of the problem and the esthetic/functional benefit of the patient. OBJECTIVE: This article aims at reviewing the literature relating the advantages, disadvantages and clinical implications of asymmetric extractions to orthodontics. METHODS: Keywords were selected in English and Portuguese and the EndNote 9 program was used for data base search in PubMed, Web of Science (WSc and LILACS. The selected articles were case reports, original articles and prospective or retrospective case-control studies concerning asymmetrical extractions of permanent teeth for the treatment of malocclusions. CONCLUSION: According to the literature reviewed asymmetric extractions can make some specific treatment mechanics easier. Cases finished with first permanent molars in Class II or III relationship in one or both sides seem not to cause esthetic or functional problems. However, diagnosis knowledge and mechanics control are essential for treatment success.

  19. Asymmetric Evolutionary Games.

    Directory of Open Access Journals (Sweden)

    Alex McAvoy


    Full Text Available 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.

  20. Asymmetric Evolutionary Games. (United States)

    McAvoy, Alex; Hauert, Christoph


    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.

  1. Hydrogen-atom transfer in reactions of organic radicals with [Co-II(por)](center dot) (por = porphyrinato) and in subsequent addition of [Co(H)(por)] to olefins

    NARCIS (Netherlands)

    de Bruin, B.; Dzik, W.I.; Li, S.; Wayland, B.B.


    The mechanisms for hydrogen-atom transfer from the cyanoisopropyl radical C-center dot(CH3)(2)CN to [Co-II(por)](center dot) (yielding [Co-III(H)(por)] and CH2=C(CH3)(CN); por = porphyrinato) and the insertion of vinyl acetate (CH2=CHOAc) into the Co-H bond of [Co(H)(por)] (giving

  2. Catalytic asymmetric fluorinations. (United States)

    Bobbio, Carla; Gouverneur, Véronique


    The appearance of structurally diverse fluorinating reagents displaying a large spectrum of reactivity has been critical to the development of the catalytic asymmetric fluorination processes known to date. In this article, we discuss how this area of research emerged and which strategies have allowed for the successful development of both nucleophilic and electrophilic catalytic enantioselective fluorinations. We also present the fundamental understanding of catalytic activity and enantioselectivity for the most efficient processes and highlight the first synthetic application with the preparation of a complex fluorinated target.

  3. Asymmetric synthesis v.4

    CERN Document Server

    Morrison, James


    Asymmetric Synthesis, Volume 4: The Chiral Carbon Pool and Chiral Sulfur, Nitrogen, Phosphorus, and Silicon Centers describes the practical methods of obtaining chiral fragments. Divided into five chapters, this book specifically examines initial chiral transmission and extension. The opening chapter describes the so-called chiral carbon pool, the readily available chiral carbon fragments used as building blocks in synthesis. This chapter also provides a list of 375 chiral building blocks, along with their commercial sources, approximate prices, and methods of synthesis. Schemes involving

  4. Asymmetric Organocatalytic Cycloadditions

    DEFF Research Database (Denmark)

    Mose, Rasmus


    were pioneered by Otto Paul Hermann Diels and Kurt Alder who discovered what later became known as the Diels Alder reaction. The Diels Alder reaction is a [4+2] cycloaddition in which a π4 component reacts with a π2 component via a cyclic transition state to generate a 6 membered ring. This reaction...... undergo cascade reactions with different electron deficient dienophiles in Diels Alder – nucleophilic ring closing reactions. This methodology opens up for the direct asymmetric formation of hydroisochromenes and hydroisoquinolines which may possess interesting biological activities. It is also...

  5. Monoiron hydrogenase catalysis: hydrogen activation with the formation of a dihydrogen, Fe-H(delta-)...H(delta+)-O, bond and methenyl-H4MPT+ triggered hydride transfer. (United States)

    Yang, Xinzheng; Hall, Michael B


    A fully optimized resting state model with a strong Fe-H(delta-)...H(delta+)-O dihydrogen bond for the active site of the third type of hydrogenase, [Fe]-hydrogenase, is proposed from density functional theory (DFT) calculations on the reformulated active site from the recent X-ray crystal structure study of C176A (Cys176 was mutated to an alanine) mutated [Fe]-hydrogenase in the presence of dithiothreitol. The computed vibrational frequencies for this new active site model possess an average error of only +/-4.5 cm(-1) with respect to the wild-type [Fe]-hydrogenase. Based on this resting state model, a new mechanism with the following unusual aspects for hydrogen activation catalyzed by [Fe]-hydrogenase is also proposed from DFT calculations. (1) Unexpected dual pathways for H(2) cleavage with proton transfer to Cys176-sulfur or 2-pyridinol's oxygen for the formation and regeneration of the resting state with an Fe-H(delta-)...H(delta+)-O dihydrogen bond before the appearance of methenyl-H(4)MPT(+) (MPT(+)). (2) The strong dihydrogen bond in this resting state structure prevents D(2)/H(2)O exchange. (3) Only upon the arrival of MPT(+) with its strong hydride affinity can D(2)/H(2)O exchange take place as the arrival of MPT(+) triggers the breaking of the strong Fe-H(delta-)...H(delta+)-O dihydrogen bond by taking a hydride from the iron center and initiating the next H(2) (D(2)) cleavage. This new mechanism is completely different than that previously proposed (J. Am. Chem. Soc. 2008, 130, 14036) which was based on an active site model related to an earlier crystal structure. Here, Fe's role is H(2) capture and hydride formation without MPT(+) while the pyridone's special role involves the protection of the hydride by the dihydrogen bond.

  6. Tetramethylammonium hydrogen terephthalate

    Directory of Open Access Journals (Sweden)

    Leila Dolatyari


    Full Text Available The asymmetric unit of the title salt, C4H12N+·C8H5O4−, contains one half of a tetramethylammonium cation and one half of a hydrogen terephthalate monoanion. The N atom of the ammonium cation lies on a twofold rotation axis and the centre of mass of the terephthalate anion is on a centre of inversion. In the crystal, the centrosymmetric terephthalate ions are linked by a very short symmetric O—H...O hydrogen bond [O...O = 2.4610 (19 Å] into a one-dimensional polymeric chain along [1-12]. The tetramethylammonium cations and terephthalate anions are then connected through a pair of bifurcated acceptor C—H...O hydrogen bonds, generating a three-dimensional supramolecular network. The carboxylate groups at both ends of the terephthalate anion are charge-shared with an equal probability of 0.5.

  7. Synthesis, single-crystal, DNA interaction, spectrophotometric and spectroscopic characterization of the hydrogen-bonded charge transfer complex of 2-aminopyrimidine with π-acceptor chloranilic acid at different temperature in acetonitrile. (United States)

    Zulkarnain; Miyan, Lal; Ahmad, Afaq; Fazle Alam, Md; Younus, Hina


    The charge transfer (CT) interaction of 2-aminopyrimidine (AP) with chloranilic acid (CLA) as π-acceptor was investigated spectrophotometrically in acetonitrile at different temperatures in the range of 25-50°C. The 1:1 stoichiometry of the synthesized CT complex was detected using straight line method. Benesi-Hildebrand equation was used to determine the association constant (KCT), molar extinction coefficient (ε) and other physical parameters. Various thermodynamics parameters such as enthalpy (ΔH), entropy (ΔS) and free energy (ΔG) were determined using UV-Visible spectrophotometry in acetonitrile at different temperatures. (1)H NMR, FTIR, ESI-MS, elemental analyses, and UV-Visible techniques were used to characterize the hydrogen-bonded CT complex. (1)H NMR spectroscopy was also used for the analysis of the CT complex where both hydrogen bond and charge transfer were present in its molecular composition. The interaction of the selected organic compound with Ct-DNA was well investigated using fluorescence spectroscopic method. Stern-Volmer constant (Ksv) was used to estimate the fluorescence quenching efficiency. Circular dichroism (CD) spectroscopy was employed to measure the conformational change of DNA in the presence of CT complex. Furthermore, the drug CT complex detected changes in its viscosity. The charge transfer complex was formed as a result of the transfer of the lone pair of electrons from donor to the acceptor and exhibits well resolved charge transfer bands in the regions where absorption by both donor and acceptor were absent. The thermal composition and stability of the CT complex were analyzed using thermogravimetric and differential thermal analysis (TGA and DTA) studies. The X-ray crystal structure was used for the interpretation of the structure of the [(AP)(+) (CLA)(-)] CT complex. The crystal structure indicated that cation and anion are linked through strong N(+)H----O(-) type of hydrogen bond. Copyright © 2017 Elsevier B.V. All

  8. Asymmetric inclusion process. (United States)

    Reuveni, Shlomi; Eliazar, Iddo; Yechiali, Uri


    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.

  9. SUPPORTING INFORMATION Transfer hydrogenation reactions ...

    Indian Academy of Sciences (India)

    1. Mass spectra of C1, C2, C3 and C4 S2-S5. 2. Mass spectrum of hydride complex of C1 S6. 3. NMR spectra of L2, L3, C2 and C3 S7-S19. 4. 1H and 2H NMR spectra of 1-phenylethanol-1-2H1 and 1-phenylethanol S20-S27. employing C1, C2, C3 and C4. 5. HPLC Chromatogram S28-S42. Figure S1: Mass spectrum of C4.

  10. Predicting tensorial electrophoretic effects in asymmetric colloids (United States)

    Mowitz, Aaron J.; Witten, T. A.


    We formulate a numerical method for predicting the tensorial linear response of a rigid, asymmetrically charged body to an applied electric field. This prediction requires calculating the response of the fluid to the Stokes drag forces on the moving body and on the countercharges near its surface. To determine the fluid's motion, we represent both the body and the countercharges using many point sources of drag known as Stokeslets. Finding the correct flow field amounts to finding the set of drag forces on the Stokeslets that is consistent with the relative velocities experienced by each Stokeslet. The method rigorously satisfies the condition that the object moves with no transfer of momentum to the fluid. We demonstrate that a sphere represented by 1999 well-separated Stokeslets on its surface produces flow and drag force like a solid sphere to 1% accuracy. We show that a uniformly charged sphere with 3998 body and countercharge Stokeslets obeys the Smoluchowski prediction [F. Morrison, J. Colloid Interface Sci. 34, 210 (1970), 10.1016/0021-9797(70)90171-2] for electrophoretic mobility when the countercharges lie close to the sphere. Spheres with dipolar and quadrupolar charge distributions rotate and translate as predicted analytically to 4% accuracy or better. We describe how the method can treat general asymmetric shapes and charge distributions. This method offers promise as a way to characterize and manipulate asymmetrically charged colloid-scale objects from biology (e.g., viruses) and technology (e.g., self-assembled clusters).

  11. Worldwide clean energy system technology using hydrogen (WE-NET). subtask 5. Development of hydrogen transfer and storage technology (research and development of technologies for hydrogen transport and storage by hydrogen absorbing alloys); Suiso riyo kokusai clean energy system gijutsu (WE-NET). subtask 5. Suiso yuso chozo gijutsu no kaihatsu (bunsan yuso chozoyo suiso kyuzo gokin no kaihatsu)

    Energy Technology Data Exchange (ETDEWEB)



    This report describes a guiding principle of new hydrogen absorbing alloy design, case studies on the stationary hydrogen storage systems for multiple dwelling houses using hydrogen absorbing alloys and on the hydrogen fuel tank systems for a motor vehicle, and survey on development status in the world. As a result of the investigation of alloys, it was concluded that realization of hydrogen absorbing alloys with new target properties of the WE-NET Project is not easy through the current technology. It was found that two kinds of Mg-based and V-based high capacity materials must be selected as target alloys among current alloys, and that three techniques, i.e., ultra-fine microstructure, composite, and amorphousness, are effective for improving the hydrogen discharge property which has been a problem of these alloys. It was desired that the latest techniques are established by integrating these materials and techniques. It is necessary to promote the development of brake-through new materials by new concepts and technologies through the cooperation of national institutes, universities, and companies. 124 refs., 56 figs., 11 tabs.

  12. Symmetric Decomposition of Asymmetric Games. (United States)

    Tuyls, Karl; Pérolat, Julien; Lanctot, Marc; Ostrovski, Georg; Savani, Rahul; Leibo, Joel Z; Ord, Toby; Graepel, Thore; Legg, Shane


    We introduce new theoretical insights into two-population asymmetric games allowing for an elegant symmetric decomposition into two single population symmetric games. Specifically, we show how an asymmetric bimatrix game (A,B) can be decomposed into its symmetric counterparts by envisioning and investigating the payoff tables (A and B) that constitute the asymmetric game, as two independent, single population, symmetric games. We reveal several surprising formal relationships between an asymmetric two-population game and its symmetric single population counterparts, which facilitate a convenient analysis of the original asymmetric game due to the dimensionality reduction of the decomposition. The main finding reveals that if (x,y) is a Nash equilibrium of an asymmetric game (A,B), this implies that y is a Nash equilibrium of the symmetric counterpart game determined by payoff table A, and x is a Nash equilibrium of the symmetric counterpart game determined by payoff table B. Also the reverse holds and combinations of Nash equilibria of the counterpart games form Nash equilibria of the asymmetric game. We illustrate how these formal relationships aid in identifying and analysing the Nash structure of asymmetric games, by examining the evolutionary dynamics of the simpler counterpart games in several canonical examples.

  13. Minimal asymmetric dark matter

    Directory of Open Access Journals (Sweden)

    Sofiane M. Boucenna


    Full Text Available In the early Universe, any particle carrying a conserved quantum number and in chemical equilibrium with the thermal bath will unavoidably inherit a particle–antiparticle asymmetry. A new particle of this type, if stable, would represent a candidate for asymmetric dark matter (DM with an asymmetry directly related to the baryon asymmetry. We study this possibility for a minimal DM sector constituted by just one (generic SU(2L multiplet χ carrying hypercharge, assuming that at temperatures above the electroweak phase transition an effective operator enforces chemical equilibrium between χ and the Higgs boson. We argue that limits from DM direct detection searches severely constrain this scenario, leaving as the only possibilities scalar or fermion multiplets with hypercharge y=1, preferentially quintuplets or larger SU(2 representations, and with a mass in the few TeV range.

  14. Asymmetric black dyonic holes

    Directory of Open Access Journals (Sweden)

    I. Cabrera-Munguia


    Full Text Available A 6-parametric asymptotically flat exact solution, describing a two-body system of asymmetric black dyons, is studied. The system consists of two unequal counterrotating Kerr–Newman black holes, endowed with electric and magnetic charges which are equal but opposite in sign, separated by a massless strut. The Smarr formula is generalized in order to take into account their contribution to the mass. The expressions for the horizon half-length parameters σ1 and σ2, as functions of the Komar parameters and of the coordinate distance, are displayed, and the thermodynamic properties of the two-body system are studied. Furthermore, the seven physical parameters satisfy a simple algebraic relation which can be understood as a dynamical scenario, in which the physical properties of one body are affected by the ones of the other body.

  15. Asymmetric Realized Volatility Risk

    Directory of Open Access Journals (Sweden)

    David E. Allen


    Full Text Available In this paper, we document that realized variation measures constructed from high-frequency returns reveal a large degree of volatility risk in stock and index returns, where we characterize volatility risk by the extent to which forecasting errors in realized volatility are substantive. Even though returns standardized by ex post quadratic variation measures are nearly Gaussian, this unpredictability brings considerably more uncertainty to the empirically relevant ex ante distribution of returns. Explicitly modeling this volatility risk is fundamental. We propose a dually asymmetric realized volatility model, which incorporates the fact that realized volatility series are systematically more volatile in high volatility periods. Returns in this framework display time varying volatility, skewness and kurtosis. We provide a detailed account of the empirical advantages of the model using data on the S&P 500 index and eight other indexes and stocks.

  16. High-performance liquid chromatographic method to evaluate the hydrogen atom transfer during reaction between 1,1-diphenyl-2-picryl-hydrazyl radical and antioxidants

    Energy Technology Data Exchange (ETDEWEB)

    Boudier, Ariane; Tournebize, Juliana [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France); Bartosz, Grzegorz [Department of Molecular Biophysics, University of Lodz, Lodz (Poland); El Hani, Safae; Bengueddour, Rachid [Laboratoire de Nutrition et Sante, Biology Department, Faculty of Sciences, Ibn Tofail University, Kenitra (Morocco); Sapin-Minet, Anne [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France); Leroy, Pierre, E-mail: [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France)


    Highlights: Black-Right-Pointing-Pointer Both 1,1-diphenyl-2-picrylhydrazyl radical and its product measurement by HPLC. Black-Right-Pointing-Pointer Lowest limit of detection by monitoring 1,1-diphenyl-2-picryl-hydrazine. Black-Right-Pointing-Pointer Adsorption problem of the radical on HPLC parts have been pointed out. - Abstract: 1,1-Diphenyl-2-picrylhydrazyl (DPPH{center_dot}) is a stable nitrogen centred radical widely used to evaluate direct radical scavenging properties of various synthetic or natural antioxidants (AOs). The bleaching rate of DPPH{center_dot} absorbance at 515 nm is usually monitored for this purpose. In order to avoid the interference of complex coloured natural products used as antioxidant supplements or cosmetics, HPLC systems have been reported as alternative techniques to spectrophotometry. They also rely upon measurement of DPPH{center_dot} quenching rate and none of them permits to identify and measure 1,1-diphenyl-2-picryl-hydrazine (DPPH-H), the reduced product of DPPH{center_dot} resulting from hydrogen atom transfer (HAT), which is the main mechanism of the reaction between DPPH{center_dot} and AOs. We presently report an HPLC method devoted to the simultaneous measurement of DPPH{center_dot} and DPPH-H. Both were fully separated on a C18 column eluted with acetonitrile-10 mM ammonium citrate buffer pH 6.8 (70:30, v/v) and detected at 330 nm. Adsorption process of DPPH{center_dot} onto materials of the HPLC system was pointed out. Consequently, the linearity range observed for DPPH{center_dot} was restricted, thus a much lower limit of detection was obtained for DPPH-H than for DPPH{center_dot} using standards (0.02 and 14 {mu}M, respectively). The method was applied to three commonly used AOs, i.e. Trolox{sup Registered-Sign }, ascorbic acid and GSH, and compared with spectrophotometry. Further application to complex matrices (cell culture media, vegetal extracts) and nanomaterials demonstrated (i) its usefulness because of

  17. Development of a novel enzyme-targeting radiosensitizer (KORTUC) containing hydrogen peroxide for intratumoral injection for patients with low linear energy transfer-radioresistant neoplasms


    TOKUHIRO, SHIHO; Ogawa, Yasuhiro; TSUZUKI, KAZUHIRO; Akima, Ryo; Ue, Hironobu; Kariya, Shinji; NISHIOKA, AKIHITO


    The therapeutic effect of radiotherapy using linear accelerators for relatively large tumors of more than several centimeters in diameter is reduced to one third due to a large number of hypoxic tumor cells and a significant amount of anti-oxidative enzymes including peroxidase/catalase. The most effective method by which to inject hydrogen peroxide into tumor tissue was examined. This proved difficult as 3% w/v hydrogen peroxide solution (Oxydol) is an antiseptic agent for skin lesions. Thus...

  18. DFT and ONIOM(DFT:MM) studies on Co-C bond cleavage and hydrogen transfer in B12-dependent methylmalonyl-CoA mutase. Stepwise or concerted mechanism? (United States)

    Li, Xin; Chung, Lung Wa; Paneth, Piotr; Morokuma, Keiji


    The considerable protein effect on the homolytic Co-C bond cleavage to form the 5'-deoxyadenosyl (Ado) radical and cob(II)alamin and the subsequent hydrogen transfer from the methylmalonyl-CoA substrate to the Ado radical in the methylmalonyl-CoA mutase (MMCM) have been extensively studied by DFT and ONIOM(DFT/MM) methods. Several quantum models have been used to systematically study the protein effect. The calculations have shown that the Co-C bond dissociation energy is very much reduced in the protein, compared to that in the gas phase. The large protein effect can be decomposed into the cage effect, the effect of coenzyme geometrical distortion, and the protein MM effect. The largest contributor is the MM effect, which mainly consists of the interaction of the QM part of the coenzyme with the MM part of the coenzyme and the surrounding residues. In particular, Glu370 plays an important role in the Co-C bond cleavage process. These effects tremendously enhance the stability of the Co-C bond cleavage state in the protein. The initial Co-C bond cleavage and the subsequent hydrogen transfer were found to occur in a stepwise manner in the protein, although the concerted pathway for the Co-C bond cleavage coupled with the hydrogen transfer is more favored in the gas phase. The assumed concerted transition state in the protein has more deformation of the coenzyme and the substrate and has less interaction with the protein than the stepwise route. Key factors and residues in promoting the enzymatic reaction rate have been discussed in detail.

  19. Hydrogen sensor (United States)

    Duan, Yixiang; Jia, Quanxi; Cao, Wenqing


    A hydrogen sensor for detecting/quantitating hydrogen and hydrogen isotopes includes a sampling line and a microplasma generator that excites hydrogen from a gas sample and produces light emission from excited hydrogen. A power supply provides power to the microplasma generator, and a spectrometer generates an emission spectrum from the light emission. A programmable computer is adapted for determining whether or not the gas sample includes hydrogen, and for quantitating the amount of hydrogen and/or hydrogen isotopes are present in the gas sample.

  20. Magnetically Modified Asymmetric Supercapacitors Project (United States)

    National Aeronautics and Space Administration — This Small Business Innovation Research Phase I project is for the development of an asymmetric supercapacitor that will have improved energy density and cycle life....

  1. Multicatalyst system in asymmetric catalysis

    CERN Document Server

    Zhou, Jian


    This book introduces multi-catalyst systems by describing their mechanism and advantages in asymmetric catalysis.  Helps organic chemists perform more efficient catalysis with step-by-step methods  Overviews new concepts and progress for greener and economic catalytic reactions  Covers topics of interest in asymmetric catalysis including bifunctional catalysis, cooperative catalysis, multimetallic catalysis, and novel tandem reactions   Has applications for pharmaceuticals, agrochemicals, materials, and flavour and fragrance

  2. Asymmetric Ion-Pairing Catalysis (United States)

    Brak, Katrien


    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

  3. Quantum chemical investigation of the intra- and intermolecular proton transfer reactions and hydrogen bonding interactions in 4-amino-5-(2-hydroxyphenyl)-2H-1,2,4-triazole-3(4H)-thione. (United States)

    Özdemir, Namık


    The intramolecular thione-thiol tautomerism and intermolecular double proton transfer reaction of the hydrogen-bonded thione and thiol dimers in the title triazole compound were studied at the B3LYP level of theory using 6-311++G(d,p) basis function. The influence of the solvent on the single and double proton transfer reactions was examined in three solvents (chloroform, methanol and water) using the polarizable continuum model (PCM) approximation. The computational results show that the thione tautomer is the most stable isomer with a very high tautomeric energy barrier both in the gas phase and in solution phase, indicating a quite disfavored process. The solvent effect is found to be sizable with increasing polarity. In the double proton transfer reaction, the thione dimer is found to be more stable than thiol dimer both in the gas phase and in solution phase. The energetic and thermodynamic parameters of the double proton transfer process show that the double proton exchange from thione dimer to thiol dimer is thermodynamically unfavored. However, the exchange from thiol dimer to thione dimer for the gas phase and water phase seems to be feasible with a low barrier height and with a negative value in enthalpy and free energy changes. In addition, the hydrogen bonding interactions were analyzed in the gas phase regarding their geometries and energies. It is found that all complex formations are enthalpically favored, and the stability of the H-bonds comes in the order of S1-H2···N2>N2-H2···S1>N3-H3B···O1. Finally, non-linear optical properties were carried out at the same calculation level in the gas phase.

  4. Asymmetric Gepner models (revisited)

    Energy Technology Data Exchange (ETDEWEB)

    Gato-Rivera, B. [NIKHEF Theory Group, Kruislaan 409, 1098 SJ Amsterdam (Netherlands)] [Instituto de Fisica Fundamental, CSIC, Serrano 123, Madrid 28006 (Spain); Schellekens, A.N., E-mail: t58@nikhef.n [NIKHEF Theory Group, Kruislaan 409, 1098 SJ Amsterdam (Netherlands)] [Instituto de Fisica Fundamental, CSIC, Serrano 123, Madrid 28006 (Spain)] [IMAPP, Radboud Universiteit, Nijmegen (Netherlands)


    We reconsider a class of heterotic string theories studied in 1989, based on tensor products of N=2 minimal models with asymmetric simple current invariants. We extend this analysis from (2,2) and (1,2) spectra to (0,2) spectra with SO(10) broken to the Standard Model. In the latter case the spectrum must contain fractionally charged particles. We find that in nearly all cases at least some of them are massless. However, we identify a large subclass where the fractional charges are at worst half-integer, and often vector-like. The number of families is very often reduced in comparison to the 1989 results, but there are no new tensor combinations yielding three families. All tensor combinations turn out to fall into two classes: those where the number of families is always divisible by three, and those where it is never divisible by three. We find an empirical rule to determine the class, which appears to extend beyond minimal N=2 tensor products. We observe that distributions of physical quantities such as the number of families, singlets and mirrors have an interesting tendency towards smaller values as the gauge groups approaches the Standard Model. We compare our results with an analogous class of free fermionic models. This displays similar features, but with less resolution. Finally we present a complete scan of the three family models based on the triply-exceptional combination (1,16{sup *},16{sup *},16{sup *}) identified originally by Gepner. We find 1220 distinct three family spectra in this case, forming 610 mirror pairs. About half of them have the gauge group SU(3)xSU(2){sub L}xSU(2){sub R}xU(1){sup 5}, the theoretical minimum, and many others are trinification models.

  5. Solvent and H/D isotope effects on the proton transfer pathways in heteroconjugated hydrogen-bonded phenol-carboxylic acid anions observed by combined UV-vis and NMR spectroscopy. (United States)

    Koeppe, Benjamin; Guo, Jing; Tolstoy, Peter M; Denisov, Gleb S; Limbach, Hans-Heinrich


    Heteroconjugated hydrogen-bonded anions A···H···X(-) of phenols (AH) and carboxylic/inorganic acids (HX) dissolved in CD2Cl2 and CDF3/CDF2Cl have been studied by combined low-temperature UV-vis and (1)H/(13)C NMR spectroscopy (UVNMR). The systems constitute small molecular models of hydrogen-bonded cofactors in proteins such as the photoactive yellow protein (PYP). Thus, the phenols studied include the PYP cofactor 4-hydroxycinnamic acid methyl thioester, and the more acidic 4-nitrophenol and 2-chloro-4-nitrophenol which mimic electronically excited cofactor states. It is shown that the (13)C chemical shifts of the phenolic residues of A···H···X(-), referenced to the corresponding values of A···H···A(-), constitute excellent probes for the average proton positions. These shifts correlate with those of the H-bonded protons, as well as with the H/D isotope effects on the (13)C chemical shifts. A combined analysis of UV-vis and NMR data was employed to elucidate the proton transfer pathways in a qualitative way. Dual absorption bands of the phenolic moiety indicate a double-well situation for the shortest OHO hydrogen bonds studied. Surprisingly, when the solvent polarity is low the carboxylates are protonated whereas the proton shifts toward the phenolic oxygens when the polarity is increased. This finding indicates that because of stronger ion-dipole interactions small anions are stabilized at high solvent polarity and large anions exhibiting delocalized charges at low solvent polarities. It also explains the large acidity difference of phenols and carboxylic acids in water, and the observation that this difference is strongly reduced in the interior of proteins when both partners form mutual hydrogen bonds.

  6. Asymmetric catalysis at the mesoscale: gold nanoclusters embedded in chiral self-assembled monolayer as heterogeneous catalyst for asymmetric reactions. (United States)

    Gross, Elad; Liu, Jack H; Alayoglu, Selim; Marcus, Matthew A; Fakra, Sirine C; Toste, F Dean; Somorjai, Gabor A


    Research to develop highly versatile, chiral, heterogeneous catalysts for asymmetric organic transformations, without quenching the catalytic reactivity, has met with limited success. While chiral supramolecular structures, connected by weak bonds, are highly active for homogeneous asymmetric catalysis, their application in heterogeneous catalysis is rare. In this work, asymmetric catalyst was prepared by encapsulating metallic nanoclusters in chiral self-assembled monolayer (SAM), immobilized on mesoporous SiO2 support. Using olefin cyclopropanation as an example, it was demonstrated that by controlling the SAM properties, asymmetric reactions can be catalyzed by Au clusters embedded in chiral SAM. Up to 50% enantioselectivity with high diastereoselectivity were obtained while employing Au nanoclusters coated with SAM peptides as heterogeneous catalyst for the formation of cyclopropane-containing products. Spectroscopic measurements correlated the improved enantioselectivity with the formation of a hydrogen-bonding network in the chiral SAM. These results demonstrate the synergetic effect of the catalytically active metallic sites and the surrounding chiral SAM for the formation of a mesoscale enantioselective catalyst.

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

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


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

  8. Asymmetric Flexible Supercapacitor Stack (United States)


    Electrical double layer supercapacitor is very significant in the field of electrical energy storage which can be the solution for the current revolution in the electronic devices like mobile phones, camera flashes which needs flexible and miniaturized energy storage device with all non-aqueous components. The multiwalled carbon nanotubes (MWNTs) have been synthesized by catalytic chemical vapor deposition technique over hydrogen decrepitated Mischmetal (Mm) based AB3alloy hydride. The polymer dispersed MWNTs have been obtained by insitu polymerization and the metal oxide/MWNTs were synthesized by sol-gel method. Morphological characterizations of polymer dispersed MWNTs have been carried out using scanning electron microscopy (SEM), transmission electron microscopy (TEM and HRTEM). An assymetric double supercapacitor stack has been fabricated using polymer/MWNTs and metal oxide/MWNTs coated over flexible carbon fabric as electrodes and nafion®membrane as a solid electrolyte. Electrochemical performance of the supercapacitor stack has been investigated using cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy.

  9. Asymmetric Flexible Supercapacitor Stack

    Directory of Open Access Journals (Sweden)

    Leela Mohana Reddy A


    Full Text Available AbstractElectrical double layer supercapacitor is very significant in the field of electrical energy storage which can be the solution for the current revolution in the electronic devices like mobile phones, camera flashes which needs flexible and miniaturized energy storage device with all non-aqueous components. The multiwalled carbon nanotubes (MWNTs have been synthesized by catalytic chemical vapor deposition technique over hydrogen decrepitated Mischmetal (Mm based AB3alloy hydride. The polymer dispersed MWNTs have been obtained by insitu polymerization and the metal oxide/MWNTs were synthesized by sol-gel method. Morphological characterizations of polymer dispersed MWNTs have been carried out using scanning electron microscopy (SEM, transmission electron microscopy (TEM and HRTEM. An assymetric double supercapacitor stack has been fabricated using polymer/MWNTs and metal oxide/MWNTs coated over flexible carbon fabric as electrodes and nafion®membrane as a solid electrolyte. Electrochemical performance of the supercapacitor stack has been investigated using cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy.

  10. Influence of adduct stereochemistry and hydrogen-bonding solvents on photoinduced charge transfer in a covalent benzo[a]pyrene diol epoxide-nucleoside adduct on picosecond time scales

    Energy Technology Data Exchange (ETDEWEB)

    O' Connor, D. (Univ. of Texas, Austin, TX (United States)); Shafirovich, V.Y.; Geacintov, N.E. (New York Univ., NY (United States))


    Photoinduced electron transfer occurs with different rate constants upon picosecond laser pulse excitation of the stereoisomeric (+)-trans- and (-)-cis-benzo[a]pyrene diol epoxide-N[sup 2]-deoxyguanosine covalently linked adducts (BPDE-N[sup 2]-dG, bond with 10S absolute configuration) in polar solvents (N,N[prime]-dimethylformamide (DMF), and the hydrogen-bonding liquids H[sub 2]O, D[sub 2]O, formamide (FA), and N-methylformamide (NMF)). In the case of (+)-trans-BPDE-dG in DMF, photoinduced electron transfer occurs in the normal Marcus region, from dG to the pyrenyl residue singlet with a rate constant k[sub s] = (9.1 [+-] 0.9) x 10[sup 9] s[sup [minus]1], which is followed by a slower recombination (k[sub r] = (1.8 + 0.5) x 10[sup 9] s[sup [minus]1]) in the inverted Marcus region. In the cis-stereoisomeric adduct, both rate constants are enhanced by a factor of approximately 5. The presence of the hydrogen-bonding network in NMF and FA exerts opposite effects on these rate constants, decreasing k[sub s] and increasing k[sub r] by factors of 2-5. In aqueous solutions these effects are even more pronounced, and radical ions are not observed since k[sub r] [much gt] k[sub s]. A kinetic isotope effect on the delay of the pyrenyl singlets in H[sub 2]O and D[sub 2]O (k[sub s](H[sub 2]O)/k[sub s](D[sub 2]O) = 1.3-1.5) suggests that a proton-coupled electron transfer mechanism may be operative in aqueous solutions. 51 refs., 10 figs., 2 tabs.

  11. Asymmetric distances for binary embeddings. (United States)

    Gordo, Albert; Perronnin, Florent; Gong, Yunchao; Lazebnik, Svetlana


    In large-scale query-by-example retrieval, embedding image signatures in a binary space offers two benefits: data compression and search efficiency. While most embedding algorithms binarize both query and database signatures, it has been noted that this is not strictly a requirement. Indeed, asymmetric schemes that binarize the database signatures but not the query still enjoy the same two benefits but may provide superior accuracy. In this work, we propose two general asymmetric distances that are applicable to a wide variety of embedding techniques including locality sensitive hashing (LSH), locality sensitive binary codes (LSBC), spectral hashing (SH), PCA embedding (PCAE), PCAE with random rotations (PCAE-RR), and PCAE with iterative quantization (PCAE-ITQ). We experiment on four public benchmarks containing up to 1M images and show that the proposed asymmetric distances consistently lead to large improvements over the symmetric Hamming distance for all binary embedding techniques.

  12. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong


    The employment of metal salts is quite limited in asymmetric catalysis, although it would provide an additional arsenal of safe and inexpensive reagents to create molecular functions with high optical purity. Cation chelation by polyethers increases the salts' solubility in conventional organic...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...... and KCN, are selectively bound to the catalyst, providing exceptionally high enantioselectivities for kinetic resolutions, elimination reactions (fluoride base), and Strecker synthesis (cyanide nucleophile). Asymmetric cation-binding catalysis was recently expanded to silicon-based reagents, enabling...

  13. Organocatalytic asymmetric arylation of indoles enabled by azo groups (United States)

    Qi, Liang-Wen; Mao, Jian-Hui; Zhang, Jian; Tan, Bin


    Arylation is a fundamental reaction that can be mostly fulfilled by electrophilic aromatic substitution and transition-metal-catalysed aryl functionalization. Although the azo group has been used as a directing group for many transformations via transition-metal-catalysed aryl carbon-hydrogen (C-H) bond activation, there remain significant unmet challenges in organocatalytic arylation. Here, we show that the azo group can effectively act as both a directing and activating group for organocatalytic asymmetric arylation of indoles via formal nucleophilic aromatic substitution of azobenzene derivatives. Thus, a wide range of axially chiral arylindoles have been achieved in good yields with excellent enantioselectivities by utilizing chiral phosphoric acid as catalyst. Furthermore, highly enantioenriched pyrroloindoles bearing two contiguous quaternary chiral centres have also been obtained via a cascade enantioselective formal nucleophilic aromatic substitution-cyclization process. This strategy should be useful in other related research fields and will open new avenues for organocatalytic asymmetric aryl functionalization.

  14. 41 CFR 50-204.68 - Hydrogen. (United States)


    ... 41 Public Contracts and Property Management 1 2010-07-01 2010-07-01 true Hydrogen. 50-204.68..., Vapors, Fumes, Dusts, and Mists § 50-204.68 Hydrogen. The in-plant transfer, handling, storage, and utilization of hydrogen shall be in accordance with Compressed Gas Association Pamphlets G-5.1-1961 and G-5.2...

  15. Does asymmetric correlation affect portfolio optimization? (United States)

    Fryd, Lukas


    The classical portfolio optimization problem does not assume asymmetric behavior of relationship among asset returns. The existence of asymmetric response in correlation on the bad news could be important information in portfolio optimization. The paper applies Dynamic conditional correlation model (DCC) and his asymmetric version (ADCC) to propose asymmetric behavior of conditional correlation. We analyse asymmetric correlation among S&P index, bonds index and spot gold price before mortgage crisis in 2008. We evaluate forecast ability of the models during and after mortgage crisis and demonstrate the impact of asymmetric correlation on the reduction of portfolio variance.

  16. Palladium nanoparticles supported on fibrous-structured silica nanospheres (KCC-1): An efficient and selective catalyst for the transfer hydrogenation of alkenes

    KAUST Repository

    Qureshi, Ziyauddin


    An efficient palladium catalyst supported on fibrous silica nanospheres (KCC-1) has been developed for the hydrogenation of alkenes and α,β-unsaturated carbonyl compounds, providing excellent yields of the corresponding products with remarkable chemoselectivity. Comparison (high-resolution TEM, chemisorption) with analogous mesoporous (MCM-41, SBA-15) silica-supported Pd nanocatalysts prepared under identical conditions, demonstrates the advantage of employing the fibrous KCC-1 morphology versus traditional supports because it ensures superior accessibility of the catalytically active cores along with excellent Pd dispersion at high metal loading. This morphology ultimately leads to higher catalytic activity for the KCC-1-supported nanoparticles. The protocol developed for hydrogenation is advantageous and environmentally benign owing to the use of HCOOH as a source of hydrogen, water as a solvent, and because of efficient catalyst recyclability and durability. The recycled catalyst has been analyzed by XPS spectroscopy and TEM showing only minor changes in the oxidation state of Pd and in the morphology after the reaction, thus confirming the robustness of the catalyst.

  17. Hydroxamic acids in asymmetric synthesis. (United States)

    Li, Zhi; Yamamoto, Hisashi


    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. Because of 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 the 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.

  18. Hydroxide ion versus chloride and methoxide as an exogenous ligand reveals the influence of hydrogen bonding with second-sphere coordination water molecules in the electron transfer kinetics of Mn complexes. (United States)

    El Ghachtouli, Sanae; Guillot, Régis; Aukauloo, Ally; Dorlet, Pierre; Anxolabéhère-Mallart, Elodie; Costentin, Cyrille


    We recently reported on the synthesis of a new pentadentate N(4)O ligand, tBuL(-), together with the X-ray diffraction structure of the corresponding mononuclear manganese(III)-hydroxo complex namely [(tBuL)Mn(III)OH](ClO(4)), (1 (ClO(4))). [El Ghachtouli et al. Energy Environ. Sci. 2011, 4, 2041.] In the present work, we evidence through electrochemical analysis that complex 1(+), in the presence of water, shows a peculiar behavior toward electron-transfer kinetics. The synthesis, single-crystal X-ray diffraction, and EPR spectroscopic characterization of two other mononuclear manganese(III)-chlorido and methoxo complexes-namely, [(tBuL)Mn(III)Cl](PF(6)), (2(PF(6))) and [(tBuL)Mn(III)OMe](ClO(4)), (3(ClO(4)))-are also reported. 2(PF(6)) and 3(ClO(4)) compounds will serve as reference complexes for the electron-transfer kinetics investigation. The peculiar behavior of 1(ClO(4)) is attributed to the specificity of hydroxide anion as ligand presumably allowing intermolecular hydrogen-bonding interactions and thus affecting electron-transfer properties. © 2012 American Chemical Society

  19. Porphyrin Cobalt(III “Nitrene Radical” Reactivity; Hydrogen Atom Transfer from Ortho-YH Substituents to the Nitrene Moiety of Cobalt-Bound Aryl Nitrene Intermediates (Y = O, NH

    Directory of Open Access Journals (Sweden)

    Monalisa Goswami


    Full Text Available In the field of cobalt(II porphyrin-catalyzed metallo-radical reactions, organic azides have emerged as successful nitrene transfer reagents. In the pursuit of employing ortho-YH substituted (Y = O, NH aryl azides in Co(II porphyrin-catalyzed nitrene transfer reactions, unexpected hydrogen atom transfer (HAT from the OH or NH2 group in the ortho-position to the nitrene moiety of the key radical-intermediate was observed. This leads to formation of reactive ortho-iminoquinonoid (Y = O and phenylene diimine (Y = NH species. These intermediates convert to subsequent products in non-catalyzed reactions, as is typical for these free organic compounds. As such, the observed reactions prevent the anticipated cobalt-mediated catalytic radical-type coupling of the nitrene radical intermediates to alkynes or alkenes. Nonetheless, the observed reactions provide valuable insights into the reactivity of transition metal nitrene-radical intermediates, and give access to ortho-iminoquinonoid and phenylene diimine intermediates from ortho-YH substituted aryl azides in a catalytic manner. The latter can be employed as intermediates in one-pot catalytic transformations. From the ortho-hydroxy aryl azide substrates both phenoxizinones and benzoxazines could be synthesized in high yields. From the ortho-amino aryl azide substrates azabenzene compounds were obtained as the main products. Computational studies support these observations, and reveal that HAT from the neighboring OH and NH2 moiety to the nitrene radical moiety has a low energy barrier.

  20. Hydrogen Generator (United States)


    A unit for producing hydrogen on site is used by a New Jersey Electric Company. The hydrogen is used as a coolant for the station's large generator; on-site production eliminates the need for weekly hydrogen deliveries. High purity hydrogen is generated by water electrolysis. The electrolyte is solid plastic and the control system is electronic. The technology was originally developed for the Gemini spacecraft.

  1. Asymmetric Synthesis via Chiral Aziridines

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Harden, Adrian; Wyatt, Paul


    A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines)]. In the b...

  2. Structure of asymmetrical peptide dendrimers

    NARCIS (Netherlands)

    Okrugin, B.M.; Neelov, I.M.; Leermakers, F.A.M.; Borisov, Oleg V.


    Structural properties of asymmetric peptide dendrimers up to the 11th generation are studied on the basis of the self-consistent field Scheutjens-Fleer numerical approach. It is demonstrated that large scale properties such as, e.g., the gyration radius, are relatively weakly affected by the

  3. Unusual Intramolecular Hydrogen Transfer in 3,5-Di(triphenylethylenyl) BODIPY Synthesis and 1,2-Migratory Shift in Subsequent Scholl Type Reaction

    KAUST Repository

    Chua, Ming Hui


    The straightforward synthesis of 3,5-di(triphenylethylenyl) BODIPYs 1–3 from the condensation of 2-(triphenylethylenyl) pyrrole with aryl aldehydes are surprisingly found to produce side products that are hydrogenated at one of the two triphenylethylene substituents. It was also observed that the subsequent Scholl type reaction of 1 resulted in a “1,2-migratory shift” of one triphenylethylene substituent in addition to a ring closing reaction. Preliminary investigations, including DFT calculations and isolation of intermediates, were conducted to study these unusual observations on BODIPY chemistry.

  4. Secondary coordination sphere accelerates hole transfer for enhanced hydrogen photogeneration from [FeFe]-hydrogenase mimic and CdSe QDs in water


    Min Wen; Xu-Bing Li; Jing-Xin Jian; Xu-Zhe Wang; Hao-Lin Wu; Bin Chen; Chen-Ho Tung; Li-Zhu Wu


    Achieving highly efficient hydrogen (H2) evolution via artificial photosynthesis is a great ambition pursued by scientists in recent decades because H2 has high specific enthalpy of combustion and benign combustion product. [FeFe]-Hydrogenase ([FeFe]-H2ase) mimics have been demonstrated to be promising catalysts for H2 photoproduction. However, the efficient photocatalytic H2 generation system, consisting of PAA-g-Fe2S2, CdSe QDs and H2A, suffered from low stability, probably due to the hole ...

  5. Probing the Conformational and Functional Consequences of Disulfide Bond Engineering in Growth Hormone by Hydrogen-Deuterium Exchange Mass Spectrometry Coupled to Electron Transfer Dissociation

    DEFF Research Database (Denmark)

    Seger, Signe T; Breinholt, Jens; Faber, Johan H


    Human growth hormone (hGH), and its receptor interaction, is essential for cell growth. To stabilize a flexible loop between helices 3 and 4, while retaining affinity for the hGH receptor, we have engineered a new hGH variant (Q84C/Y143C). Here, we employ hydrogen-deuterium exchange mass...... spectrometry (HDX-MS) to map the impact of the new disulfide bond on the conformational dynamics of this new hGH variant. Compared to wild type hGH, the variant exhibits reduced loop dynamics, indicating a stabilizing effect of the introduced disulfide bond. Furthermore, the disulfide bond exhibits longer...

  6. Three-dimensional Radiative Transfer Simulations of the Scattering Polarization of the Hydrogen Lyalpha Line in a Magnetohydrodynamic Model of the Chromosphere-Corona Transition Region

    Czech Academy of Sciences Publication Activity Database

    Štěpán, Jiří; Trujillo Bueno, J.; Leenaarts, J.; Carlsson, M.


    Roč. 803, č. 2 (2015), 65/1-65/15 ISSN 0004-637X R&D Projects: GA ČR GPP209/12/P741 Grant - others:EU(XE) COST action MP1104 Institutional support: RVO:67985815 Keywords : polarization * radiative transfer * scattering Subject RIV: BN - Astronomy, Celestial Mechanics, Astrophysics Impact factor: 5.909, year: 2015

  7. Biomimetic hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Krassen, Henning


    Hydrogenases catalyze the reduction of protons to molecular hydrogen with outstanding efficiency. An electrode surface which is covered with active hydrogenase molecules becomes a promising alternative to platinum for electrochemical hydrogen production. To immobilize the hydrogenase on the electrode, the gold surface was modified by heterobifunctional molecules. A thiol headgroup on one side allowed the binding to the gold surface and the formation of a self-assembled monolayer. The other side of the molecules provided a surface with a high affinity for the hydrogenase CrHydA1 from Chlamydomonas reinhardtii. With methylviologen as a soluble energy carrier, electrons were transferred from carboxy-terminated electrodes to CrHydA1 and conducted to the active site (H-cluster), where they reduce protons to molecular hydrogen. A combined approach of surface-enhanced infrared absorption spectroscopy, gas chromatography, and surface plasmon resonance allowed quantifying the hydrogen production on a molecular level. Hydrogen was produced with a rate of 85 mol H{sub 2} min{sup -1} mol{sup -1}. On a 1'- benzyl-4,4'-bipyridinum (BBP)-terminated surface, the electrons were mediated by the monolayer and no soluble electron carrier was necessary to achieve a comparable hydrogen production rate (approximately 50% of the former system). The hydrogen evolution potential was determined to be -335 mV for the BBP-bound hydrogenase and -290 mV for the hydrogenase which was immobilized on a carboxy-terminated mercaptopropionic acid SAM. Therefore, both systems significantly reduce the hydrogen production overpotential and allow electrochemical hydrogen production at an energy level which is close to the commercially applied platinum electrodes (hydrogen evolution potential of -270 mV). In order to couple hydrogen production and photosynthesis, photosystem I (PS1) from Synechocystis PCC 6803 and membrane-bound hydrogenase (MBH) from Ralstonia eutropha were bound to each other

  8. UV-Induced Hydrogen-Atom-Transfer Processes in 3-Thio-1,2,4-triazole Isolated in Ar and H2 Low-Temperature Matrixes. (United States)

    Rostkowska, Hanna; Lapinski, Leszek; Nowak, Maciej J


    The UV-induced thione → thiol phototautomeric reaction has been studied for monomeric 3-thio-1,2,4-triazole (3-ST) isolated in low-temperature Ar and n-H2 (normal hydrogen) matrixes. Prior to any UV irradiation, monomers of 3-ST isolated in solid Ar or solid n-H2 adopted mainly the most stable thione tautomeric form, as revealed by the IR spectra. Upon UV (λ > 275 nm) irradiation of 3-ST isolated in Ar matrixes, the IR bands due to this thione form decreased, while a set of initially weak bands increased in intensity. Growing bands indicated generation of a photoproduct, which was identified as the thiol tautomer with labile hydrogen atoms attached to sulfur and N(2) atoms. The UV-induced spectral changes allowed also identification of another minor thiol tautomer of 3-ST, which was present in the matrix prior to any irradiation and did not change its population upon exposure to UV light. The identification of the observed isomeric forms was supported by comparison of their separated experimental IR spectra with the spectra theoretically predicted for the various structures of 3-ST. The thione → thiol phototautomerization that was the main UV-induced process observed for 3-ST in Ar matrixes did not occur for monomers of the compound trapped in solid n-H2.

  9. Hydrogen bonded supramolecular materials

    CERN Document Server

    Li, Zhan-Ting


    This book is an up-to-date text covering topics in utilizing hydrogen bonding for constructing functional architectures and supramolecular materials. The first chapter addresses the control of photo-induced electron and energy transfer. The second chapter summarizes the formation of nano-porous materials. The following two chapters introduce self-assembled gels, many of which exhibit unique functions. Other chapters cover the advances in supramolecular liquid crystals and the versatility of hydrogen bonding in tuning/improving the properties and performance of materials. This book is designed

  10. Highly enantioselective phase-transfer-catalyzed alkylation of protected alpha-amino acid amides toward practical asymmetric synthesis of vicinal diamines, alpha-amino ketones, and alpha-amino alcohols. (United States)

    Ooi, Takashi; Takeuchi, Mifune; Kato, Daisuke; Uematsu, Yukitaka; Tayama, Eiji; Sakai, Daiki; Maruoka, Keiji


    Highly enantioselective alkylation of protected glycine diphenylmethyl (Dpm) amide 1 and Weinreb amide 10 has been realized under phase-transfer conditions by the successful utilization of designer chiral quaternary ammonium salts of type 4 as catalyst. Particularly, remarkable reactivity of the chiral ammonium enolate derived from 1b and 4c allowed the reaction with less reactive simple secondary alkyl halides with high efficiency and enantioselectivity. An additional unique feature of this chiral ammonium enolate is its ability to recognize the chirality of beta-branched primary alkyl halides, which provides impressive levels of kinetic resolution and double stereodifferentiation during the alkylation, allowing for two alpha- and gamma-stereocenters to be controlled. Combined with the subsequent reduction using LiAlH4 in cyclopentyl methyl ether (CPME), this system offers a facile access to structurally diverse optically active vicinal diamines. Furthermore, the optically active alpha-amino acid Weinreb amide 11 can be efficiently converted to the corresponding amino ketone by a simple treatment with Grignard reagents. In addition, reduction and alkylation of the optically active alpha-amino ketone into both syn and anti alpha-amino alcohols with almost complete relative and absolute stereochemical control have been achieved. With (S,S)- and (R,R)-4 in hand, the present approach renders both enantiomers of alpha-amino amides including Weinreb amides readily available with enormous structural variation and also establishes a general and practical route to vicinal diamines, alpha-amino ketones, and alpha-amino alcohols with the desired stereochemistry.

  11. Effects of counterion and solvent on proton location and proton transfer dynamics of N-H···N hydrogen bond of monoprotonated 1,8-bis(dimethylamino)naphthalene. (United States)

    Masuda, Yuichi; Mori, Yukie; Sakurai, Kazumi


    The proton location and proton transfer (PT) dynamics of a hydrogen bond are under the influence of the static and dynamical properties of the solvent and counterions. In the present study, the N-H distances were determined for salts of 1,8-bis(dimethylamino)naphthalene, DMANH(+)X(-) (X(-) = BPh4(-), ClO4(-), and Cl(-)), in acetonitrile (AN) solution, and DMANH(+)Br(-) in water by observing the (15)N spin-lattice relaxation caused by the (15)N-(1)H magnetic dipolar coupling under assumption that the PT time was shorter than the NH reorientation time (∼10(-11) s). The obtained N-H distances decreased in the following order: DMANH(+)BPh4(-) > DMANH(+)ClO4(-) > DMANH(+)Br(-)/H2O > DMANH(+)Cl(-), indicating that interactions with the environment affect the PT potentials. To understand the results at the molecular level, Car-Parrinello molecular dynamics simulations were performed for DMANH(+), DMANH(+) in water, and DMANH(+)-Cl(-) ion-pair in AN. The results of simulation suggest that (1) the N-H distance decreases in the presence of a solvent and counterion; (2) the PT time is probably ∼10(-12) s, which confirms the above assumption used for the NMR relaxation data analyses; and (3) fluctuation of the interactions with the solvent or counterion has a significant role in PT. Quantum nuclear effects on the hydrogen bond were also examined.

  12. A DFT investigation on interactions between asymmetric derivatives of cisplatin and nucleobase guanine (United States)

    Tai, Truong Ba; Nhat, Pham Vu


    The interactions of hydrolysis products of cisplatin and its asymmetric derivatives cis- and trans-[PtCl2(iPram)(Mepz)] with guanine were studied using DFT methods. These interactions are dominated by electrostatic effects, namely hydrogen bond contributions and there exists a charge flow from H-atoms of ligands to the O-atoms of guanine. The replacement of NH3 moieties by larger functional groups accompanies with a moderate reaction between PtII and guanine molecule, diminishing the cytotoxicity of the drug. The asymmetric and symmetric NH2 stretching modes of complexes having strong hydrogen bond interactions are red shifted importantly as compared to complexes without presence of hydrogen bond interactions.

  13. Hydrogen peroxide oxidation of mustard-model sulfides catalyzed by iron and manganese tetraarylporphyrines. Oxygen transfer to sulfides versus H(2)O(2) dismutation and catalyst breakdown. (United States)

    Marques, A; Marin, M; Ruasse, M F


    Fe(III)- and Mn(III)-meso-tetraarylporphyrin catalysis of H(2)O(2) oxidation of dibenzyl and phenyl-2-chloroethyl sulfides, 1, is investigated in ethanol with the aim of designing catalytic systems for mustard decontamination. The sulfide conversion, the sulfoxide and sulfone yields, the oxygen transfer from H(2)O(2) to the sulfide, and the catalyst stability depend markedly on the metal, on the substituents of its ligand, and on the presence or the absence of a cocatalyst, imidazole or ammonium acetate. With Fe, sulfones, the only oxidation products, are readily obtained whatever the ligand (TPP, F(20)TPP, or TDCPP) and the cocatalyst; the oxygen transfer is fairly good, up to 95% when the catalyst concentration is small ([1]/[Cat] = 420); the catalyst breakdown is insignificant only in the absence of any cocatalyst. With Mn, the sulfide conversion is achieved completely when the ligand is TDCPP or TSO(3)PP, but not F(20)TPP or TPP; a mixture of sulfoxide, 2, and sulfone, 3, is always obtained with [2]/[3] = 3.5-0.85 depending on the ligand and the cocatalyst (electron withdrawing substituents favor 3 and NH(4)OAc, 2). The catalyst stability is very good, but the oxygen transfer is poor whatever the ligand and the cocatalyst. These results are discussed in terms of a scheme in which sulfide oxygenation, H(2)O(2) dismutation, and oxidative ligand breaking compete. It is shown that the efficiency of the oxygen transfer is related not only to the rate constant of the dismutation route but also to the concentration of the active metal-oxo intermediate, most likely a perferryl or permanganyl species, i.e., to the rate of its formation.

  14. Cyclodextrins in Asymmetric and Stereospecific Synthesis

    Directory of Open Access Journals (Sweden)

    Fliur Macaev


    Full Text Available Since their discovery, cyclodextrins have widely been used as green and easily available alternatives to promoters or catalysts of different chemical reactions in water. This review covers the research and application of cyclodextrins and their derivatives in asymmetric and stereospecific syntheses, with their division into three main groups: (1 cyclodextrins promoting asymmetric and stereospecific catalysis in water; (2 cyclodextrins’ complexes with transition metals as asymmetric and stereospecific catalysts; and (3 cyclodextrins’ non-metallic derivatives as asymmetric and stereospecific catalysts. The scope of this review is to systematize existing information on the contribution of cyclodextrins to asymmetric and stereospecific synthesis and, thus, to facilitate further development in this direction.

  15. A Note on Asymmetric Thick Branes

    Directory of Open Access Journals (Sweden)

    D. Bazeia


    Full Text Available We study asymmetric thick braneworld scenarios, generated after adding a constant to the superpotential associated with the scalar field. We study in particular models with odd and even polynomial superpotentials, and we show that asymmetric brane can be generated irrespective of the potential being symmetric or asymmetric. We study in addition the nonpolynomial sine-Gordon like model, also constructed with the inclusion of a constant in the standard superpotential, and we investigate gravitational stability of the asymmetric brane. The results suggest robustness of the new braneworld scenarios and add further possibilities of the construction of asymmetric branes.

  16. Z-H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H2 Evolution. (United States)

    Belkova, Natalia V; Filippov, Oleg A; Shubina, Elena S


    The ability of neutral transition-metal hydrides to serve as a source of hydride ion H- or proton H+ is well appreciated. The hydride ligands possessing a partly negative charge are proton accepting sites, forming a dihydrogen bond, M-Hδ- ⋅⋅⋅δ+ HX (M=transition metal or metalloid). On the other hand, some metal hydrides are able to serve as a proton source and give hydrogen bond of M-Hδ+ ⋅⋅⋅X type (X=organic base). In this paper we analyse recent works on transition-metal and boron hydrides showing i) how formation of an intermolecular complex between the reactants changes the Z-H (M-H and X-H) bond polarity and ii) what is the implication of such activation in the mechanisms of hydrides reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Geodesics in Asymmetric Metric Spaces

    Directory of Open Access Journals (Sweden)

    Mennucci Andrea C. G.


    Full Text Available In a recent paper [17] we studied asymmetric metric spaces; in this context we studied the length of paths, introduced the class of run-continuous paths; and noted that there are different definitions of “length spaces” (also known as “path-metric spaces” or “intrinsic spaces”. In this paper we continue the analysis of asymmetric metric spaces.We propose possible definitions of completeness and (local compactness.We define the geodesics using as admissible paths the class of run-continuous paths.We define midpoints, convexity, and quasi-midpoints, but without assuming the space be intrinsic.We distinguish all along those results that need a stronger separation hypothesis. Eventually we discuss how the newly developed theory impacts the most important results, such as the existence of geodesics, and the renowned Hopf-Rinow (or Cohn-Vossen theorem.

  18. Electron Jet of Asymmetric Reconnection (United States)

    Khotyaintsev, Yu. V.; Graham, D. B.; Norgren, C.; Eriksson, E.; Li, W.; Johlander, A.; Vaivads, A.; Andre, M.; Pritchett, P. L.; Retino, A.; hide


    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(sub parallel lines) amplitudes reaching up to 300 mV/m 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.

  19. Hydrogen Embrittlement (United States)

    Woods, Stephen; Lee, Jonathan A.


    Hydrogen embrittlement (HE) is a process resulting in a decrease in the fracture toughness or ductility of a metal due to the presence of atomic hydrogen. In addition to pure hydrogen gas as a direct source for the absorption of atomic hydrogen, the damaging effect can manifest itself from other hydrogen-containing gas species such as hydrogen sulfide (H2S), hydrogen chloride (HCl), and hydrogen bromide (HBr) environments. It has been known that H2S environment may result in a much more severe condition of embrittlement than pure hydrogen gas (H2) for certain types of alloys at similar conditions of stress and gas pressure. The reduction of fracture loads can occur at levels well below the yield strength of the material. Hydrogen embrittlement is usually manifest in terms of singular sharp cracks, in contrast to the extensive branching observed for stress corrosion cracking. The initial crack openings and the local deformation associated with crack propagation may be so small that they are difficult to detect except in special nondestructive examinations. Cracks due to HE can grow rapidly with little macroscopic evidence of mechanical deformation in materials that are normally quite ductile. This Technical Memorandum presents a comprehensive review of experimental data for the effects of gaseous Hydrogen Environment Embrittlement (HEE) for several types of metallic materials. Common material screening methods are used to rate the hydrogen degradation of mechanical properties that occur while the material is under an applied stress and exposed to gaseous hydrogen as compared to air or helium, under slow strain rates (SSR) testing. Due to the simplicity and accelerated nature of these tests, the results expressed in terms of HEE index are not intended to necessarily represent true hydrogen service environment for long-term exposure, but rather to provide a practical approach for material screening, which is a useful concept to qualitatively evaluate the severity of

  20. Asymmetric information and macroeconomic dynamics (United States)

    Hawkins, Raymond J.; Aoki, Masanao; Roy Frieden, B.


    We show how macroeconomic dynamics can be derived from asymmetric information. As an illustration of the utility of this approach we derive the equilibrium density, non-equilibrium densities and the equation of motion for the response to a demand shock for productivity in a simple economy. Novel consequences of this approach include a natural incorporation of time dependence into macroeconomics and a common information-theoretic basis for economics and other fields seeking to link micro-dynamics and macro-observables.

  1. Comprehensive asymmetric dark matter model


    Lonsdale, Stephen J.; Volkas, Raymond R.


    Asymmetric dark matter (ADM) is motivated by the similar cosmological mass densities measured for ordinary and dark matter. We present a comprehensive theory for ADM that addresses the mass density similarity, going beyond the usual ADM explanations of similar number densities. It features an explicit matter-antimatter asymmetry generation mechanism, has one fully worked out thermal history and suggestions for other possibilities, and meets all phenomenological, cosmological and astrophysical...

  2. Stereodirection of an α-ketoester at sub-molecular sites on chirally modified Pt(111): Heterogeneous asymmetric catalysis

    DEFF Research Database (Denmark)

    Demers-Carpentier, V.; Rasmussen, A.M.H.; Goubert, G.


    Chirally modified Pt catalysts are used in the heterogeneous asymmetric hydrogenation of α-ketoesters. Stereoinduction is believed to occur through the formation of chemisorbed modifier–substrate complexes. In this study, the formation of diastereomeric complexes by coadsorbed methyl 3,3,3-triflu......Chirally modified Pt catalysts are used in the heterogeneous asymmetric hydrogenation of α-ketoesters. Stereoinduction is believed to occur through the formation of chemisorbed modifier–substrate complexes. In this study, the formation of diastereomeric complexes by coadsorbed methyl 3...

  3. A new insight into the chemistry of iridium(III) complexes bearing phenyl phenylphosphonite cyclometalate and chelating pyridyl triazolate: the excited-state proton transfer tautomerism via an inter-ligand PO-H···N hydrogen bond. (United States)

    Lin, Cheng-Huei; Liao, Jia-Ling; Wu, Yu-Sin; Liao, Kuan-Yu; Chi, Yun; Chen, Chi-Lin; Lee, Gene-Hsiang; Chou, Pi-Tai


    Treatment of [IrCl3(tht)3], where tht = tetrahydrothiophene, with two equiv. of phenyl diphenylphosphinite (pdpitH) gave [Ir(pdpitH)(pdpit)(tht)Cl2] (1), which on further reaction with 3-t-butyl-5-(2-pyridyl)-1,2,4-triazole (bptzH) and NaOAc using a one-pot reaction afforded [Ir(pdpit)2(bptz)] (2). In sharp contrast, the reaction of [IrCl3(tht)3], pdpitH, and bptzH in the presence of a stronger base, Na2CO3, afforded a phenyl phenylphosphonite (pppo)-containing Ir(III) complex [Ir(pdpit)(pppo)(bptz)] (3) that reveals a strong PO-H-N inter-ligand hydrogen bond (H-bond), as evidenced by the single crystal X-ray structural analysis. For confirmation, addition of diazomethane to a diethylether solution of 3 led to the isolation of two methylated Ir(III) isomeric complexes, i.e. [Ir(pdpit)(pppoMe)(bptz)] (4) and [Ir(pdpit)(pppo)(bptzMe)] (5), possessing either a PO-Me or N-Me bonding fragment, respectively. The absorption spectrum of 3 in CH2Cl2 resembles that of 4, implying the dominant PO-H character in solution. Despite the prevailing PO-H character both in the solid crystal and in solution, its corresponding emission resembles that of 5, leading us to propose a mechanism incorporating the excited-state inter-ligand proton transfer (ESILPT) from PO-H to N-H isomeric form via the pre-existing PO···H···N hydrogen bond. The thermodynamics of proton transfer tautomerism are discussed on the basis of absorption/emission spectroscopy in combination with computational approaches; additional support is given by the relationship between emission pattern versus the position of protons and methyl substituents. The results demonstrate for the first time a paradigm of excited-state proton transfer for the transition metal complexes in the triplet manifold.

  4. Up-down asymmetric tokamaks

    CERN Document Server

    Ball, Justin


    Bulk toroidal rotation has proven capable of stabilising both dangerous MHD modes and turbulence. In this thesis, we explore a method to drive rotation in large tokamaks: up-down asymmetry in the magnetic equilibrium. We seek to maximise this rotation by finding optimal up-down asymmetric flux surface shapes. First, we use the ideal MHD model to show that low order external shaping (e.g. elongation) is best for creating up-down asymmetric flux surfaces throughout the device. Then, we calculate realistic up-down asymmetric equilibria for input into nonlinear gyrokinetic turbulence analysis. Analytic gyrokinetics shows that, in the limit of fast shaping effects, a poloidal tilt of the flux surface shaping has little effect on turbulent transport. Since up-down symmetric surfaces do not transport momentum, this invariance to tilt implies that devices with mirror symmetry about any line in the poloidal plane will drive minimal rotation. Accordingly, further analytic investigation suggests that non-mirror symmetri...

  5. Modelling and simulations of a Monolith Reactor for three-phase hydrogenation reactions – Rules and recommendations for mass transfer analysis


    Duran-Martinez, Freddy; Julcour-Lebigue, Carine; Billet, Anne-Marie; Larachi, Faïçal


    International audience; A strategy for the scale-up of a monolith reactor dedicated to gas-liquid catalytic reactions is worked out; focus is made on the crucial step of gas-liquid mass transfer modelling via a steady-state numerical study based on a single channel and single unit cell representation, using a frame moving with the bubble and solving the liquid phase only. The relevance of this simplified approach is assessed through a specific case (given bubble shape, channel diameter and fl...

  6. Modeling Droplet Heat and Mass Transfer during Spray Bar Pressure Control of the Multipurpose Hydrogen Test Bed (MHTB) Tank in Normal Gravity (United States)

    Kartuzova, O.; Kassemi, M.


    A CFD model for simulating pressure control in cryogenic storage tanks through the injection of a subcooled liquid into the ullage is presented and applied to the 1g MHTB spray bar cooling experiments. An Eulerian-Lagrangian approach is utilized to track the spray droplets and capture the interaction between the discrete droplets and the continuous ullage phase. The spray model is coupled with the VOF model by performing particle tracking in the ullage, removing particles from the ullage when they reach the interface, and then adding their contributions to the liquid. A new model for calculating the droplet-ullage heat and mass transfer is developed. In this model, a droplet is allowed to warm up to the saturation temperature corresponding to the ullage vapor pressure, after which it evaporates while remaining at the saturation temperature. The droplet model is validated against the results of the MHTB spray-bar cooling experiments with 50% and 90% tank fill ratios. The predictions of the present T-sat based model are compared with those of a previously developed kinetic-based droplet mass transfer model. The predictions of the two models regarding the evolving tank pressure and temperature distributions, as well as the droplets' trajectories and temperatures, are examined and compared in detail. Finally, the ullage pressure and local vapor and liquid temperature evolutions are validated against the corresponding data provided by the MHTB spray bar mixing experiment.

  7. Secondary coordination sphere accelerates hole transfer for enhanced hydrogen photogeneration from [FeFe]-hydrogenase mimic and CdSe QDs in water (United States)

    Wen, Min; Li, Xu-Bing; Jian, Jing-Xin; Wang, Xu-Zhe; Wu, Hao-Lin; Chen, Bin; Tung, Chen-Ho; Wu, Li-Zhu


    Achieving highly efficient hydrogen (H2) evolution via artificial photosynthesis is a great ambition pursued by scientists in recent decades because H2 has high specific enthalpy of combustion and benign combustion product. [FeFe]-Hydrogenase ([FeFe]-H2ase) mimics have been demonstrated to be promising catalysts for H2 photoproduction. However, the efficient photocatalytic H2 generation system, consisting of PAA-g-Fe2S2, CdSe QDs and H2A, suffered from low stability, probably due to the hole accumulation induced photooxidation of CdSe QDs and the subsequent crash of [FeFe]-H2ase mimics. In this work, we take advantage of supramolecular interaction for the first time to construct the secondary coordination sphere of electron donors (HA−) to CdSe QDs. The generated secondary coordination sphere helps realize much faster hole removal with a ~30-fold increase, thus leading to higher stability and activity for H2 evolution. The unique photocatalytic H2 evolution system features a great increase of turnover number to 83600, which is the highest one obtained so far for photocatalytic H2 production by using [FeFe]-H2ase mimics as catalysts. PMID:27417065

  8. Secondary coordination sphere accelerates hole transfer for enhanced hydrogen photogeneration from [FeFe]-hydrogenase mimic and CdSe QDs in water (United States)

    Wen, Min; Li, Xu-Bing; Jian, Jing-Xin; Wang, Xu-Zhe; Wu, Hao-Lin; Chen, Bin; Tung, Chen-Ho; Wu, Li-Zhu


    Achieving highly efficient hydrogen (H2) evolution via artificial photosynthesis is a great ambition pursued by scientists in recent decades because H2 has high specific enthalpy of combustion and benign combustion product. [FeFe]-Hydrogenase ([FeFe]-H2ase) mimics have been demonstrated to be promising catalysts for H2 photoproduction. However, the efficient photocatalytic H2 generation system, consisting of PAA-g-Fe2S2, CdSe QDs and H2A, suffered from low stability, probably due to the hole accumulation induced photooxidation of CdSe QDs and the subsequent crash of [FeFe]-H2ase mimics. In this work, we take advantage of supramolecular interaction for the first time to construct the secondary coordination sphere of electron donors (HA-) to CdSe QDs. The generated secondary coordination sphere helps realize much faster hole removal with a ~30-fold increase, thus leading to higher stability and activity for H2 evolution. The unique photocatalytic H2 evolution system features a great increase of turnover number to 83600, which is the highest one obtained so far for photocatalytic H2 production by using [FeFe]-H2ase mimics as catalysts.

  9. Secondary coordination sphere accelerates hole transfer for enhanced hydrogen photogeneration from [FeFe]-hydrogenase mimic and CdSe QDs in water. (United States)

    Wen, Min; Li, Xu-Bing; Jian, Jing-Xin; Wang, Xu-Zhe; Wu, Hao-Lin; Chen, Bin; Tung, Chen-Ho; Wu, Li-Zhu


    Achieving highly efficient hydrogen (H2) evolution via artificial photosynthesis is a great ambition pursued by scientists in recent decades because H2 has high specific enthalpy of combustion and benign combustion product. [FeFe]-Hydrogenase ([FeFe]-H2ase) mimics have been demonstrated to be promising catalysts for H2 photoproduction. However, the efficient photocatalytic H2 generation system, consisting of PAA-g-Fe2S2, CdSe QDs and H2A, suffered from low stability, probably due to the hole accumulation induced photooxidation of CdSe QDs and the subsequent crash of [FeFe]-H2ase mimics. In this work, we take advantage of supramolecular interaction for the first time to construct the secondary coordination sphere of electron donors (HA(-)) to CdSe QDs. The generated secondary coordination sphere helps realize much faster hole removal with a ~30-fold increase, thus leading to higher stability and activity for H2 evolution. The unique photocatalytic H2 evolution system features a great increase of turnover number to 83600, which is the highest one obtained so far for photocatalytic H2 production by using [FeFe]-H2ase mimics as catalysts.

  10. Iridium Cyclooctene Complex That Forms a Hyperpolarization Transfer Catalyst before Converting to a Binuclear C-H Bond Activation Product Responsible for Hydrogen Isotope Exchange. (United States)

    Iali, Wissam; Green, Gary G R; Hart, Sam J; Whitwood, Adrian C; Duckett, Simon B


    [IrCl(COE)2]2 (1) reacts with pyridine (py) and H2 to form crystallographically characterized IrCl(H)2(COE)(py)2 (2). 2 undergoes py loss to form 16-electron IrCl(H)2(COE)(py) (3), with equivalent hydride ligands. When this reaction is studied with parahydrogen, 1 efficiently achieves hyperpolarization of free py (and nicotinamide, nicotine, 5-aminopyrimidine, and 3,5-lutudine) via signal amplification by reversible exchange (SABRE) and hence reflects a simple and readily available precatayst for this process. 2 reacts further over 48 h at 298 K to form crystallographically characterized (Cl)(H)(py)(μ-Cl)(μ-H)(κ-μ-NC5H4)Ir(H)(py)2 (4). This dimer is active in the hydrogen isotope exchange process that is used in radiopharmaceutical preparations. Furthermore, while [Ir(H)2(COE)(py)3]PF6 (6) forms upon the addition of AgPF6 to 2, its stability precludes its efficient involvement in SABRE.

  11. Exocellular electron transfer in anaerobic microbial communities

    NARCIS (Netherlands)

    Stams, A.J.M.; Bok, de F.A.M.; Plugge, C.M.; Eekert, van M.H.A.; Dolfing, J.; Schraa, G.


    Exocellular electron transfer plays an important role in anaerobic microbial communities that degrade organic matter. Interspecies hydrogen transfer between microorganisms is the driving force for complete biodegradation in methanogenic environments. Many organic compounds are degraded by obligatory

  12. Hydrogen Bibliography

    Energy Technology Data Exchange (ETDEWEB)


    The Hydrogen Bibliography is a compilation of research reports that are the result of research funded over the last fifteen years. In addition, other documents have been added. All cited reports are contained in the National Renewable Energy Laboratory (NREL) Hydrogen Program Library.

  13. Hydrogen exchange

    DEFF Research Database (Denmark)

    Jensen, Pernille Foged; Rand, Kasper Dyrberg


    Hydrogen exchange (HX) monitored by mass spectrometry (MS) is a powerful analytical method for investigation of protein conformation and dynamics. HX-MS monitors isotopic exchange of hydrogen in protein backbone amides and thus serves as a sensitive method for probing protein conformation...... and dynamics along the entire protein backbone. This chapter describes the exchange of backbone amide hydrogen which is highly quenchable as it is strongly dependent on the pH and temperature. The HX rates of backbone amide hydrogen are sensitive and very useful probes of protein conformation......, as they are distributed along the polypeptide backbone and form the fundamental hydrogen-bonding networks of basic secondary structure. The effect of pressure on HX in unstructured polypeptides (poly-dl-lysine and oxidatively unfolded ribonuclease A) and native folded proteins (lysozyme and ribonuclease A) was evaluated...

  14. LG tools for asymmetric wargaming (United States)

    Stilman, Boris; Yakhnis, Alex; Yakhnis, Vladimir


    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

  15. Water reactive hydrogen fuel cell power system (United States)

    Wallace, Andrew P; Melack, John M; Lefenfeld, Michael


    A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into the fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

  16. Water reactive hydrogen fuel cell power system (United States)

    Wallace, Andrew P; Melack, John M; Lefenfeld, Michael


    A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into a fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

  17. Loan sales under asymmetric information


    Vargas Martínez, Mónica


    Loans are illiquid assets that can be sold in a secondary market even that buyers have no certainty about their quality. I study a model in which a lender has access to new investment opportunities when all her assets are illiquid. To raise funds, the lender may either borrow using her assets as collateral, or she can sell them in a secondary market. Given asymmetric information about assets quality, the lender cannot recover the total value of her assets. There is then a role for the governm...

  18. Pt-Enhanced Mesoporous Ti3+/TiO2 with Rapid Bulk to Surface Electron Transfer for Photocatalytic Hydrogen Evolution. (United States)

    Lian, Zichao; Wang, Wenchao; Li, Guisheng; Tian, Fenghui; Schanze, Kirk S; Li, Hexing


    Pt-doped mesoporous Ti3+ self-doped TiO2 (Pt-Ti3+/TiO2) is in situ synthesized via an ionothermal route, by treating metallic Ti in an ionic liquid containing LiOAc, HOAc, and a H2PtCl6 aqueous solution under mild ionothermal conditions. Such Ti3+-enriched environment, as well as oxygen vacancies, is proven to be effective for allowing the in situ reduction of Pt4+ ions uniformly located in the framework of the TiO2 bulk. The photocatalytic H2 evolution of Pt-Ti3+/TiO2 is significantly higher than that of the photoreduced Pt loaded on the original TiO2 and commercial P25. Such greatly enhanced activity is due to the various valence states of Pt (Ptn+, n = 0, 2, or 3), forming Pt-O bonds embedded in the framework of TiO2 and ultrafine Pt metal nanoparticles on the surface of TiO2. Such Ptn+-O bonds could act as the bridges for facilitating the photogenerated electron transfer from the bulk to the surface of TiO2 with a higher electron carrier density (3.11 × 1020 cm-3), about 2.5 times that (1.25 × 1020 cm-3) of the photoreduced Pt-Ti3+/TiO2 sample. Thus, more photogenerated electrons could reach the Pt metal for reducing protons to H2.

  19. Recent advances in osmium-catalyzed hydrogenation and dehydrogenation reactions. (United States)

    Chelucci, Giorgio; Baldino, Salvatore; Baratta, Walter


    CONSPECTUS: A current issue in metal-catalyzed reactions is the search for highly efficient transition-metal complexes affording high productivity and selectivity in a variety of processes. Moreover, there is also a great interest in multitasking catalysts that are able to efficiently promote different organic transformations by careful switching of the reaction parameters, such as temperature, solvent, and cocatalyst. In this context, osmium complexes have shown the ability to catalyze efficiently different types of reactions involving hydrogen, proving at the same time high thermal stability and simple synthesis. In the catalytic reduction of C═X (X = O, N) bonds by both hydrogenation (HY) and transfer hydrogenation (TH) reactions, the most interest has been focused on homogeneous systems based on rhodium, iridium, and in particular ruthenium catalysts, which have proved to catalyze chemo- and stereoselective hydrogenations with remarkable efficiency. By contrast, osmium catalysts have received much less attention because they are considered less active on account of their slower ligand exchange kinetics. Thus, this area remained almost neglected until recent studies refuted these prejudices. The aim of this Account is to highlight the impressive developments achieved over the past few years by our and other groups on the design of new classes of osmium complexes and their applications in homogeneous catalytic reactions involving the hydrogenation of carbon-oxygen and carbon-nitrogen bonds by both HY and TH reactions as well as in alcohol deydrogenation (DHY) reactions. The work described in this Account demonstrates that osmium complexes are emerging as powerful catalysts for asymmetric and non-asymmetric syntheses, showing a remarkably high catalytic activity in HY and TH reactions of ketones, aldehydes, imines, and esters as well in DHY reactions of alcohols. Thus, for instance, the introduction of ligands with an NH function, possibly in combination with a

  20. Hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Donath, E.


    This report mentioned that not very severe demands for purity were made on the hydrogen used in hydrogenation of coal or similar raw materials, because the catalysts were not very sensitive to poisoning. However, the hydrogenation plants tried to remove most impurities anyway by means of oil washes. The report included a table giving the amount of wash oil used up and the amount of hydrogen lost by dissolving into the wash oil used up and the amount of hydrogen lost by dissolving into the wash oil in order to remove 1% of various impurities from 1000 m/sup 3/ of the circulating gas. The amounts of wash oil used up were 1.1 m/sup 3/ for removing 1% nitrogen, 0.3 m/sup 3/ for 1% carbon monoxide, 0.03 m/sup 3/ for 1% methane. The amount of hydrogen lost was 28 m/sup 3/ for 1% nitrogen, 9 m/sup 3/ for 1% methane and ranged from 9 m/sup 3/ to 39 m/sup 3/ for 1% carbon monoxide and 1 m/sup 3/ to 41 m/sup 3/ for carbon dioxide depending on whether the removal was done in liquid phase or vapor phase and with or without reduction of the oxide to methane. Next the report listed and described the major processes used in German hydrogenation plants to produce hydrogen. Most of them produced water gas, which then had its carbon monoxide changed to carbon dioxide, and the carbon oxides washed out with water under pressure and copper hydroxide solution. The methods included the Winkler, Pintsch-Hillebrand, and Schmalfeldt-Wintershall processes, as well as roasting of coke in a rotating generator, splitting of gases formed during hydrogenation, and separation of cokery gas into its components by the Linde process.

  1. Asymmetric liberations in exterior resonances (United States)

    Beauge, C.


    The purpose of this paper is to present a general analysis of the planar circular restricted problem of three bodies in the case of exterior mean-motion resonances. Particularly, our aim is to map the phase space of various commensurabilities and determine the singular solutions of the averaged system, comparing them to the well-known case of interior resonances. In some commensurabilities (e.g. 1/2, 1/3) we show the existence of asymmetric librations; that is, librations in which the stationary value of the critical angle theta = (p+q) lambda1-p lambda-q pi is not equal to either zero or pi. The origin, stability and morphogenesis of these solutions are discussed and compared to symmetric librations. However, in some other resonances (e.g. 2/3, 3/4), these fixed points of the mean system seem to be absent. Librations in such cases are restricted to theta = O mod(pi). Asymmetric singular solutions of the plane circular problem are unknown in the case of interior resonances and cannot be reproduced by the reduced Andoyer Hamiltonian known as the Second Fundamental Model for Resonance. However, we show that the extended version of this Hamiltonian function, in which harmonics up to order two are considered, can reproduce fairly well the principal topological characteristics of the phase space and thereby constitutes a simple and useful analytical approximation for these resonances.

  2. Asymmetric Laguerre-Gaussian beams (United States)

    Kovalev, A. A.; Kotlyar, V. V.; Porfirev, A. P.


    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.

  3. Thin lenses of asymmetric power

    Directory of Open Access Journals (Sweden)

    W. F. Harris


    Full Text Available It is generally supposed that thin systems, including refracting surfaces and thin lenses, have powers that are necessarily symmetric.  In other words they have powers which can be represented assymmetric dioptric power matrices and in the familar spherocylindrical form used in optometry and ophthalmology.  This paper shows that this is not correct and that it is indeed possible for a thin system to have a power that is not symmetric and which cannot be expressed in spherocylindrical form.  Thin systems of asymmetric power are illustratedby means of a thin lens that is modelled with small prisms and is chosen to have a dioptric power ma-trix that is antisymmetric.  Similar models can be devised for a thin system whose dioptric power matrix is any  2 2 ×  matrix.  Thus any power, symmetric, asymmetric or antisymmetric, is possible for a thin system.  In this sense our understanding of the power of thin systems is now complete.

  4. Baseline Testing of the Club Car Carryall With Asymmetric Ultracapacitors (United States)

    Eichenberg, Dennis J.


    The NASA John H. Glenn Research Center initiated baseline testing of the Club Car Carryall with asymmetric ultracapacitors as a way to reduce pollution in industrial settings, reduce fossil fuel consumption, and reduce operating costs for transportation systems. The Club Car Carryall provides an inexpensive approach to advance the state of the art in electric vehicle technology in a practical application. The project transfers space technology to terrestrial use via non-traditional partners, and provides power system data valuable for future space applications. The work was done under the Hybrid Power Management (HPM) Program, which includes the Hybrid Electric Transit Bus (HETB). The Carryall is a state of the art, ground up, electric utility vehicle. A unique aspect of the project was the use of a state of the art, long life ultracapacitor energy storage system. Innovative features, such as regenerative braking through ultracapacitor energy storage, are planned. Regenerative braking recovers much of the kinetic energy of the vehicle during deceleration. The Carryall was tested with the standard lead acid battery energy storage system, as well as with an asymmetric ultracapacitor energy storage system. The report concludes that the Carryall provides excellent performance, and that the implementation of asymmetric ultracapacitors in the power system can provide significant performance improvements.

  5. Biomimetic Production of Hydrogen (United States)

    Gust, Devens


    The basic reaction for hydrogen generation is formation of molecular hydrogen from two electrons and two protons. Although there are many possible sources for the protons and electrons, and a variety of mechanisms for providing the requisite energy for hydrogen synthesis, the most abundant and readily available source of protons and electrons is water, and the most attractive source of energy for powering the process is sunlight. Not surprisingly, living systems have evolved to take advantage of these sources for materials and energy. Thus, biology provides paradigms for carrying out the reactions necessary for hydrogen production. Photosynthesis in green plants uses sunlight as the source of energy for the oxidation of water to give molecular oxygen, protons, and reduction potential. Some photosynthetic organisms are capable of using this reduction potential, in the form of the reduced redox protein ferredoxin, to reduce protons and produce molecular hydrogen via the action of an hydrogenase enzyme. A variety of other organisms metabolize the reduced carbon compounds that are ultimately the major products of photosynthesis to produce molecular hydrogen. These facts suggest that it might be possible to use light energy to make molecular hydrogen via biomimetic constructs that employ principles similar to those used by natural organisms, or perhaps with hybrid "bionic" systems that combine biomimetic materials with natural enzymes. It is now possible to construct artificial photosynthetic systems that mimic some of the major steps in the natural process.(1) Artificial antennas based on porphyrins, carotenoids and other chromophores absorb light at various wavelengths in the solar spectrum and transfer the harvested excitation energy to artificial photosynthetic reaction centers.(2) In these centers, photoinduced electron transfer uses the energy from light to move an electron from a donor to an acceptor moiety, generating a high-energy charge-separated state

  6. Asymmetric Warfare and the Will to Win

    National Research Council Canada - National Science Library

    Herrera, Cary


    This thesis explores the will to win in asymmetric war. Asymmetric war, in which one side has an overwhelming advantage over its opponent, will likely be the war of the future for the United States in the post-Cold War uni-polar world...

  7. Renewable resource management under asymmetric information

    DEFF Research Database (Denmark)

    Jensen, Frank; Andersen, Peder; Nielsen, Max


    Asymmetric information between fishermen and the regulator is important within fisheries. The regulator may have less information about stock sizes, prices, costs, effort, productivity and catches than fishermen. With asymmetric information, a strong analytical tool is principal-agent analysis. I...

  8. Asymmetric Quantum Codes on Toric Surfaces

    DEFF Research Database (Denmark)

    Hansen, Johan P.


    Asymmetric quantum error-correcting codes are quantum codes defined over biased quantum channels: qubit-flip and phase-shift errors may have equal or different probabilities. The code construction is the Calderbank-Shor-Steane construction based on two linear codes. We present families of toric...... surfaces, toric codes and associated asymmetric quantum error-correcting codes....

  9. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach


    Chauhan, Pankaj; Chimni, Swapandeep Singh


    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.

  10. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach (United States)

    Chauhan, Pankaj


    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

  11. Worst Asymmetrical Short-Circuit Current

    DEFF Research Database (Denmark)

    Arana Aristi, Iván; Holmstrøm, O; Grastrup, L


    In a typical power plant, the production scenario and the short-circuit time were found for the worst asymmetrical short-circuit current. Then, a sensitivity analysis on the missing generator values was realized in order to minimize the uncertainty of the results. Afterward the worst asymmetrical...

  12. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach

    Directory of Open Access Journals (Sweden)

    Pankaj Chauhan


    Full Text Available 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.

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

    KAUST Repository

    Borrmann, Ruediger


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

  14. Asymmetric MoS2 /Graphene/Metal Sandwiches: Preparation, Characterization, and Application. (United States)

    Toth, Peter S; Velický, Matĕj; Bissett, Mark A; Slater, Thomas J A; Savjani, Nicky; Rabiu, Aminu K; Rakowski, Alexander M; Brent, Jack R; Haigh, Sarah J; O'Brien, Paul; Dryfe, Robert A W


    The polarizable organic/water interface is used to construct MoS2 /graphene nanocomposites, and various asymmetrically dual-decorated graphene sandwiches are synthesized. High-resolution transmission electron microscopy and 3D electron tomography confirm their structure. These dual-decorated graphene-based hybrids show excellent hydrogen evolution activity and promising capacitance performance. © 2016 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Industrial asymmetric synthesis by use of metal-BINAP catalysts; Kinzoku-BINAP sakutai shokubai wo mochiita fusai gosei gijutsu no kaihatsu

    Energy Technology Data Exchange (ETDEWEB)

    Kumobayashi, H.; Sayo, N.; Akutagawa, S.; Sakaguchi, T.; Tsuruta, H. [Takasago International Corporation, Kanagawa (Japan). Central Research Laboratory


    This article covers the history and present progress of the industrial asymmetric synthesis by use of BINAP (2,2`-bis(diphenylphosphino)-1,1`-binaphthyl)-metal catalysts. Especially, the historic discovery of the BINAP-rhodium(I)-catalyzed 1,3-hydrogen migration of N,N-diethylgeranylamine (GDEA) and the achievement of practical preparation of optically active BINAP, led to the establishment of the first industrial process for efficient production of l-menthol employing asymmetric catalysts. Continuing efforts have been devoted to the exploration of new catalytic reactions using new BINAP-metal complexes and their applications to industrial asymmetric synthesis. Among them, asymmetric hydrogenation of functionalyzed olefins and ketones by use of BINAP-ruthenium (II) complexes provides fruitful results. Today, a wide range of chiral compounds including the pharmaceutical intermediates 4-acetoxy-2-azetidinone (4-AA) and 1,2-propanediol (2-PPD) are produced in industrial scale in Takasago. 47 refs., 8 figs., 9 tabs.

  16. Ultrafast vibrational population transfer dynamics in 2-acetylcyclopentanone studied by 2D IR spectroscopy. (United States)

    Park, Sungnam; Ji, Minbiao


    2-Acetylcyclopentanone (2-ACP), which is a β-dicarbonyl compound, undergoes keto-enol isomerization, and its enol tautomers are stabilized by a cyclic intramolecular hydrogen bond. 2-ACP (keto form) has symmetric and asymmetric vibrational modes of the two carbonyl groups at 1748 and 1715 cm(-1) , respectively, which are well separated from the carbonyl modes of its enol tautomers in the FTIR spectrum. We have investigated 2-ACP dissolved in carbon tetrachloride by 2D IR spectroscopy and IR pump-probe spectroscopy. Vibrational population transfer dynamics between the two carbonyl modes were observed by 2D IR spectroscopy. To extract the population exchange dynamics (i.e., the down- and uphill population transfer rate constants), we used the normalized volumes of the cross-peaks with respect to the diagonal peaks at the same emission frequency and the survival and conditional probability functions. As expected, the downhill population transfer time constant (3.2 ps) was measured to be smaller than the uphill population transfer time constant (3.8 ps). In addition, the vibrational population relaxation dynamics of the two carbonyl modes were observed to be the same within the experimental error and were found to be much slower than vibrational population transfer between two carbonyl modes. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Asymmetric Digital Subscriber Line (ADSL

    Directory of Open Access Journals (Sweden)

    Slavko Šarić


    Full Text Available ADSL (Asymmetric Digital Subscriber Line is a technologythat allows transmission at 8.488 Mbps over the existingtelephone copper line (speed range depending on the distance.ADSL circuit connects the ADSL modems by twisted-pairtelephone lines creating three infonnation channels: high speedsimplex (maximum 9 Mbps, medium speed duplex channel(maximum 2 Mbps and plain old telephone service channel.ADSL technology supports up to seven synchronous channelsthat can be configured to meet the needs of the end user.One could simultaneously view four movies stored in MPEG 1fonnat on separate television sets (MPEG 1 transmitted at 1.5Mbps, hold a video-conference (transmitted at 348 kbps,download data files from a server at 128 kbps via ISDN andeven receive a telephone call.

  18. Research on asymmetric searchable encryption (United States)

    Yu, Zonghua; Wu, Yudong


    Cloud server side to ease the user's local storage pressure at the same time, there are hidden data on the hidden dangers, the user often choose to upload the data in the form of cipher text to the cloud server. However, the classic data encryption and decryption algorithms are not provided search function, affecting the user's efficiency. To this end, an asymmetric searchable encryption scheme is proposed. The scheme can be used for any person can generate a trapdoor, cipher text can be free modified, the key pair generated by the user themselves, encrypt the identity, S-shaped virtual and other five loopholes to improve. The analysis results show that the scheme solves the above five vulnerabilities in the original scheme, so that the information semantics of both parties of communication can be guaranteed.

  19. Turbulent mixed convection in asymmetrically heated vertical channel

    Directory of Open Access Journals (Sweden)

    Mokni Ameni


    Full Text Available In this paper an investigation of mixed convection from vertical heated channel is undertaken. The aim is to explore the heat transfer obtained by adding a forced flow, issued from a flat nozzle located in the entry section of a channel, to the up-going fluid along its walls. Forced and free convection are combined studied in order to increase the cooling requirements. The study deals with both symmetrically and asymmetrically heated channel. The Reynolds number based on the nozzle width and the jet velocity is assumed to be 3 103 and 2.104; whereas, the Rayleigh number based on the channel length and the wall temperature difference varies from 2.57 1010 to 5.15 1012. The heating asymmetry effect on the flow development including the mean velocity and temperature the local Nusselt number, the mass flow rate and heat transfer are examined.

  20. Embedded-atom method potential for modeling hydrogen and hydrogen-defect interaction in tungsten (United States)

    Wang, Li-Fang; Shu, Xiaolin; Lu, Guang-Hong; Gao, Fei


    An embedded-atom method potential has been developed for modeling hydrogen in body-centered-cubic (bcc) tungsten by fitting to an extensive database of density functional theory (DFT) calculations. Comprehensive evaluations of the new potential are conducted by comparing various hydrogen properties with DFT calculations and available experimental data, as well as all the other tungsten–hydrogen potentials. The new potential accurately reproduces the point defect properties of hydrogen, the interaction among hydrogen atoms, the interplay between hydrogen and a monovacancy, and the thermal diffusion of hydrogen in tungsten. The successful validation of the new potential confirms its good reliability and transferability, which enables large-scale atomistic simulations of tungsten–hydrogen system. The new potential is afterward employed to investigate the interplay between hydrogen and other defects, including [1 1 1] self-interstitial atoms (SIAs) and vacancy clusters in tungsten. It is found that both the [1 1 1] SIAs and the vacancy clusters exhibit considerable attraction for hydrogen. Hydrogen solution and diffusion in strained tungsten are also studied using the present potential, which demonstrates that tensile (compressive) stress facilitates (impedes) hydrogen solution, and isotropic tensile (compressive) stress impedes (facilitates) hydrogen diffusion while anisotropic tensile (compressive) stress facilitates (impedes) hydrogen diffusion.

  1. Crystal structures of three hydrogen-bonded 1:2 compounds of chloranilic acid with 2-pyridone, 3-hydroxypyridine and 4-hyroxypyridine

    Directory of Open Access Journals (Sweden)

    Kazuma Gotoh


    Full Text Available The crystal structures of the 1:2 compounds of chloranilic acid (systematic name: 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone with 2-pyridone, 3-hydroxypyridine and 4-hyroxypyridine, namely, bis(2-pyridone chloranilic acid, 2C5H5NO·C6H2Cl2O4, (I, bis(3-hydroxypyridinium chloranilate, 2C5H6NO+·C6Cl2O42−, (II, and bis(4-hydroxypyridinium chloranilate, 2C5H6NO+·C6Cl2O42−, (III, have been determined at 120 K. In the crystal of (I, the base molecule is in the lactam form and no acid–base interaction involving H-atom transfer is observed. The acid molecule lies on an inversion centre and the asymmetric unit consists of one half-molecule of chloranilic acid and one 2-pyridone molecule, which are linked via a short O—H...O hydrogen bond. 2-Pyridone molecules form a head-to-head dimer via a pair of N—H...O hydrogen bonds, resulting in a tape structure along [201]. In the crystals of (II and (III, acid–base interactions involving H-atom transfer are observed and the divalent cations lie on an inversion centre. The asymmetric unit of (II consists of one half of a chloranilate anion and one 3-hydroxypyridinium cation, while that of (III comprises two independent halves of anions and two 4-hydroxypyridinium cations. The primary intermolecular interaction in (II is a bifurcated O—H...(O,O hydrogen bond between the cation and the anion. The hydrogen-bonded units are further linked via N—H...O hydrogen bonds, forming a layer parallel to the bc plane. In (III, one anion is surrounded by four cations via O—H...O and C—H...O hydrogen bonds, while the other is surrounded by four cations via N—H...O and C—H...Cl hydrogen bonds. These interactions link the cations and the anions into a layer parallel to (301.

  2. Hydrogen program overview

    Energy Technology Data Exchange (ETDEWEB)

    Gronich, S. [Dept. of Energy, Washington, DC (United States). Office of Utility Technologies


    This paper consists of viewgraphs which summarize the following: Hydrogen program structure; Goals for hydrogen production research; Goals for hydrogen storage and utilization research; Technology validation; DOE technology validation activities supporting hydrogen pathways; Near-term opportunities for hydrogen; Market for hydrogen; and List of solicitation awards. It is concluded that a full transition toward a hydrogen economy can begin in the next decade.

  3. Design of control algorithm over technical condition of hydrogen generators based on hydro-reactive compositions


    Abramov, Yuriy; Borisenko, Vitaliy; Krivtsova, Valentina


    In order to describe the process of hydrogen generation, a system of differential equations is applied, which is matched with a transfer function of the hydrogen generator. A transfer function of the hydrogen generator is used for the transition to the frequency domain of research. We obtained an expression for the asymptotic logarithmic amplitude-frequency characteristic of the hydrogen generator. This characteristic is used to identify a simplified description of the hydrogen generator, whi...

  4. Hydrogen usage

    Energy Technology Data Exchange (ETDEWEB)


    This short tabular report listed the number of m/sup 3/ of hydrogen required for a (metric) ton of product for various combinations of raw material and product in a hydrogenation procedure. In producing auto gasoline, bituminous coal required 2800 m/sup 3/, brown coal required 2400 m/sup 3/, high-temperature-carbonization tar required 2100 m/sup 3/, bituminous coal distillation tar required 1300 m/sup 3/, brown-coal low-temperature-carbonization tar required 850 m/sup 3/, petroleum residues required 900 m/sup 3/, and gas oil required 500 m/sup 3/. In producing diesel oil, brown coal required 1900 m/sup 3/, whereas petroleum residues required 500 m/sup 3/. In producing diesel oil, lubricants, and paraffin by the TTH (low-temperature-hydrogenation) process, brown-coal low-temperature-carbonization tar required 550 m/sup 3/. 1 table.

  5. (R,R-Disynephrine ether bis(hydrogen sulfate

    Directory of Open Access Journals (Sweden)

    William Arbuckle


    Full Text Available The asymmetric unit of the title compound [systematic name: (R,R-2,4-bis(4-hydroxyphenyl-N,N′-dimethyl-3-oxapentane-1,5-diammonium bis(hydrogen sulfate], C18H26N2O32+·2HSO4−, contains one half-cation and one hydrogen sulfate anion. The cation has crystallographically imposed twofold symmetry with the rotation axis passing through the central ether O atom. Hydrogen bonds between the hydroxy group and amine H atoms of the cation to two hydrogen sulfate anions link the three ions in a ring motif. A three-dimensional network is accomplished by additional O—H...O hydrogen bonds between the anions and by N—H...O hydrogen bonds between the cations. Disorder with equally occupied sites affects the H-atom position in the anion.

  6. Influence of convective conditions in radiative peristaltic flow of pseudoplastic nanofluid in a tapered asymmetric channel

    Energy Technology Data Exchange (ETDEWEB)

    Hayat, T. [Department of Mathematics, Quaid-I-Azam University 45320, Islamabad 44000 (Pakistan); Nonlinear Analysis and Applied Mathematics (NAAM) Research Group, Department of Mathematics, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia); Iqbal, Rija [Department of Mathematics, Quaid-I-Azam University 45320, Islamabad 44000 (Pakistan); Tanveer, Anum, E-mail: [Department of Mathematics, Quaid-I-Azam University 45320, Islamabad 44000 (Pakistan); Alsaedi, A. [Nonlinear Analysis and Applied Mathematics (NAAM) Research Group, Department of Mathematics, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)


    This paper looks at the influences of magnetohydrodynamics (MHD) and thermal radiation on peristaltic transport of a pseudoplastic nanofluid in a tapered asymmetric channel. The tapered channel walls satisfy convective boundary conditions. The governing equations for the balance of mass, momentum, temperature and volume fraction for pseudoplastic nanofluid are first formulated and then utilized for long wavelength and small Reynolds number considerations. Effects of involved parameters on the flow characteristics have been plotted and examined. It is observed that the heat transfer Biot number shows a dual behavior on the temperature of nanofluid particles whereas the mass transfer Biot number with its increasing values enhances the fluid temperature. - Highlights: • Mathematical model for peristalsis of pseudoplastic nanofluid is formulated. • Analysis has been made in a tapered asymmetric channel. • Magnetohydrodynamic aspects have been outlined. • Influence of thermal radiation is investigated. • Convective conditions for both heat and mass transfer are present.

  7. Strengthening of hydrogen bonding with the push-pull effect (United States)

    Tao, Yunwen; Zou, Wenli; Kraka, Elfi


    Theoretical studies of hydrogen-bonding based on cluster models tend to overlook the peripheral monomers which are influential. By revisiting thirteen hydrogen-bonded complexes of H2O, HF and NH3, the "push-pull" effect is identified as a general mechanism that strengthens a hydrogen bond. Enhanced Lp (X) →σ∗ (X‧ - H) charge transfer is proved to be the core of the "push-pull" effect. The charge transfer can convert an electrostatic hydrogen bond into a covalent hydrogen bond.

  8. Modelling asymmetric growth in crowded plant communities

    DEFF Research Database (Denmark)

    Damgaard, Christian


    A class of models that may be used to quantify the effect of size-asymmetric competition in crowded plant communities by estimating a community specific degree of size-asymmetric growth for each species in the community is suggested. The model consists of two parts: an individual size......-asymmetric growth part, where growth is assumed to be proportional to a power function of the size of the individual, and a term that reduces the relative growth rate as a decreasing function of the individual plant size and the competitive interactions from other plants in the neighbourhood....

  9. Nondeterministic self-assembly with asymmetric interactions (United States)

    Tesoro, S.; Göpfrich, K.; Kartanas, T.; Keyser, U. F.; Ahnert, S. E.


    We investigate general properties of nondeterministic self-assembly with asymmetric interactions, using a computational model and DNA tile assembly experiments. By contrasting symmetric and asymmetric interactions we show that the latter can lead to self-limiting cluster growth. Furthermore, by adjusting the relative abundance of self-assembly particles in a two-particle mixture, we are able to tune the final sizes of these clusters. We show that this is a fundamental property of asymmetric interactions, which has potential applications in bioengineering, and provides insights into the study of diseases caused by protein aggregation.

  10. Chiral fullerenes from asymmetric catalysis. (United States)

    Maroto, Enrique E; Izquierdo, Marta; Reboredo, Silvia; Marco-Martínez, Juan; Filippone, Salvatore; Martín, Nazario


    Fullerenes are among the most studied molecules during the last three decades, and therefore, a huge number of chemical reactions have been tested on these new carbon allotropes. However, the aim of most of the reactions carried out on fullerenes has been to afford chemically modified fullerenes that are soluble in organic solvents or even water in the search for different mechanical, optical, or electronic properties. Therefore, although a lot of effort has been devoted to the chemical functionalization of these molecular allotropes of carbon, important aspects in the chemistry of fullerenes have not been properly addressed. In particular, the synthesis of chiral fullerenes at will in an efficient manner using asymmetric catalysis has not been previously addressed in fullerene science. Thus, despite the fact that the chirality of fullerenes has always been considered a fundamental issue, the lack of a general stereoselective synthetic methodology has restricted the use of enantiopure fullerene derivatives, which have usually been obtained only after highly expensive HPLC isolation on specific chiral columns or prepared from a pool of chiral starting materials. In this Account, we describe the first stereodivergent catalytic enantioselective syntheses in fullerene science, which have allowed the highly efficient synthesis of enantiomerically pure derivatives with total control of the stereochemical result using metallic catalysts and/or organocatalysts under very mild conditions. Density functional theory calculations strongly support the experimental findings for the assignment of the absolute configuration of the new stereocenters, which has also been ascertained by application of the sector rule and single-crystal X-ray diffraction. The use of the curved double bond of fullerene cages as a two-π-electron component in a variety of stereoselective cycloaddition reactions represents a challenging goal considering that, in contrast to most of the substituted

  11. Versatile Hydrogen

    Indian Academy of Sciences (India)

    Hydrogen is probably the most intriguing ele- ment in the periodic table. Although it is only the seventh most abundant element on earth, it is the most abundant element in the uni- verse. It combines with almost all the ele- ments of the periodic table, except for a few transition elements, to form binary compounds of the type E.

  12. Modeling of asymmetrical boost converters

    Directory of Open Access Journals (Sweden)

    Eliana Isabel Arango Zuluaga


    Full Text Available The asymmetrical interleaved dual boost (AIDB is a fifth-order DC/DC converter designed to interface photovoltaic (PV panels. The AIDB produces small current harmonics to the PV panels, reducing the power losses caused by the converter operation. Moreover, the AIDB provides a large voltage conversion ratio, which is required to step-up the PV voltage to the large dc-link voltage used in grid-connected inverters. To reject irradiance and load disturbances, the AIDB must be operated in a closed-loop and a dynamic model is required. Given that the AIDB converter operates in Discontinuous Conduction Mode (DCM, classical modeling approaches based on Continuous Conduction Mode (CCM are not valid. Moreover, classical DCM modeling techniques are not suitable for the AIDB converter. Therefore, this paper develops a novel mathematical model for the AIDB converter, which is suitable for control-pur-poses. The proposed model is based on the calculation of a diode current that is typically disregarded. Moreover, because the traditional correction to the second duty cycle reported in literature is not effective, a new equation is designed. The model accuracy is contrasted with circuital simulations in time and frequency domains, obtaining satisfactory results. Finally, the usefulness of the model in control applications is illustrated with an application example.

  13. Modeling of asymmetrical boost converters

    Directory of Open Access Journals (Sweden)

    Eliana Isabel Arango Zuluaga


    Full Text Available The asymmetrical interleaved dual boost (AIDB is a fifth-order DC/DC converter designed to interface photovoltaic (PV panels. The AIDB produces small current harmonics to the PV panels, reducing the power losses caused by the converter operation. Moreover, the AIDB provides a large voltage conversion ratio, which is required to step-up the PV voltage to the large dc-link voltage used in grid-connected inverters. To reject irradiance and load disturbances, the AIDB must be operated in a closed-loop and a dynamic model is required. Given that the AIDB converter operates in Discontinuous Conduction Mode (DCM, classical modeling approaches based on Continuous Conduction Mode (CCM are not valid. Moreover, classical DCM modeling techniques are not suitable for the AIDB converter. Therefore, this paper develops a novel mathematical model for the AIDB converter, which is suitable for control-pur-poses. The proposed model is based on the calculation of a diode current that is typically disregarded. Moreover, because the traditional correction to the second duty cycle reported in literature is not effective, a new equation is designed. The model accuracy is contrasted with circuital simulations in time and frequency domains, obtaining satisfactory results. Finally, the usefulness of the model in control applications is illustrated with an application example.

  14. Stereocontrolled synthesis of substituted chiral piperidines via one-pot asymmetric 6π-azaelectrocyclization: asymmetric syntheses of (-)-dendroprimine, (+)-7-epidendroprimine, (+)-5-epidendroprimine, and (+)-5,7-epidendroprimine. (United States)

    Kobayashi, Toyoharu; Hasegawa, Futoshi; Hirose, Yoshikatsu; Tanaka, Katsunori; Mori, Hajime; Katsumura, Shigeo


    The asymmetric one-pot 6π-azaelectrocyclization of alkenyl vinyl stannane, ethyl (Z)-2-iodo-4-oxobutenoate, and (-)-7-isopropyl-cis-aminoindanol in the presence of a Pd(0) catalyst stereoselectively produced the tetracyclic aminoacetal compounds, resulting from the four-bond formation accompanying by controlling the stereochemistry at the two asymmetric centers. The produced cyclic aminoacetals can be regarded as synthetic precursors of substituted chiral piperidines, and the syntheses of 2,4- and 2,4,6-substituted piperidines were realized from the obtained aminoacetals by the stereoselective hydrogenation of the double bond conjugated with the C-4 ester group and alkylation at the aminoacetal moiety. In addition, the stereoselective synthesis of an indolizidine alkaloid, (-)-dendroprimine, and its three stereoisomers, (+)-7-epidendroprimine, (+)-5-epidendroprimine, and (+)-5,7-epidendroprimine, were achieved.

  15. Biocatalytic asymmetric phosphorylation of mevalonate

    NARCIS (Netherlands)

    Matsumi, R.; Hellriegel, C.; Schoenenberger, B.; Milesi, T.; Oost, van der J.; Wohlgemuth, R.


    The excellent selectivity of the mevalonate kinase-catalyzed phosphorylation of mevalonate simplifies lengthy multi-step routes to (R)-mevalonate-5-phosphate to a one-step biocatalytic reaction, because the phosphate group can be transferred directly and without any additional reaction steps

  16. Effect of hydrogen bonding on infrared absorption intensity

    CERN Document Server

    Athokpam, Bijyalaxmi; McKenzie, Ross H


    We consider how the infrared intensity of an O-H stretch in a hydrogen bonded complex varies as the strength of the H-bond varies from weak to strong. We obtain trends for the fundamental and overtone transitions as a function of donor-acceptor distance R, which is a common measure of H-bond strength. Our calculations use a simple two-diabatic state model that permits symmetric and asymmetric bonds, i.e. where the proton affinity of the donor and acceptor are equal and unequal, respectively. The dipole moment function uses a Mecke form for the free OH dipole moment, associated with the diabatic states. The transition dipole moment is calculated using one-dimensional vibrational eigenstates associated with the H-atom transfer coordinate on the ground state adiabatic surface of our model. Over 20-fold intensity enhancements for the fundamental are found for strong H-bonds, where there are significant non-Condon effects. The isotope effect on the intensity yields a non-monotonic H/D intensity ratio as a function...

  17. Asymmetrical Warfare, Transformation, and Foreign Language Capability

    National Research Council Canada - National Science Library

    Porter, Clifford F


    .... There is no doubt that the current global war on terrorism is an asymmetrical war against an unpredictable enemy rather than the predictable or symmetrical threats against self-important dictators or the Soviet Union...

  18. Asymmetric cryptography based on wavefront sensing. (United States)

    Peng, Xiang; Wei, Hengzheng; Zhang, Peng


    A system of asymmetric cryptography based on wavefront sensing (ACWS) is proposed for the first time to our knowledge. One of the most significant features of the asymmetric cryptography is that a trapdoor one-way function is required and constructed by analogy to wavefront sensing, in which the public key may be derived from optical parameters, such as the wavelength or the focal length, while the private key may be obtained from a kind of regular point array. The ciphertext is generated by the encoded wavefront and represented with an irregular array. In such an ACWS system, the encryption key is not identical to the decryption key, which is another important feature of an asymmetric cryptographic system. The processes of asymmetric encryption and decryption are formulized mathematically and demonstrated with a set of numerical experiments.

  19. Congenital asymmetric crying face: a case report

    Directory of Open Access Journals (Sweden)

    Semra Kara


    Full Text Available Congenital asymmetric crying face is an anomalia caused by unilateral absence or weakness of depressor anguli oris muscle The major finding of the disease is the absence or weakness in the outer and lower movement of the commissure during crying. The other expression muscles are normal and the face is symmetric at rest. The asymmetry in congenital asymmetric crying face is most evident during infancy but decreases by age. Congenital asymmetric crying face can be associated with cervicofacial, musclebone, respiratory, genitourinary and central nervous system anomalia. It is diagnosed by physical examination. This paper presents a six days old infant with Congenital asymmetric crying face and discusses the case in terms of diagnosis and disease features.

  20. Modeling Asymmetric Volatility In Oil Prices

    National Research Council Canada - National Science Library

    Syed Aun Hassan


    .... The paper uses daily crude oil price data for the past 10 years to test and model the oil price volatility by fitting different variations of GARCH including a univariate asymmetric GARCH model to the series...

  1. Asymmetric dense matter in holographic QCD

    Directory of Open Access Journals (Sweden)

    Shin Ik Jae


    Full Text Available We study asymmetric dense matter in holographic QCD.We construct asymmetric dense matter by considering two quark flavor branes with dierent quark masses in a D4/D6/D6 model. To calculate the symmetry energy in nuclear matter, we consider two quarks with equal masses and observe that the symmetry energy increases with the total charge showing the stiff dependence. This behavior is universal in the sense that the result is independent of parameters in the model. We also study strange (or hyperon matter with one light and one intermediate mass quarks. In addition to the vacuum properties of asymmetric matter, we calculate meson masses in asymmetric dense matter and discuss our results in the light of in-medium kaon masses.

  2. Hydrogen in metals

    CSIR Research Space (South Africa)

    Carter, TJ


    Full Text Available The effects of hydrogen on various metals and the use of metal hydrides for hydrogen storage are discussed. The mechanisms of, and differences between, hydrogen embrittlement and hydrogen attack of ferritic steels are compared, common sources...

  3. Designing Asymmetric Multiferroics with Strong Magnetoelectric Coupling


    Lu, X. Z.; Xiang, H. J.


    Multiferroics offer exciting opportunities for electric-field control of magnetism. Unfortunately, single-phase multiferroics suitable for such applications at room temperature has not been discovered. Here, we propose the concept of a new type of multiferroics, namely, "asymmetric multiferroic". In asymmetric multiferroics, two locally stable ferroelectric states are not symmetrically equivalent, leading to different magnetic properties between these two states. Furthermore, we predict from ...

  4. Stable Bound States of Asymmetric Dark Matter


    Wise, Mark B.; Zhang, Yue


    The simplest renormalizable effective field theories with asymmetric dark matter bound states contain two additional gauge singlet fields one being the dark matter and the other a mediator particle that the dark matter annihilates into. We examine the physics of one such model with a Dirac fermion as the dark matter and a real scalar mediator. For a range of parameters the Yukawa coupling of the dark matter to the mediator gives rise to stable asymmetric dark matter bound states. We derive pr...

  5. Transfer of Short-Term Motor Learning across the Lower Limbs as a Function of Task Conception and Practice Order (United States)

    Stockel, Tino; Wang, Jinsung


    Interlimb transfer of motor learning, indicating an improvement in performance with one limb following training with the other, often occurs asymmetrically (i.e., from non-dominant to dominant limb or vice versa, but not both). In the present study, we examined whether interlimb transfer of the same motor task could occur asymmetrically and in…

  6. Characteristics of Braced Excavation under Asymmetrical Loads

    Directory of Open Access Journals (Sweden)

    Changjie Xu


    Full Text Available Numerous excavation practices have shown that large discrepancies exist between field monitoring data and calculated results when the conventional symmetry-plane method (with half-width is used to design the retaining structure under asymmetrical loads. To examine the characteristics of a retaining structure under asymmetrical loads, we use the finite element method (FEM to simulate the excavation process under four different groups of asymmetrical loads and create an integrated model to tackle this problem. The effects of strut stiffness and wall length are also investigated. The results of numerical analysis clearly imply that the deformation and bending moment of diaphragm walls are distinct on different sides, indicating the need for different rebar arrangements when the excavation is subjected to asymmetrical loads. This study provides a practical approach to designing excavations under asymmetrical loads. We analyze and compare the monitoring and calculation data at different excavation stages and find some general trends. Several guidelines on excavation design under asymmetrical loads are drawn.

  7. Prospects of asymmetrically H-terminated zigzag germanene nanoribbons for spintronic application

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Varun, E-mail: [Nanomaterials Research Group, ABV-Indian Institute of Information Technology and Management (IIITM), Gwalior 474015 (India); Srivastava, Pankaj [Nanomaterials Research Group, ABV-Indian Institute of Information Technology and Management (IIITM), Gwalior 474015 (India); Jaiswal, Neeraj K. [Discipline of Physics, Indian Institute of Information Technology, Design & Manufacturing, Jabalpur, Dumna Airport Road, Jabalpur 482005 (India)


    Highlights: • Asymmetric hydrogen termination of Zigzag Germanene Nanoribbons (ZGeNR) is presented with their plausible spintronic device application. • It is revealed that asymmetric terminations are energetically more favourable compared to symmetric terminations. • The magnetic moment analysis depicts that asymmetric ZGeNR have a magnetic ground state with a preferred ferromagnetic (FM) coupling. • Presented doped asymmetric ZGeNR exhibits a half-metallic character which makes them qualify for spin-filtering device. - Abstract: First-principles investigations have been performed to explore the spin based electronic and transport properties of asymmetrically H-terminated zigzag germanene nanoribbons (2H−H ZGeNR). Investigations reveal a significant formation energy difference (ΔE{sub F} = E{sub F(2H-H)} − E{sub F(H-H)} ∼ −0.49 eV), highlighting more energetic stability for asymmetric edge termination compared to symmetric edge termination, irrespective of the ribbon width. Further, magnetic moment analysis and total energy calculations were performed to unveil that these structures have a magnetic ground state with preferred ferromagnetic (FM) coupling. The calculated E-k structures project a unique bipolar semiconducting behaviour for 2H−H ZGeNR which is contrast to H-terminated ZGeNR. Half-metallic transformation has also been revealed via suitable p-type or n-type doping for these structures. Finally, transport calculations were performed to highlight the selective contributions of spin-down (spin-up) electrons in the I–V characteristics of the doped 2H−H ZGeNR, suggesting their vitality for spintronic device applications.

  8. Asymmetric Bessel-Gauss beams. (United States)

    Kotlyar, V V; Kovalev, A A; Skidanov, R V; Soifer, V A


    We propose a three-parameter family of asymmetric Bessel-Gauss (aBG) beams with integer and fractional orbital angular momentum (OAM). The aBG beams are described by the product of a Gaussian function by the nth-order Bessel function of the first kind of complex argument, having finite energy. The aBG beam's asymmetry degree depends on a real parameter c≥0: at c=0, the aBG beam is coincident with a conventional radially symmetric Bessel-Gauss (BG) beam; with increasing c, the aBG beam acquires a semicrescent shape, then becoming elongated along the y axis and shifting along the x axis for c≫1. In the initial plane, the intensity distribution of the aBG beams has a countable number of isolated optical nulls on the x axis, which result in optical vortices with unit topological charge and opposite signs on the different sides of the origin. As the aBG beam propagates, the vortex centers undergo a nonuniform rotation with the entire beam about the optical axis (c≫1), making a π/4 turn at the Rayleigh range and another π/4 turn after traveling the remaining distance. At different values of the c parameter, the optical nulls of the transverse intensity distribution change their position, thus changing the OAM that the beam carries. An isolated optical null on the optical axis generates an optical vortex with topological charge n. A vortex laser beam shaped as a rotating semicrescent has been generated using a spatial light modulator.

  9. The mechanism of asymmetric pipe-wall thinning behind an orifice by combined effect of swirling flow and orifice bias

    Energy Technology Data Exchange (ETDEWEB)

    Fujisawa, Nobuyuki [Visualization Research Center, Niigata University, 8050, Ikarashi 2-Nocho, Nishi-ku, Niigata 950-2181 (Japan); Yamagata, Takayuki, E-mail: [Visualization Research Center, Niigata University, 8050, Ikarashi 2-Nocho, Nishi-ku, Niigata 950-2181 (Japan); Kanno, Syo; Ito, Akihiro [Graduate School of Science and Technology, Niigata University, 8050, Ikarashi 2-Nocho, Nishi-ku, Niigata 950-2181 (Japan); Takano, Tsuyoshi [Visualization Research Center, Niigata University, 8050, Ikarashi 2-Nocho, Nishi-ku, Niigata 950-2181 (Japan)


    Highlights: Black-Right-Pointing-Pointer The mechanism of asymmetric pipe-wall thinning is clarified. Black-Right-Pointing-Pointer Flow fields and pipe-wall thinning are evaluated experimentally for orifice flow. Black-Right-Pointing-Pointer We demonstrate combined effects of swirling flows and orifice biases on flows. Black-Right-Pointing-Pointer Strong swirling flows and orifice biases cause an asymmetric pipe-wall thinning. - Abstract: In this paper, the mechanism of asymmetric pipe-wall thinning caused by flow accelerated corrosion behind an orifice in a circular pipe is studied by measuring the velocity fields by PIV and the mass transfer coefficients by naphthalene sublimation method. An attention is placed on the variations of the velocity fields and mass flux under the combined effect of swirling flow and orifice bias. The present measurement indicates that the flow field become asymmetric about the pipe axis due to the influence of swirling flow at large swirl intensity S = 0.3 in combination with an allowable orifice bias as small as 0.8% of a pipe diameter of standard steel pipes. This flow phenomenon results in the asymmetric distribution of mass transfer coefficient along the pipe-wall behind the orifice. The position of enhanced mass transfer occurs on the shorter orifice side near the orifice due to the flow reattachment, while the flow on the longer orifice side remains the same distribution of mass transfer coefficient as the case without swirl. These variations of velocity field and mass transfer data suggest that the mechanism of asymmetric pipe-wall thinning behind the orifice is due to the combined effect of swirling flow and orifice bias.

  10. Redox-controlled hydrogen bonding: turning a superbase into a strong hydrogen-bond donor. (United States)

    Wild, Ute; Neuhäuser, Christiane; Wiesner, Sven; Kaifer, Elisabeth; Wadepohl, Hubert; Himmel, Hans-Jörg


    Herein the synthesis, structures and properties of hydrogen-bonded aggregates involving redox-active guanidine superbases are reported. Reversible hydrogen bonding is switched on by oxidation of the hydrogen-donor unit, and leads to formation of aggregates in which the hydrogen-bond donor unit is sandwiched by two hydrogen-bond acceptor units. Further oxidation (of the acceptor units) leads again to deaggregation. Aggregate formation is associated with a distinct color change, and the electronic situation could be described as a frozen stage on the way to hydrogen transfer. A further increase in the basicity of the hydrogen-bond acceptor leads to deprotonation reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Complexation-tailored morphology of asymmetric block copolymer membranes

    KAUST Repository

    Madhavan, Poornima


    Hydrogen-bond formation between polystyrene-b-poly (4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) and -OH/-COOH functionalized organic molecules was used to tune morphology of asymmetric nanoporous membranes prepared by simultaneous self-assembly and nonsolvent induced phase separation. The morphologies were characterized by field emmision scanning electron microscopy (FESEM) and atomic force microscopy (AFM). Hydrogen bonds were confirmed by infrared (IR), and the results were correlated to rheology characterization. The OH-functionalized organic molecules direct the morphology into hexagonal order. COOH-functionalized molecules led to both lamellar and hexagonal structures. Micelle formation in solutions and their sizes were determined using dynamic light scattering (DLS) measurements and water fluxes of 600-3200 L/m 2·h·bar were obtained. The pore size of the plain BCP membrane was smaller than with additives. The following series of additives led to pores with hexagonal order with increasing pore size: terephthalic acid (COOH-bifunctionalized) < rutin (OH-multifunctionalized) < 9-anthracenemethanol (OH-monofunctionalized) < 3,5-dihydroxybenzyl alcohol (OH-trifunctionalized). © 2013 American Chemical Society.

  12. Hydrogen storage via polyhydride complexes

    Energy Technology Data Exchange (ETDEWEB)

    Jensen, C.M. [Univ. of Hawaii, Honolulu, HI (United States)


    Polyhydride metal complexes are being developed for application to hydrogen storage. Complexes have been found which catalyze the reversible hydrogenation of unsaturated hydrocarbons. This catalytic reaction could be the basis for a low temperature, hydrogen storage system with a available hydrogen density greater than 7 weight percent. The P-C-P pincer complexes, RhH{sub 2}(C{sub 6}H{sub 3}-2,6-(CH{sub 2}PBu{sup t}{sub 2}){sub 2}) and IrH{sub 2}(C{sub 6}H{sub 3}-2,6-(CH{sub 2}PBu{sup t}{sub 2}){sub 2}) have unprecedented, long term stability at elevated temperatures. The novel iridium complex catalyzes the transfer dehydrogenation of cycloctane to cyclooctene at the rate of 716 turnovers/h which is 2 orders of magnitude greater than that found for previously reported catalytic systems which do not require the sacrificial hydrogenation of a large excess of hydrogen acceptor.

  13. Magnetic refrigerator for hydrogen liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Numazawa, T [National Institute for Materials Science, Tsukuba (Japan); Kamlya, K. [Japan Atomic Energy Agency, Naka (Japan); Utaki, T. [Osaka University, Osaka (Japan); Matsumoto, K. [Kanazawa University, Kanazawa (Japan)


    This paper reviews the development status of magnetic refrigeration system for hydrogen liquefaction. There is no doubt that hydrogen is one of most important energy sources in the near future. In particular, liquid hydrogen can be utilized for infrastructure construction consisting of storage and transportation. Liquid hydrogen is in cryogenic temperatures and therefore high efficient liquefaction method must be studied. Magnetic refrigeration which uses the magneto-caloric effect has potential to realize not only the higher liquefaction efficiency > 50 %, but also to be environmentally friendly and cost effective. Our hydrogen magnetic refrigeration system consists of Carnot cycle for liquefaction stage and AMR (active magnetic regenerator) cycle for precooling stages. For the Carnot cycle, we develop the high efficient system > 80 % liquefaction efficiency by using the heat pipe. For the AMR cycle, we studied two kinds of displacer systems, which transferred the working fluid. We confirmed the AMR effect with the cooling temperature span of 12 K for 1.8 T of the magnetic field and 6 second of the cycle. By using the simulation, we estimate the total efficiency of the hydrogen liquefaction plant for 10 kg/day. A FOM of 0.47 is obtained in the magnetic refrigeration system operation temperature between 20 K and 77 K including LN2 work input.

  14. Highly hydrogenated graphene through microwave exfoliation of graphite oxide in hydrogen plasma: towards electrochemical applications. (United States)

    Eng, Alex Yong Sheng; Sofer, Zdenek; Šimek, Petr; Kosina, Jiri; Pumera, Martin


    Hydrogenated graphenes exhibit a variety of properties with potential applications in devices, ranging from a tunable band gap to fluorescence, ferromagnetism, and the storage of hydrogen. We utilize a one-step microwave-irradiation process in hydrogen plasma to create highly hydrogenated graphene from graphite oxides. The procedure serves the dual purposes of deoxygenation and concurrent hydrogenation of the carbon backbone. The effectiveness of the hydrogenation process is investigated on three different graphite oxides (GOs), which are synthesized by using the Staudenmaier, Hofmann, and Hummers methods. A systematic characterization of our hydrogenated graphenes is performed using UV/Vis spectroscopy, SEM, AFM, Raman spectroscopy, FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), combustible elemental analysis, and electrical conductivity measurements. The highest hydrogenation extent is observed in hydrogenated graphene produced from the Hummers-method GO, with a hydrogen content of 19 atomic % in the final product. In terms of the removal of oxygen groups, microwave exfoliation yields graphenes with very similar oxygen contents despite differences in their parent GOs. In addition, we examine the prospective application of hydrogenated graphenes as electrochemical transducers through a cyclic voltammetry (CV) study. The highly hydrogenated graphenes exhibit fast heterogeneous electron-transfer rates, suggestive of their suitability for electrochemical applications in electrodes, supercapacitors, batteries, and sensors. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Influence of Adsorption Geometry in the Heterogeneous Enantioselective Catalytic Hydrogenation of a Prototypical Enone


    Beaumont, SK; Kyriakou, G; Watson, DJ; Vaughan, OPH; Papageorgiou, AC; Lambert, RM


    Asymmetric catalysis is of paramount importance in organic synthesis and, in current practice, is achieved by means of homogeneous catalysts. The ability to catalyze such reactions heterogeneously would have a major impact both in the research laboratory and in the production of fine chemicals and pharmaceuticals, yet heterogeneous asymmetric hydrogenation of C═C bonds remains hardly explored. Very recently, we demonstrated how chiral ligands that anchor robustly to the surface of Pd nanopart...

  16. Electrochemical Hydrogen Peroxide Generator (United States)

    Tennakoon, Charles L. K.; Singh, Waheguru; Anderson, Kelvin C.


    Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials

  17. The hydrogen; L'hydrogene

    Energy Technology Data Exchange (ETDEWEB)



    The hydrogen as an energy system represents nowadays a main challenge (in a scientific, economical and environmental point of view). The physical and chemical characteristics of hydrogen are at first given. Then, the challenges of an hydrogen economy are explained. The different possibilities of hydrogen production are described as well as the distribution systems and the different possibilities of hydrogen storage. Several fuel cells are at last presented: PEMFC, DMFC and SOFC. (O.M.)

  18. Asymmetrical soft palate cleft repair: preliminary results. (United States)

    Bütow, K-W; Engelbrecht, H; Naidoo, S


    The reconstructions of the asymmetrical soft palate cleft is a surgical challenge when it comes to achieving symmetry and optimal soft palate muscular function. Three different versions of the intravelar veloplasty have been used: the intravelar veloplasty (1969) (type I), the modification according to anatomical defects (1991) (type II), and the modification using part of Sommerlad's technique and part of Ivanov's technique (2008) (type III). The perioperative outcomes of the type II and type III intravelar veloplasty were assessed and compared in asymmetrical cleft cases. Two hundred and seventy-seven soft palate clefts were reconstructed: 153 type II and 124 type III. Of these, 49 were asymmetrical (17.7%); 23 underwent the type II procedure and 26 the type III procedure. Of the type II procedure cases, 30.4% remained asymmetrical postoperatively compared to 3.8% of the type III cases. The uvula appeared subjectively atrophic in 47.8% of the type II cases and in 7.7% of type III cases. Oro-nasal fistula occurred in 13.0% of the type II cases and 3.8% of the type III cases. Speech results will only be assessed after 4 years of age. The type III modified intravelar veloplasty has had a major beneficial impact on patients who had an asymmetrical soft palate cleft. Copyright © 2014. Published by Elsevier Ltd.

  19. Control of apoptosis by asymmetric cell division. (United States)

    Hatzold, Julia; Conradt, Barbara


    Asymmetric cell division and apoptosis (programmed cell death) are two fundamental processes that are important for the development and function of multicellular organisms. We have found that the processes of asymmetric cell division and apoptosis can be functionally linked. Specifically, we show that asymmetric cell division in the nematode Caenorhabditis elegans is mediated by a pathway involving three genes, dnj-11 MIDA1, ces-2 HLF, and ces-1 Snail, that directly control the enzymatic machinery responsible for apoptosis. Interestingly, the MIDA1-like protein GlsA of the alga Volvox carteri, as well as the Snail-related proteins Snail, Escargot, and Worniu of Drosophila melanogaster, have previously been implicated in asymmetric cell division. Therefore, C. elegans dnj-11 MIDA1, ces-2 HLF, and ces-1 Snail may be components of a pathway involved in asymmetric cell division that is conserved throughout the plant and animal kingdoms. Furthermore, based on our results, we propose that this pathway directly controls the apoptotic fate in C. elegans, and possibly other animals as well.

  20. Control of apoptosis by asymmetric cell division.

    Directory of Open Access Journals (Sweden)

    Julia Hatzold


    Full Text Available Asymmetric cell division and apoptosis (programmed cell death are two fundamental processes that are important for the development and function of multicellular organisms. We have found that the processes of asymmetric cell division and apoptosis can be functionally linked. Specifically, we show that asymmetric cell division in the nematode Caenorhabditis elegans is mediated by a pathway involving three genes, dnj-11 MIDA1, ces-2 HLF, and ces-1 Snail, that directly control the enzymatic machinery responsible for apoptosis. Interestingly, the MIDA1-like protein GlsA of the alga Volvox carteri, as well as the Snail-related proteins Snail, Escargot, and Worniu of Drosophila melanogaster, have previously been implicated in asymmetric cell division. Therefore, C. elegans dnj-11 MIDA1, ces-2 HLF, and ces-1 Snail may be components of a pathway involved in asymmetric cell division that is conserved throughout the plant and animal kingdoms. Furthermore, based on our results, we propose that this pathway directly controls the apoptotic fate in C. elegans, and possibly other animals as well.

  1. A sampling theory for asymmetric communities. (United States)

    Noble, Andrew E; Temme, Nico M; Fagan, William F; Keitt, Timothy H


    We introduce the first analytical model of asymmetric community dynamics to yield Hubbell's neutral theory in the limit of functional equivalence among all species. Our focus centers on an asymmetric extension of Hubbell's local community dynamics, while an analogous extension of Hubbell's metacommunity dynamics is deferred to an appendix. We find that mass-effects may facilitate coexistence in asymmetric local communities and generate unimodal species abundance distributions indistinguishable from those of symmetric communities. Multiple modes, however, only arise from asymmetric processes and provide a strong indication of non-neutral dynamics. Although the exact stationary distributions of fully asymmetric communities must be calculated numerically, we derive approximate sampling distributions for the general case and for nearly neutral communities where symmetry is broken by a single species distinct from all others in ecological fitness and dispersal ability. In the latter case, our approximate distributions are fully normalized, and novel asymptotic expansions of the required hypergeometric functions are provided to make evaluations tractable for large communities. Employing these results in a bayesian analysis may provide a novel statistical test to assess the consistency of species abundance data with the neutral hypothesis. Copyright © 2010 Elsevier Ltd. All rights reserved.

  2. Low Viscosity Imides Based on Asymmetric Oxydiphthalic Anhydride (United States)

    Chuang, Kathy C.; Criss, Jim M., Jr.; Mintz, Eric A.; Scheiman, Daniel A.; Nguyen, Baochau N.; McCorkle, Linda S.


    A series of low-melt viscosity imide resins were prepared from asymmetric oxydiphthalic dianhydride (a-ODPA) and 4-phenylethynylphthalic anhydride as the endcap, along with 3,4' - oxydianiline (3,4' -ODA), 3,4' -methylenedianiline (3,4' -MDA), 3,3' -methylenedianiline (3,3' - MDA) and 3,3'-diaminobenzophenone (3,3'-DABP), using a solvent-free melt process. These imide oligomers displays low-melt viscosities (2-15 poise) at 260-280 C, which made them amenable to low-cost resin transfer molding (RTM) process. The a-ODPA based RTM resins exhibits glass transition temperatures (Tg's) in the range of 265-330 C after postcure at 343 C. The mechanical properties of these polyimide/carbon fiber composites fabricated by RTM will be discussed.

  3. Asymmetric similarity-weighted ensembles for image segmentation

    DEFF Research Database (Denmark)

    Cheplygina, V.; Van Opbroek, A.; Ikram, M. A.


    Supervised classification is widely used for image segmentation. To work effectively, these techniques need large amounts of labeled training data, that is representative of the test data. Different patient groups, different scanners or different scanning protocols can lead to differences between...... the images, thus representative data might not be available. Transfer learning techniques can be used to account for these differences, thus taking advantage of all the available data acquired with different protocols. We investigate the use of classifier ensembles, where each classifier is weighted...... according to the similarity between the data it is trained on, and the data it needs to segment. We examine 3 asymmetric similarity measures that can be used in scenarios where no labeled data from a newly introduced scanner or scanning protocol is available. We show that the asymmetry is informative...

  4. Synthesis of New Chiral Ligands Based on Thiophene Derivatives for Use in Catalytic Asymmetric Oxidation of Sulfides

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Yong Chul; Ahn, Dae Jun; Lee, Woo Sun; Lee, Seung Han; Ahn, Kwang Hyun [Chonnam National University, Gwangju (Korea, Republic of)


    We discovered that the vanadium complexes of new Schiff base ligands and prepared from thiophene derivatives efficiently catalyze the asymmetric oxidation of sulfides by hydrogen peroxide to provide sulfoxides with enantioselectivities up to 79% ee and in yields up to 89%. Notably, Schiff base showed better or similar enantioselectivity than the well-studied Schiff base. These results suggest possible applications of Schiff bases derived from and in other catalytic asymmetric reactions. Chiral sulfoxides are important functional groups for various applications. For example, the biological activities of sulfoxide containing drugs such as omeprazole are strongly related to the chirality of the sulfoxide group; for this reason, esomeprazole, the enantiomerically pure form of omeprazole, was later developed. There are several chiral sulfoxide based drugs that have been introduced by the pharmaceutical industry including armodafinil, aprikalim, oxisurane, and ustiloxin. Chiral sulfoxides have also been utilized as chiral auxiliaries in asymmetric syntheses of chiral intermediates.

  5. Reverse osmosis separation of some metal ions from mining effluents using heterogeneous asymmetric membranes

    Energy Technology Data Exchange (ETDEWEB)

    Gashi, S.T.; Daci, N.M.; Selimi, T.J. (University of Prishtina, Prishtine (Yugoslavia). Dept. of Chemistry, Faculty of Science)


    Heterogeneous asymmetric membranes made from a blend of cellulose acetate and powdered coal were studied. The membranes were characterized in terms of pure water permeability constant A, solute transport parameter D[sub AM]/K[delta] and mass transfer coefficient k of sodium chloride solution as the reference system. These membranes were used for treatment of mining and industrial effluents. Good separation and very high productivity were obtained at low operating pressure. (author). 3 refs, 3 tabs.

  6. Asymmetric microscope. Fusho no kenbisho [exclamation point

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Tadashi. (Tokyo Institute of Technology, Tokyo (Japan))


    It is difficult for a conventional optical analysis means to determine the configuration of a substance with an ultra low optical purity. Recently, an asymmetric microscope has been reported as a new concept for solving the above-mentioned problem. Specifically, a product with slight asymmetry is obtained by using the substance with an ultra low optical purity as the chiral initiation, and then the asymmetry of the product is amplified dramatically due to the asymmetric autocatalysis, thus obtaining a product having a high optical purity. A new means is to determine the configuration of the original substance having the low optical purity from the configuration of the substance having the high optical purity. According to this method, the chirality of the substance having the low optical purity is transcribed to alkanol, and the chirality is amplified due to the asymmetric autocatalysis, thus the absolute configuration of the original compound can be determined from the absolute configuration of the final product. (NEDO)

  7. Multi-agent Bargaining under Asymmetric Information

    DEFF Research Database (Denmark)

    Asplund, Marcus; Genesove, David

    information aspect is due to partly unobserved individual valuations of an elevator. We tailor Hellwig (2003) to the features of the retrofitting problem and use this to predict which building characteristics should make it easier for owners to agree. Data from Copenhagen broadly support the model......It is well know that asymmetric information might lead to underprovision of public goods. To test the theoretical prediction, we study the decision to retrofit an elevator into an old apartment building, in which each owner has to agree on how the investment cost is split. The asymmetric......'s predictions. We use transaction data to estimate the market value of an elevator and conclude that for approximately 30-40 percent of the buildings without an elevator the aggregate increase in value exceeds the investment cost....

  8. Asymmetric synthesis II more methods and applications

    CERN Document Server

    Christmann, Mathias


    After the overwhelming success of 'Asymmetric Synthesis - The Essentials', narrating the colorful history of asymmetric synthesis, this is the second edition with latest subjects and authors. While the aim of the first edition was mainly to honor the achievements of the pioneers in asymmetric syntheses, the aim of this new edition was bringing the current developments, especially from younger colleagues, to the attention of students. The format of the book remained unchanged, i.e. short conceptual overviews by young leaders in their field including a short biography of the authors. The growing multidisciplinary research within chemistry is reflected in the selection of topics including metal catalysis, organocatalysis, physical organic chemistry, analytical chemistry, and its applications in total synthesis. The prospective reader of this book is a graduate or undergraduate student of advanced organic chemistry as well as the industrial chemist who wants to get a brief update on the current developments in th...

  9. Pad B Liquid Hydrogen Storage Tank (United States)

    Hall, Felicia


    Kennedy Space Center is home to two liquid hydrogen storage tanks, one at each launch pad of Launch Complex 39. The liquid hydrogen storage tank at Launch Pad B has a significantly higher boil off rate that the liquid hydrogen storage tank at Launch Pad A. This research looks at various calculations concerning the at Launch Pad B in an attempt to develop a solution to the excess boil off rate. We will look at Perlite levels inside the tank, Boil off rates, conductive heat transfer, and radiant heat transfer through the tank. As a conclusion to the research, we will model the effects of placing an external insulation to the tank in order to reduce the boil off rate and increase the economic efficiency of the liquid hydrogen storage tanks.

  10. Project H - A Complete Spaceport Hydrogen Solution (United States)

    Notardonato, William


    This slide presentation reviews Project H, and its importance in the development of Kennedy Space Center (KSC) as a Spaceport capable of multiple launches. It is known that current KSC cryogenic technology results in only approximately 55 % of purchased hydrogen being used. The rest is lost at various points in the process: transfer from transporting vehicle to tank, storage tank boil off, and from the tank to the intended propulsion tanks. Project H's goals would be to have local hydrogen production and liquifaction capability, and to increase the efficiency of hydrogen operations to greater than 80 %. The project envisions two phases: Phase 1 will build a smaller scale demonstration system, and phase 2 will build a full scale spaceport system. This initial project has proposed ideas for local hydrogen production, gaseous distribution, integrated refrigeration and storage, and high efficiency transfer lines that merit further investigation.

  11. Algebraic Davis decomposition and asymmetric Doob inequalities


    Hong, Guixiang; Junge, Marius; Parcet, Javier


    In this paper we investigate asymmetric forms of Doob maximal inequality. The asymmetry is imposed by noncommutativity. Let $(\\M,\\tau)$ be a noncommutative probability space equipped with a weak-$*$ dense filtration of von Neumann subalgebras $(\\M_n)_{n \\ge 1}$. 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 $x \\in L_p(\\M,\\tau)$ one can find $a, b \\in L_p(\\M,\\tau)$ and contractions $u_n, v_...

  12. Asymmetric multiscale behavior in PM2.5 time series: Based on asymmetric MS-DFA (United States)

    Zhang, Chen; Ni, Zhiwei; Ni, Liping


    Particulate matter with an aerodynamic diameter of 2.5 mm or less (PM2.5) is one of the most serious air pollution, considered most harmful for people by World Health Organisation. In this paper, we utilized the asymmetric multiscale detrended fluctuation analysis (A-MSDFA) method to explore the existence of asymmetric correlation properties for PM2.5 daily average concentration in two USA cities (Fresno and Los Angeles) and two Chinese cities (Hong Kong and Shanghai), and to assess the properties of these asymmetric correlations. The results show the existences of asymmetric correlations, and the degree of asymmetric for two USA cities is stronger than that of two Chinese cities. Further, most of the local exponent β(n) are smaller than 0.5, which indicates the existence of anti-persistent long-range correlation for PM2.5 time series in four cities. In addition, we reanalyze the asymmetric correlation by the A-MSDFA method with secant rolling windows of different sizes, which can investigate dynamic changes in the multiscale correlation for PM2.5 time series with changing window size. Whatever window sizes, the correlations are asymmetric and display smaller asymmetries at small scales and larger asymmetries at large scales. Moreover, the asymmetries become increasingly weaker with the increase of window sizes.

  13. Cell-sized asymmetric lipid vesicles facilitate the investigation of asymmetric membranes (United States)

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


    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.

  14. Effects of electron transfer on the stability of hydrogen bonds† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc03361c Click here for additional data file. (United States)

    Porter, Tyler M.; Heim, Gavin P.


    The measurement of the dimerization constants of hydrogen-bonded ruthenium complexes (1 2, 2 2, 3 2) linked by a self-complementary pair of 4-pyridylcarboxylic acid ligands in different redox states is reported. Using a combination of FTIR and UV/vis/NIR spectroscopies, the dimerization constants (K D) of the isovalent, neutral states, 1 2, 2 2, 3 2, were found to range from 75 to 130 M–1 (ΔG 0 = –2.56 to –2.88 kcal mol–1), while the dimerization constants (K 2–) of the isovalent, doubly-reduced states, (1 2)2–, (2 2)2–, (3 2)2–, were found to range from 2000 to 2500 M–1 (ΔG 0 = –4.5 to –4.63 kcal mol–1). From the aforementioned values and the comproportionation constant for the mixed-valent dimers, the dimerization constants (K MV) of the mixed-valent, hydrogen-bonded dimers, (1 2)–, (2 2)–, (3 2)–, were found to range from 0.5 × 106 to 1.2 × 106 M–1 (ΔG 0 = –7.78 to –8.31 kcal mol–1). On average, the hydrogen-bonded, mixed-valent states are stabilized by –5.27 (0.04) kcal mol–1 relative to the isovalent, neutral, hydrogen-bonded dimers and –3.47 (0.06) kcal mol–1 relative to the isovalent, dianionic hydrogen bonded dimers. Electron exchange in the mixed valence states imparts significant stability to hydrogen bonding. This is the first quantitative measurement of the strength of hydrogen bonds in the presence and absence of electronic exchange. PMID:29163883

  15. Heavy hydrogen in the stratosphere

    Directory of Open Access Journals (Sweden)

    T. Röckmann


    Full Text Available We report measurements of the deuterium content of molecular hydrogen (H2 obtained from a suite of air samples that were collected during a stratospheric balloon flight between 12 and 33 km at 40º N in October 2002. Strong deuterium enrichments of up to 400 permil versus Vienna Standard Mean Ocean Water (VSMOW are observed, while the H2 mixing ratio remains virtually constant. Thus, as hydrogen is processed through the H2 reservoir in the stratosphere, deuterium is accumulated in H2 . Using box model calculations we investigated the effects of H2 sources and sinks on the stratospheric enrichments. Results show that considerable isotope enrichments in the production of H2  from CH4 must take place, i.e., deuterium is transferred preferentially to H2 during the CH4 oxidation sequence. This supports recent conclusions from tropospheric H2 isotope measurements which show that H2 produced photochemically from CH4 and non-methane hydrocarbons must be enriched in deuterium to balance the tropospheric hydrogen isotope budget. In the absence of further data on isotope fractionations in the individual reaction steps of the CH4 oxidation sequence, this effect cannot be investigated further at present. Our measurements imply that molecular hydrogen has to be taken into account when the hydrogen isotope budget in the stratosphere is investigated.

  16. Influence of convective conditions in radiative peristaltic flow of pseudoplastic nanofluid in a tapered asymmetric channel (United States)

    Hayat, T.; Iqbal, Rija; Tanveer, Anum; Alsaedi, A.


    This paper looks at the influences of magnetohydrodynamics (MHD) and thermal radiation on peristaltic transport of a pseudoplastic nanofluid in a tapered asymmetric channel. The tapered channel walls satisfy convective boundary conditions. The governing equations for the balance of mass, momentum, temperature and volume fraction for pseudoplastic nanofluid are first formulated and then utilized for long wavelength and small Reynolds number considerations. Effects of involved parameters on the flow characteristics have been plotted and examined. It is observed that the heat transfer Biot number shows a dual behavior on the temperature of nanofluid particles whereas the mass transfer Biot number with its increasing values enhances the fluid temperature.

  17. Asymmetric cyclopropanation of β,γ-unsaturated α-ketoesters with stabilized sulfur ylides catalyzed by C2-symmetric ureas. (United States)

    Cheng, Ying; An, Jing; Lu, Liang-Qiu; Luo, Lan; Wang, Zheng-Yi; Chen, Jia-Rong; Xiao, Wen-Jing


    A novel organocatalytic asymmetric cyclopropanation of β,γ-unsaturated α-ketoesters with stabilized sulfur ylides using C(2)-symmetric urea as a hydrogen-bond catalyst has been described. This reaction allows an efficient access to 1,2,3-trisubstituted cyclopropane derivatives in moderate to good yields with up to 16:1 dr and 90:10 er under mild reaction conditions. The mechanism study proved that the high stereoinduction originated from the cooperative effect of the hydrogen-bond catalyst.

  18. Crystal structure of 2-methylpiperazine-1,4-diium bis(hydrogen maleate

    Directory of Open Access Journals (Sweden)

    Intissar Wecharine


    Full Text Available In the title salt, C5H14N22+·2C4H3O4−, the asymmetric unit contains two independent 2-methylpiperazinium dications, which comprise a racemic pair, and four hydrogen maleate monoanions. In the roughly planar hydrogen maleate anions, intramolecular O—H...O hydrogen bonds generate S(7 rings. In the crystal, the four independent anions are linked to the 2-methylpiperazinium cations through N—H...O hydrogen bonds, forming two-dimensional layered structures lying parallel to (001.

  19. RSA Asymmetric Cryptosystem beyond Homogeneous Transformation

    African Journals Online (AJOL)



    Dec 1, 2013 ... The Internet is an insecure open network and its use and connectivity have witnessed a significant growth, and this has made it vulnerable to all forms of attacks. A threat to a network can cause harm or interrupt the network. In this paper, we looked at the security of data and message, using asymmetric.

  20. Settling dynamics of asymmetric rigid fibers (United States)

    E.J. Tozzi; C Tim Scott; David Vahey; D.J. Klingenberg


    The three-dimensional motion of asymmetric rigid fibers settling under gravity in a quiescent fluid was experimentally measured using a pair of cameras located on a movable platform. The particle motion typically consisted of an initial transient after which the particle approached a steady rate of rotation about an axis parallel to the acceleration of gravity, with...

  1. Spatially inhomogeneous condensate in asymmetric nuclear matter

    NARCIS (Netherlands)

    Sedrakian, A

    We study the isospin singlet pairing in asymmetric nuclear matter with nonzero total momentum of the condensate Cooper pairs. The quasiparticle excitation spectrum is fourfold split compared to the usual BCS spectrum of the symmetric, homogeneous matter. A twofold splitting of the spectrum into

  2. Asymmetric volatility connectedness on the forex market

    Czech Academy of Sciences Publication Activity Database

    Baruník, Jozef; Kočenda, Evžen; Vácha, Lukáš


    Roč. 77, č. 1 (2017), s. 39-56 ISSN 0261-5606 R&D Projects: GA ČR(CZ) GA16-14179S Institutional support: RVO:67985556 Keywords : volatility * connectedness * asymmetric effects Subject RIV: AH - Economics Impact factor: 1.853, year: 2016 http:// library

  3. Asymmetric Drift and the Stellar Velocity Ellipsoid

    NARCIS (Netherlands)

    Westfall, Kyle B.; Bershady, Matthew A.; Verheijen, Marc A. W.; Andersen, David R.; Swaters, Rob A.


    We present the decomposition of the stellar velocity ellipsoid using stellar velocity dispersions within a 40° wedge about the major-axis (smaj), the epicycle approximation, and the asymmetric drift equation. Thus, we employ no fitted forms for smaj and escape interpolation errors resulting from

  4. Dynamic Conditional Correlations for Asymmetric Processes

    NARCIS (Netherlands)

    M. Asai (Manabu); M.J. McAleer (Michael)


    textabstractThe paper develops two Dynamic Conditional Correlation (DCC) models, namely the Wishart DCC (WDCC) model and the Matrix-Exponential Conditional Correlation (MECC) model. The paper applies the WDCC approach to the exponential GARCH (EGARCH) and GJR models to propose asymmetric DCC models.

  5. Asymmetric conditional volatility in international stock markets (United States)

    Ferreira, Nuno B.; Menezes, Rui; Mendes, Diana A.


    Recent studies show that a negative shock in stock prices will generate more volatility than a positive shock of similar magnitude. The aim of this paper is to appraise the hypothesis under which the conditional mean and the conditional variance of stock returns are asymmetric functions of past information. We compare the results for the Portuguese Stock Market Index PSI 20 with six other Stock Market Indices, namely the SP 500, FTSE 100, DAX 30, CAC 40, ASE 20, and IBEX 35. In order to assess asymmetric volatility we use autoregressive conditional heteroskedasticity specifications known as TARCH and EGARCH. We also test for asymmetry after controlling for the effect of macroeconomic factors on stock market returns using TAR and M-TAR specifications within a VAR framework. Our results show that the conditional variance is an asymmetric function of past innovations raising proportionately more during market declines, a phenomenon known as the leverage effect. However, when we control for the effect of changes in macroeconomic variables, we find no significant evidence of asymmetric behaviour of the stock market returns. There are some signs that the Portuguese Stock Market tends to show somewhat less market efficiency than other markets since the effect of the shocks appear to take a longer time to dissipate.

  6. Spectral inequalities for the quantum asymmetric top

    Energy Technology Data Exchange (ETDEWEB)

    Bourget, Alain; McMillen, Tyler [Department of Mathematics, California State University (Fullerton), McCarthy Hall 154, Fullerton, CA 92834 (United States)], E-mail:, E-mail:


    We consider the spectrum of the quantum asymmetric top. Unlike in the case when two or three moments of inertia are equal, when the moments of inertia are distinct all degeneracy in the spectrum of the operator is removed. We derive inequalities for the spectra based on recent results on the interlacing of Van Vleck zeros.

  7. Palladium catalysed asymmetric alkylation of benzophenone Schiff ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 4. Palladium catalysed asymmetric alkylation of benzophenone Schiff base glycine esters in ionic liquids. Dae Hyun Kim Jin Kyu Im Dae Won Kim Minserk Cheong Hoon Sik Kim Deb Kumar Mukherjee. Volume 123 Issue 4 July 2011 pp 467-476 ...

  8. RSA Asymmetric Cryptosystem beyond Homogeneous Transformation

    African Journals Online (AJOL)

    The Internet is an insecure open network and its use and connectivity have witnessed a significant growth, and this has made it vulnerable to all forms of attacks. A threat to a network can cause harm or interrupt the network. In this paper, we looked at the security of data and message, using asymmetric cryptography, with ...

  9. Mixed gas plasticization phenomena in asymmetric membranes

    NARCIS (Netherlands)

    Visser, Tymen


    This thesis describes the thorough investigation of mixed gas transport behavior of asymmetric membranes in the separation of feed streams containing plasticizing gases in order to gain more insights into the complicated behavior of plasticization. To successfully employ gas separation membranes in

  10. Study of coupled heat and mass transfer during absorption of ...

    Indian Academy of Sciences (India)

    Performance studies on MmNi4·6Al0·4 based hydrogen storage device are carried out by varying the hydrogen supply pressure, absorption (cooling fluid) temperature, overall heat transfer coefficient and hydride bed thickness. Effect of convection terms in the energy equation on hydrogen storage performance is found to ...

  11. Charge Asymmetric Cosmic Rays as a probe of Flavor Violating Asymmetric Dark Matter

    DEFF Research Database (Denmark)

    Masina, Isabella; Sannino, Francesco


    The recently introduced cosmic sum rules combine the data from PAMELA and Fermi-LAT cosmic ray experiments in a way that permits to neatly investigate whether the experimentally observed lepton excesses violate charge symmetry. One can in a simple way determine universal properties of the unknown...... component of the cosmic rays. Here we attribute a potential charge asymmetry to the dark sector. In particular we provide models of asymmetric dark matter able to produce charge asymmetric cosmic rays. We consider spin zero, spin one and spin one-half decaying dark matter candidates. We show that lepton...... flavor violation and asymmetric dark matter are both required to have a charge asymmetry in the cosmic ray lepton excesses. Therefore, an experimental evidence of charge asymmetry in the cosmic ray lepton excesses implies that dark matter is asymmetric....

  12. A Novel Bis-Thiourea Organocatalyst for the Asymmetric Aza-Henry Reaction (United States)

    Rampalakos, Constantinos; Wulff, William D.


    A novel bis-thiourea BINAM-based catalyst for the asymmetric aza-Henry reaction has been developed. This catalyst promotes the reaction of N-Boc imines with nitroalkanes to afford β-nitroamines with good yields and high enantioselectivities. This catalyst has the advantage that it can be prepared in a single step from commercially available materials. A model is proposed for the catalyst action where the both components of the reaction are activated simultaneously by hydrogen bonding. Regardless of the mechanism, the success of the present catalyst demonstrates the potential of bis-thioureas as an interesting class of relatively unexplored catalysts. PMID:23795151

  13. Determinant of asymmetric risks in Nigerian loan market: any ...

    African Journals Online (AJOL)

    Bank lending in Nigeria was dominated by the presence of asymmetric information, a wedge to financial intermediation. Using probit and correlation test methodology, evidence of low level asymmetric risk was found and the determinants of asymmetric risks in the market were not significantly different. The size of default ...

  14. Porous asymmetric SiO2-g-PMMA nanoparticles produced by phase inversion

    KAUST Repository

    Munirasu, Selvaraj


    A new kind of asymmetric organic-inorganic porous structure has been proposed. Asymmetric lattices of polymer grafted silica nanoparticles were manufactured by casting and phase inversion in water. Silica nanoparticles were first functionalized with 3-(dimethylethoxysilyl)propyl-2-bromoisobutyrate, followed by grafting of poly(methylmethacrylate) (PMMA) segments, performed by atom-transfer radical polymerization. Mechanically stable self-standing films were prepared by casting a dispersion of functionalized nanoparticles in different solvents and immersion in water. The resulting asymmetrically porous morphology and nanoparticle assembly was characterized by scanning electron and atomic force microscopy. The PMMA functionalized SiO2 hybrid material in acetone or acetone/dioxane led to the best-assembled structures. Porous asymmetric membranes were prepared by adding free PMMA and PMMA terminated with hydrophilic hydroxyl group. Nitrogen flow of 2800 L m-2 h -1 was measured at 1.3 bar demonstrating the porosity and potential application for membrane technology. © 2014 Springer Science+Business Media New York.

  15. Neutron signal transfer analysis

    CERN Document Server

    Pleinert, H; Lehmann, E


    A new method called neutron signal transfer analysis has been developed for quantitative determination of hydrogenous distributions from neutron radiographic measurements. The technique is based on a model which describes the detector signal obtained in the measurement as a result of the action of three different mechanisms expressed by signal transfer functions. The explicit forms of the signal transfer functions are determined by Monte Carlo computer simulations and contain only the distribution as a variable. Therefore an unknown distribution can be determined from the detector signal by recursive iteration. This technique provides a simple and efficient tool for analysis of this type while also taking into account complex effects due to the energy dependency of neutron interaction and single and multiple scattering. Therefore this method provides an efficient tool for precise quantitative analysis using neutron radiography, as for example quantitative determination of moisture distributions in porous buil...

  16. 2-Methyl-1H-benzimidazol-3-ium hydrogen phthalate

    Directory of Open Access Journals (Sweden)

    YuanQi Yu


    Full Text Available The asymmetric unit of the title compound, C8H9N2+·C8H5O4−, contains two independent ion pairs. In each 2-methyl-1H-benzimidazolium ion, an intramolecular O—H...O bond forms an S(7 graph-set motif. In the crystal, the components are linked by N—H...O hydrogen bonds, forming chains along [210]. Further stabilization is provided by weak C—H...O hydrogen bonds.

  17. Photobiological production of hydrogen using cyanobacteria

    Energy Technology Data Exchange (ETDEWEB)

    Borthakur, D.; McKinley, K.R.; Bylina, E.J. [Univ. of Hawaii, Honolulu, HI (United States)


    Cyanobacteria are capable of generating hydrogen using sunlight and water. In both Spirulina and Anabaena, there is a soluble reversible hydrogenase that is involved in hydrogen evolution under anaerobic conditions in the dark. In addition, the nitrogen-fixing cyanobacterium Anabaena produces hydrogen as a by-product of nitrogen fixation. Most of this hydrogen is recaptured by a membrane-bound uptake hydrogenase present in Anabaena cells. Experiments have continued to develop a gene transfer system in Spirulina in preparation for improved hydrogen production via genetic manipulation of the reversible hydrogenase. We have identified and characterized four restriction enzymes in Spirulina and cloned the genes for two methylases that protect their own DNA from cleavage by restriction enzymes. We have also cloned and sequenced parts of hupB and hupM genes involved in the synthesis of uptake hydrogenase in Anabaena. Successful cloning of these hup genes represents an important and necessary step in our project because this will enable us to construct Anabaena strains with enhanced hydrogen production ability by disrupting the hup genes involved in hydrogen uptake. We are also setting up a bio-reactor to determine the amount of hydrogen released by different Spirulina and Anabaena strains under different physiological conditions.

  18. Asymmetric total synthesis of Apocynaceae hydrocarbazole alkaloids (+)-deethylibophyllidine and (+)-limaspermidine. (United States)

    Du, Ji-Yuan; Zeng, Chao; Han, Xiao-Jie; Qu, Hu; Zhao, Xian-He; An, Xian-Tao; Fan, Chun-An


    An unprecedented asymmetric catalytic tandem aminolysis/aza-Michael addition reaction of spirocyclic para-dienoneimides has been designed and developed through organocatalytic enantioselective desymmetrization. A unified strategy based on this key tandem methodology has been divergently explored for the asymmetric total synthesis of two natural Apocynaceae alkaloids, (+)-deethylibophyllidine and (+)-limaspermidine. The present studies not only enrich the tandem reaction design concerning the asymmetric catalytic assembly of a chiral all-carbon quaternary stereocenter contained in the densely functionalized hydrocarbazole synthons but also manifest the potential for the application of the asymmetric catalysis based on the para-dienone chemistry in asymmetric synthesis of natural products.

  19. A hydrogen ice cube

    NARCIS (Netherlands)

    Peters, C.J.; Schoonman, J.; Schrauwers, A.


    Hydrogen is considered to be a highly promising energy carrier. Nonetheless, before hydrogen can become the fuel of choice for the future a number of slight problems will have to be overcome. For example, how can hydrogen be safely stored? Motor vehicles running on hydrogen may be clean in concept

  20. Compressible cell gas models for asymmetric fluid criticality (United States)

    Cerdeiriña, Claudio A.; Orkoulas, Gerassimos


    We thoroughly describe a class of models recently presented by Fisher and coworkers [Phys. Rev. Lett. 116, 040601 (2016)], 10.1103/PhysRevLett.116.040601. The crucial feature of such models, termed compressible cell gases (CCGs), is that the individual cell volumes of a lattice gas are allowed to fluctuate. They are studied via the seldom-used (μ , p , T ) ensemble, which leads to their exact mapping onto the Ising model. Remarkably, CCGs obey complete scaling, a formulation for the thermodynamic behavior of fluids near the gas-liquid critical point that accommodates features inherent to the asymmetric nature of this phase transition like the Yang-Yang (YY) and singular coexistence-curve diameter anomalies. The CCG0 models generated when volumes vary freely reveal local free volume fluctuations as the origin of these phenomena. Local energy-volume coupling is found to be another relevant microscopic factor. Furthermore, the CCG class is greatly extended by using the decoration transformation, with an interesting example being the Sastry-Debenedetti-Sciortino-Stanley model for hydrogen bonding in low-temperature water. The magnitude of anomalies is characterized by a single parameter, the YY ratio, which for the models so far considered here ranges from -∞ to 1/2 .

  1. Hydrogen Plasma Processing of Iron Ore (United States)

    Sabat, Kali Charan; Murphy, Anthony B.


    Iron is currently produced by carbothermic reduction of oxide ores. This is a multiple-stage process that requires large-scale equipment and high capital investment, and produces large amounts of CO2. An alternative to carbothermic reduction is reduction using a hydrogen plasma, which comprises vibrationally excited molecular, atomic, and ionic states of hydrogen, all of which can reduce iron oxides, even at low temperatures. Besides the thermodynamic and kinetic advantages of a hydrogen plasma, the byproduct of the reaction is water, which does not pose any environmental problems. A review of the theory and practice of iron ore reduction using a hydrogen plasma is presented. The thermodynamic and kinetic aspects are considered, with molecular, atomic and ionic hydrogen considered separately. The importance of vibrationally excited hydrogen molecules in overcoming the activation energy barriers, and in transferring energy to the iron oxide, is emphasized. Both thermal and nonthermal plasmas are considered. The thermophysical properties of hydrogen and argon-hydrogen plasmas are discussed, and their influence on the constriction and flow in the of arc plasmas is considered. The published R&D on hydrogen plasma reduction of iron oxide is reviewed, with both the reduction of molten iron ore and in-flight reduction of iron ore particles being considered. Finally, the technical and economic feasibility of the process are discussed. It is shown that hydrogen plasma processing requires less energy than carbothermic reduction, mainly because pelletization, sintering, and cokemaking are not required. Moreover, the formation of the greenhouse gas CO2 as a byproduct is avoided. In-flight reduction has the potential for a throughput at least equivalent to the blast furnace process. It is concluded that hydrogen plasma reduction of iron ore is a potentially attractive alternative to standard methods.

  2. Pulsatile flow in a compliant stenosed asymmetric model (United States)

    Usmani, Abdullah Y.; Muralidhar, K.


    Time-varying velocity field in an asymmetric constricted tube is experimentally studied using a two-dimensional particle image velocimetry system. The geometry resembles a vascular disease which is characterized by arterial narrowing due to plaque deposition. The present study compares the nature of flow patterns in rigid and compliant asymmetric constricted tubes for a range of dimensionless parameters appearing in a human artery. A blood analogue fluid is employed along with a pump that mimics cardioflow conditions. The peak Reynolds number range is Re 300-800, while the Womersley number range considered in experiments is Wo 6-8. These values are based on the peak velocity in a straight rigid tube connected to the model, over a pulsation frequency range of 1.2-2.4 Hz. The medial-plane velocity distribution is used to investigate the nature of flow patterns. Temporal distribution of stream traces and hemodynamic factors including WSS, TAWSS and OSI at important phases of the pulsation cycle are discussed. The flow patterns obtained from PIV are compared to a limited extent against numerical simulation. Results show that the region downstream of the constriction is characterized by a high-velocity jet at the throat, while a recirculation zone, attached to the wall, evolves in time. Compliant models reveal large flow disturbances upstream during the retrograde flow. Wall shear stress values are lower in a compliant model as compared to the rigid. Cross-plane flow structures normal to the main flow direction are visible at select phases of the cycle. Positive values of largest Lyapunov exponent are realized for wall movement and are indicative of chaotic motion transferred from the flow to the wall. These exponents increase with Reynolds number as well as compliance. Period doubling is observed in wall displacement of highly compliant models, indicating possible triggering of hemodynamic events in a real artery that may cause fissure in the plaque deposits.

  3. Nanolithography on hydrogen terminateed silicon by scanning probe microscopy

    NARCIS (Netherlands)

    Schönenberger, Christian; Kramer, Niels; Kramer, N.


    Scanning-probe microscopes (SPM), i.e. the scanning-tunneling and force microscopes, can be used to locally oxidize hydrogen-terminated silicon and hydrogenated amorphous silicon. Because of its reliability and potential for pattern transfer, this lithography process has found great attention and

  4. Intermolecular hydrogen bonds: From temperature-driven proton ...

    Indian Academy of Sciences (India)

    Abstract. We have combined neutron scattering and a range of numerical simulations to study hydrogen bonds in condensed matter. Two examples from a recent thesis will be presented. The first concerns proton transfer with increasing temperature in short inter- molecular hydrogen bonds [1,2]. These bonds have unique ...

  5. Settling dynamics of asymmetric rigid fibers (United States)

    Tozzi, E. J.; Scott, C. T.; Vahey, D.; Klingenberg, D. J.


    The three-dimensional motion of asymmetric rigid fibers settling under gravity in a quiescent fluid was experimentally measured using a pair of cameras located on a movable platform. The particle motion typically consisted of an initial transient after which the particle approached a steady rate of rotation about an axis parallel to the acceleration of gravity, with its center of mass following a helical trajectory. Numerical and analytical methods were used to predict translational and angular velocities as well as the evolution of the fiber orientation as a function of time. A comparison of calculated and measured values shows that it is possible to quantitatively predict complex motions of particles that have highly asymmetric shape. The relations between particle shape and settling trajectory have potential applications for hydrodynamic characterization of fiber shapes and fiber separation.

  6. Enhancing molecule fluorescence with asymmetrical plasmonic antennas. (United States)

    Lu, Guowei; Liu, Jie; Zhang, Tianyue; Shen, Hongming; Perriat, Pascal; Martini, Matteo; Tillement, Olivier; Gu, Ying; He, Yingbo; Wang, Yuwei; Gong, Qihuang


    We propose and justify by the finite-difference time-domain method an efficient strategy to enhance the spontaneous emission of a fluorophore with a multi-resonance plasmonic antenna. The custom-designed asymmetrical antenna consists of two plasmonic nanoparticles with different sizes and is able to couple efficiently to free space light through multiple localized surface plasmon resonances. This design simultaneously permits a large near-field excitation near the antenna as well as a high quantum efficiency, which results in an unusual and significant enhancement of the fluorescence of a single emitter. Such an asymmetrical antenna presents intrinsic advantages over single particle or dimer based antennas made using two identical nanostructures. This promising concept can be exploited in the large domain of light-matter interaction processes involving multiple frequencies.

  7. Defect induced asymmetric pit formation on hydroxyapatite. (United States)

    Kwon, Ki-Young; Wang, Eddie; Chung, Alice; Chang, Neil; Saiz, Eduardo; Choe, Uh-Joo; Koobatian, Maxwell; Lee, Seung-Wuk


    Defect sites on bone minerals play a critical role in bone remodeling processes. We investigated single crystal hydroxyapatite (100) surfaces bearing crystal defects under acidic dissolution conditions using real-time in situ atomic force microscopy. At defect sites, surface structure-dependent asymmetric hexagonal etch pits were formed, which dominated the overall dissolution rate. Meanwhile, dissolution from the flat terraces proceeded by stochastic formation of flat bottom etch pits. The resulting pit shapes were intrinsically dictated by the HAP crystal structure. Computational modeling also predicted different step energies associated with different facets of the asymmetric etch pits. Our microscopic observations of HAP dissolution are significant for understanding the effects of local surface structure on the bone mineral remodeling process and provide useful insights for the design of novel therapies for treating osteoporosis and dental caries.

  8. Asymmetric synthesis and sensory evaluation of sedanenolide. (United States)

    Oguro, Daichi; Watanabe, Hidenori


    The synthesis and sensory evaluation of enantiomeric sets of sedanenolide (1) and 3-butylphthalide (3) are described. The asymmetric synthesis was achieved via the intramolecular Diels-Alder reaction of chiral propargylester (5) which was prepared from optically active propargyl alcohol (4) and 2,4-pentadienoic acid. The sensory evaluation of these enantiomers revealed that there were distinct differences between their aroma character and odor threshold.

  9. Catalytic Asymmetric Synthesis of Phosphine Boronates. (United States)

    Hornillos, Valentín; Vila, Carlos; Otten, Edwin; Feringa, Ben L


    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of α,β-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good yields and high enantiomeric excess. The synthetic utility of the products is demonstrated through stereospecific transformations into multifunctional optically active compounds. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Asymmetric k-Center with Minimum Coverage

    DEFF Research Database (Denmark)

    Gørtz, Inge Li


    In this paper we give approximation algorithms and inapproximability results for various asymmetric k-center with minimum coverage problems. In the k-center with minimum coverage problem, each center is required to serve a minimum number of clients. These problems have been studied by Lim et al. [A....... Lim, B. Rodrigues, F. Wang, Z. Xu, k-center problems with minimum coverage, Theoret. Comput. Sci. 332 (1–3) (2005) 1–17] in the symmetric setting....

  11. Asymmetric monetary policy effects in EMU


    Clausen, Volker; Hayo, Bernd


    This paper uses a semi-structural dynamic modelling approach to investigate asymmetric monetary transmission in Europe. A system of equations containing reaction functions for monetary policy, output and inflation equations is simultaneously estimated for France, Germany, and Italy. Extensive cross equation tests show that relatively large differences in simulated impulse responses are still consistent with the notion that the transmission mechanism is homogeneous across the three major EMU c...

  12. Asymmetric threat data mining and knowledge discovery (United States)

    Gilmore, John F.; Pagels, Michael A.; Palk, Justin


    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.

  13. Guided Modes in a Double-Well Asymmetric Potential of a Graphene Waveguide

    Directory of Open Access Journals (Sweden)

    Yi Xu


    Full Text Available The analogy between the electron wave nature in graphene electronics and the electromagnetic waves in dielectrics has suggested a series of optical-like phenomena, which is of great importance for graphene-based electronic devices. In this paper, we propose an asymmetric double-well potential on graphene as an electronic waveguide to confine the graphene electrons. The guided modes in this graphene waveguide are investigated using a modified transfer matrix method. It is found that there are two types of guided modes. The first kind is confined in one well, which is similar to the asymmetric quantum well graphene waveguide. The second kind can appear in two potential wells with double-degeneracy. Characteristics of all the possible guide modes are presented.

  14. Why hydrogen; Pourquoi l'hydrogene?

    Energy Technology Data Exchange (ETDEWEB)



    The energy consumption increase and the associated environmental risks, led to develop new energy sources. The authors present the potentialities of the hydrogen in this context of energy supply safety. They detail the today market and the perspectives, the energy sources for the hydrogen production (fossils, nuclear and renewable), the hydrogen transport, storage, distribution and conversion, the application domains, the associated risks. (A.L.B.)

  15. Rhodium/bisphosphine-thiourea-catalyzed enantioselective hydrogenation of α,β-unsaturated N-acylpyrazoles. (United States)

    Li, Pan; Hu, Xinquan; Dong, Xiu-Qin; Zhang, Xumu


    We successfully extended our Rh/bisphosphine-thiourea (ZhaoPhos) catalytic system to asymmetric hydrogenation of α,β-unsaturated N-acylpyrazoles affording products with high yields and excellent enantioselectivities (up to 97% yield, 99% ee). The pyrazole moiety played an important role in providing H-bond acceptor sites, which is critical for achieving high reactivities and enantioselectivities.

  16. Hydrogenations without Hydrogen: Titania Photocatalyzed Reductions of Maleimides and Aldehydes

    Directory of Open Access Journals (Sweden)

    David W. Manley


    Full Text Available A mild procedure for the reduction of electron-deficient alkenes and carbonyl compounds is described. UVA irradiations of substituted maleimides with dispersions of titania (Aeroxide P25 in methanol/acetonitrile (1:9 solvent under dry anoxic conditions led to hydrogenation and production of the corresponding succinimides. Aromatic and heteroaromatic aldehydes were reduced to primary alcohols in similar titania photocatalyzed reactions. A mechanism is proposed which involves two proton-coupled electron transfers to the substrates at the titania surface.

  17. Hydrogen nanobubble at normal hydrogen electrode (United States)

    Nakabayashi, S.; Shinozaki, R.; Senda, Y.; Yoshikawa, H. Y.


    Electrochemically formed hydrogen nanobubbles at a platinum rotating disk electrode (RDE) were detected by re-oxidation charge. The dissolution time course of the hydrogen nanobubbles was measured by AFM tapping topography under open-circuit conditions at stationary platinum and gold single-crystal electrodes. The bubble dissolution at platinum was much faster than that at gold because two types of diffusion, bulk and surface diffusion, proceeded at the platinum surface, whereas surface diffusion was prohibited at the gold electrode. These findings indicated that the electrochemical reaction of normal hydrogen electrode partly proceeded heterogeneously on the three-phase boundary around the hydrogen nanobubble.

  18. Hydrogen Purification Using Natural Zeolite Membranes (United States)

    DelValle, William


    The School of Science at Universidad del Turabo (UT) have a long-lasting investigation plan to study the hydrogen cleaning and purification technologies. We proposed a research project for the synthesis, phase analysis and porosity characterization of zeolite based ceramic perm-selective membranes for hydrogen cleaning to support NASA's commitment to achieving a broad-based research capability focusing on aerospace-related issues. The present study will focus on technology transfer by utilizing inorganic membranes for production of ultra-clean hydrogen for application in combustion. We tested three different natural zeolite membranes (different particle size at different temperatures and time of exposure). Our results show that the membranes exposured at 900 C for 1Hr has the most higher permeation capacity, indicated that our zeolite membranes has the capacity to permeate hydrogen.

  19. GAT 4 production and storage of hydrogen. Report July 2004; GAT 4 procduction et stockage de l'hydrogene. Rapport juillet 2004

    Energy Technology Data Exchange (ETDEWEB)



    This paper concerns two aspects of the hydrogen: the production and the storage. For both parts the challenges and a state of the art are presented. It discusses also the hydrogen production by renewable energies, by solar energy, the hydrogen of hydrocarbons reforming purification, active phases development, thermal transfer simulation. Concerning the hydrogen storage the hydrogen adsorption by large surface solid, the storage by metallic hydrides, the alanates and light hydrides, the adsorption on carbon nano-tubes, the storage in nano-structures, the thermal and mechanical simulation of the hydrogen are presented. (A.L.B.)

  20. Asymmetrical lumbosacral transitional vertebrae in dogs may promote asymmetrical hip joint development. (United States)

    Flückiger, Mark A; Steffen, Frank; Hässig, Michael; Morgan, Joseph P


    This study examines the relationship between the morphology of the lumbosacral transitional vertebra (LTV) and asymmetrical development of the hip joints in dogs. A total of 4000 dogs which had been consecutively scored for canine hip dysplasia were checked for the presence of a LTV. A LTV was noted in 138 dogs and classified depending on the morphology of the transverse processes and the degree of contact with the ilium. In dogs with an asymmetrical LTV, the hip joint was significantly more predisposed to subluxation and malformation on the side of the intermediate or sacral-like transverse process (p hip joint conformation was less affected on the side featuring a free transverse process (p hip joint, and secondary osteoarthritis. Asymmetrical hip conformation may therefore be the sequela of a LTV and mask or aggravate genetically induced canine hip dysplasia.

  1. Examining the Cultural Leadership Behaviors of Schoo l Principal s within the Context of Symmetric and Asymmetric School Culture

    Directory of Open Access Journals (Sweden)

    Betül BALKAR


    Full Text Available The aim of this study is to determine the opinions of teachers on contributions of school principals’ cultural leadership behaviors to forming symmetric and asymmetric culture. The participants of the study consisted of 27 secondary school teachers working in Gaziantep province. Data of the study were collected through semi - structured interviews and analyzed through content analysis. Contributions of each cultural leader ship behavior to symmetric and asymmetric culture types were determined by taking relations between cultural leadership behaviors and symmetric and asymmetric cultures into consideration in the process of content analysis. According to the findings of the study ; supporting development of teachers and reflecting developments and innovations on schools are among the cultural leadership behaviors contributing to forming asymmetric culture at schools. Interpreting tasks and missions of school and ensuring neces sary environment for keeping social values alive at schools are among the cultural leadership behaviors contributing to forming symmetric culture at schools. Based on the results of the study, it is suggested that school principals should follow developmen ts in educational issues and transfer these developments into school practices. They should place more importance on supporting innovative behaviors of teachers in order to create asymmetric culture at schools.

  2. Transfer Pricing

    DEFF Research Database (Denmark)

    Nielsen, Søren Bo


    Against a background of rather mixed evidence about transfer pricing practices in multinational enterprises (MNEs) and varying attitudes on the part of tax authorities, this paper explores how multiple aims in transfer pricing can be pursued across four different transfer pricing regimes. A MNE h...

  3. Hydrogen energy systems studies

    Energy Technology Data Exchange (ETDEWEB)

    Ogden, J.M.; Kreutz, T.G.; Steinbugler, M. [Princeton Univ., NJ (United States)] [and others


    In this report the authors describe results from technical and economic assessments carried out during the past year with support from the USDOE Hydrogen R&D Program. (1) Assessment of technologies for small scale production of hydrogen from natural gas. Because of the cost and logistics of transporting and storing hydrogen, it may be preferable to produce hydrogen at the point of use from more readily available energy carriers such as natural gas or electricity. In this task the authors assess near term technologies for producing hydrogen from natural gas at small scale including steam reforming, partial oxidation and autothermal reforming. (2) Case study of developing a hydrogen vehicle refueling infrastructure in Southern California. Many analysts suggest that the first widespread use of hydrogen energy is likely to be in zero emission vehicles in Southern California. Several hundred thousand zero emission automobiles are projected for the Los Angeles Basin alone by 2010, if mandated levels are implemented. Assuming that hydrogen vehicles capture a significant fraction of this market, a large demand for hydrogen fuel could evolve over the next few decades. Refueling a large number of hydrogen vehicles poses significant challenges. In this task the authors assess near term options for producing and delivering gaseous hydrogen transportation fuel to users in Southern California including: (1) hydrogen produced from natural gas in a large, centralized steam reforming plant, and delivered to refueling stations via liquid hydrogen truck or small scale hydrogen gas pipeline, (2) hydrogen produced at the refueling station via small scale steam reforming of natural gas, (3) hydrogen produced via small scale electrolysis at the refueling station, and (4) hydrogen from low cost chemical industry sources (e.g. excess capacity in refineries which have recently upgraded their hydrogen production capacity, etc.).

  4. Hydrogen in semiconductors

    CERN Document Server

    Pankove, Jacques I


    Hydrogen plays an important role in silicon technology, having a profound effect on a wide range of properties. Thus, the study of hydrogen in semiconductors has received much attention from an interdisciplinary assortment of researchers. This sixteen-chapter volume provides a comprehensive review of the field, including a discussion of hydrogenation methods, the use of hydrogen to passivate defects, the use of hydrogen to neutralize deep levels, shallow acceptors and shallow donors in silicon, vibrational spectroscopy, and hydrogen-induced defects in silicon. In addition to this detailed cove

  5. Heat Analysis of Liquid piston Compressor for Hydrogen Applications

    DEFF Research Database (Denmark)

    Kermani, Nasrin Arjomand; Rokni, Masoud


    is developed based on the mass and energy balance of the hydrogen, liquid and the wall of the compression chamber at each time step and positional node with various compression ratios to calculate the temperature distribution of the system. The amount of heat extracted from hydrogen, directly at the interface......A new hydrogen compression technology using liquid as the compression piston is investigated from heat transfer point of view. A thermodynamic model, simulating a single compression stroke, is developed to investigate the heat transfer phenomena inside the compression chamber. The model...

  6. The hydrogen bond in the solid state. (United States)

    Steiner, Thomas


    The hydrogen bond is the most important of all directional intermolecular interactions. It is operative in determining molecular conformation, molecular aggregation, and the function of a vast number of chemical systems ranging from inorganic to biological. Research into hydrogen bonds experienced a stagnant period in the 1980s, but re-opened around 1990, and has been in rapid development since then. In terms of modern concepts, the hydrogen bond is understood as a very broad phenomenon, and it is accepted that there are open borders to other effects. There are dozens of different types of X-H.A hydrogen bonds that occur commonly in the condensed phases, and in addition there are innumerable less common ones. Dissociation energies span more than two orders of magnitude (about 0.2-40 kcal mol(-1)). Within this range, the nature of the interaction is not constant, but its electrostatic, covalent, and dispersion contributions vary in their relative weights. The hydrogen bond has broad transition regions that merge continuously with the covalent bond, the van der Waals interaction, the ionic interaction, and also the cation-pi interaction. All hydrogen bonds can be considered as incipient proton transfer reactions, and for strong hydrogen bonds, this reaction can be in a very advanced state. In this review, a coherent survey is given on all these matters.

  7. Asymmetric Michael Addition of Ketones to Nitroolefins Catalyzed by a Novel Chiral Pyrrolidine-Thiourea in the Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Jun [Suzhou Univ., Suzhou (China); Chen, Weiyi [J and K Suzhou Ultrafine Material Ltd, Suzhou (China)


    A novel chiral pyrrolidine-thiourea has been developed and successfully applied to the asymmetric Michael addition of ketones with nitroolefins in ionic liquid. The corresponding products could be obtained in good yields with good enantio- and diastereoselectivities of products. In addition, the chiral catalytic system could be reused with comparable catalytic activity and stereoselectivity. Further studies are under way to expand the synthetic utility of this new reaction, as well as the application of this catalytic system in other asymmetric transformations. Organocatalytic asymmetric reactions have proved to be efficient and powerful tools in organic synthesis. Among them, the asymmetric Michael reaction of nitroolefins with carbon nucleophiles is widely recognized as one of the most important and versatile processes for the synthesis of enantioselective C-C and C-X bonds; for the nitroolefins are of special interest as excellent Michael acceptors, and the nitro functionality can be easily transformed into an amine, nitrile oxide, ketone, carboxylic acid, hydrogen, etc., providing a wide range of synthetically interesting compounds.

  8. Local control approach to ultrafast electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Vindel-Zandbergen, Patricia [Departamento de Química Física, Universidad Complutense, 28040 Madrid (Spain); Meier, Christoph [Laboratoire Colisions, Agrégats et Reactivité, UMR 5589, IRSAMC, Université Paul Sabatier, 31062 Toulouse (France); Sola, Ignacio R., E-mail: [Departamento de Química Física, Universidad Complutense, 28040 Madrid (Spain)


    We study ultrafast electron transfer between separated nuclei using local control theory. By imposing electron ionization and electron transport through the continuum, different local control formulations are used to increase the yield of retrapping the electron at the desired nuclei. The control mechanism is based on impulsive de-excitation. Both symmetric and asymmetric nuclear arrangements are analyzed, as well as the role of the nuclear motion.

  9. Handbook of hydrogen energy

    CERN Document Server

    Sherif, SA; Stefanakos, EK; Steinfeld, Aldo


    ""This book provides an excellent overview of the hydrogen economy and a thorough and comprehensive presentation of hydrogen production and storage methods.""-Scott E. Grasman, Rochester Institute of Technology, New York, USA

  10. Center for Hydrogen Storage. (United States)


    The main goals of this project were to (1) Establish a Center for Hydrogen Storage Research at Delaware State University for the preparation and characterization of selected complex metal hydrides and the determination their suitability for hydrogen ...

  11. Hydrogen production by Cyanobacteria

    Directory of Open Access Journals (Sweden)

    Chaudhuri Surabhi


    Full Text Available Abstract The limited fossil fuel prompts the prospecting of various unconventional energy sources to take over the traditional fossil fuel energy source. In this respect the use of hydrogen gas is an attractive alternate source. Attributed by its numerous advantages including those of environmentally clean, efficiency and renew ability, hydrogen gas is considered to be one of the most desired alternate. Cyanobacteria are highly promising microorganism for hydrogen production. In comparison to the traditional ways of hydrogen production (chemical, photoelectrical, Cyanobacterial hydrogen production is commercially viable. This review highlights the basic biology of cynobacterial hydrogen production, strains involved, large-scale hydrogen production and its future prospects. While integrating the existing knowledge and technology, much future improvement and progress is to be done before hydrogen is accepted as a commercial primary energy source.

  12. Hydrogen transport membranes (United States)

    Mundschau, Michael V.


    Composite hydrogen transport membranes, which are used for extraction of hydrogen from gas mixtures are provided. Methods are described for supporting metals and metal alloys which have high hydrogen permeability, but which are either too thin to be self supporting, too weak to resist differential pressures across the membrane, or which become embrittled by hydrogen. Support materials are chosen to be lattice matched to the metals and metal alloys. Preferred metals with high permeability for hydrogen include vanadium, niobium, tantalum, zirconium, palladium, and alloys thereof. Hydrogen-permeable membranes include those in which the pores of a porous support matrix are blocked by hydrogen-permeable metals and metal alloys, those in which the pores of a porous metal matrix are blocked with materials which make the membrane impervious to gases other than hydrogen, and cermets fabricated by sintering powders of metals with powders of lattice-matched ceramic.

  13. Preview-based Asymmetric Load Reduction of Wind Turbines

    DEFF Research Database (Denmark)

    Madsen, Mathias; Filsø, Jakob; Soltani, Mohsen


    Fatigue loads on wind turbines caused by an asymmetric wind field become an increasing concern when the scale of wind turbines increases. This paper presents a model based predictive approach to reduce asymmetric loads by using Light Detection And Ranging (LIDAR) measurements. The Model Predictive...... to the same controller without LIDAR data. The results showed that the MPC with LIDAR was able to reduce the asymmetric loads compared to the MPC without LIDAR while still maintaining the power reference....

  14. Asymmetric joint multifractal analysis in Chinese stock markets (United States)

    Chen, Yuwen; Zheng, Tingting


    In this paper, the asymmetric joint multifractal analysis method based on statistical physics is proposed to explore the asymmetric correlation between daily returns and trading volumes in Chinese stock markets. The result shows asymmetric multifractal correlations exist between return and trading volume in Chinese stock markets. Moreover, when the stock indexes are upward, the fluctuations of returns are always weaker than when they are downward, whether the trading volumes are more or less.

  15. Combined shear/compression structural testing of asymmetric sandwich structures


    Castanié, Bruno; Barrau, Jean-Jacques; Jaouen, Jean-Pierre; Rivallant, Samuel


    Asymmetric sandwich technology can be applied in the design of lightweight, non-pressurized aeronautical structures such as those of helicopters. A test rig of asymmetric sandwich structures subjected to compression/shear loads was designed, validated, and set up. It conforms to the standard certification procedure for composite aeronautical structures set out in the “test pyramid”, a multiscale approach. The static tests until failure showed asymmetric sandwich structures to be extremely res...

  16. Asymmetric acoustic transmission in graded beam

    Energy Technology Data Exchange (ETDEWEB)

    Jing, Li, E-mail: [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China); Wu, Jiu Hui, E-mail: [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China); Guan, Dong; Lu, Kuan [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China); Gao, Nansha [School of Marine Science and Technology, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); Songhua, Cao [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China)


    We demonstrate the dynamic effective material parameters and vibration performance of a graded beam. The structure of the beam was composed of several unit cells with different fill factors. The dispersion relations and energy band structures of each unit cell were calculated using the finite element method (FEM). The dynamic effective material parameters in each unit cell of the graded beam were determined by the dispersion relations and energy band structures. Longitudinal wave propagation was investigated using a numerical method and FEM. The results show that the graded beam allows asymmetric acoustic transmission over a wide range of frequencies.

  17. On asymmetric causal relationships in Petropolitics

    Directory of Open Access Journals (Sweden)

    Balan Feyza


    Full Text Available The aim of this paper is to examine whether the First Law of Petropolitics denominated by Friedman in 2006 is valid for OPEC countries. To do this, this paper analyses the relationship between political risk and oil supply by applying the asymmetric panel causality test suggested by Hatemi-J (2011 to these countries for the period 1984-2014. The results show that the First Law of Petropolitics is valid for Angola, Iraq, Kuwait, Libya, Nigeria, Qatar, Saudi Arabia, and the UAE, given that positive oil supply shocks significantly lead to negative political stability shocks, and negative oil supply shocks significantly lead to positive shocks in political stability.

  18. RHIC operation with asymmetric collisions in 2015

    Energy Technology Data Exchange (ETDEWEB)

    Liu, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Aschenauer, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Atoian, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Blaskiewicz, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Brown, K. A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Bruno, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Connolly, R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Ottavio, T. D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Drees, K. A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Fischer, W. [Brookhaven National Lab. (BNL), Upton, NY (United States); Gardner, C. J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Gu, X. [Brookhaven National Lab. (BNL), Upton, NY (United States); Hayes, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Huang, H. [Brookhaven National Lab. (BNL), Upton, NY (United States); Laster, J. S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Luo, Y. [Brookhaven National Lab. (BNL), Upton, NY (United States); Makdisi, Y. [Brookhaven National Lab. (BNL), Upton, NY (United States); Marr, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Marusic, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Meot, F. [Brookhaven National Lab. (BNL), Upton, NY (United States); Mernick, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Michnoff, R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Minty, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Montag, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Morris, J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Narayan, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Nayak, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Nemesure, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Pile, P. [Brookhaven National Lab. (BNL), Upton, NY (United States); Poblaguev, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Ranjbar, V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Robert-Demolaize, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Roser, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Schmidke, B. [Brookhaven National Lab. (BNL), Upton, NY (United States); Schoefer, V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Severino, F. [Brookhaven National Lab. (BNL), Upton, NY (United States); Shrey, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Smith, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Steski, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Tepikian, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Trbojevic, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Tsoupas, N. [Brookhaven National Lab. (BNL), Upton, NY (United States); Wang, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); White, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Yip, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Zaltsman, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Zeno, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Zhang, S. Y. [Brookhaven National Lab. (BNL), Upton, NY (United States)


    To study low-x shadowing/saturation physics as well as other nuclear effects [1], [2], proton-gold (p-Au, for 5 weeks) and proton-Aluminum (p-Al, for 2 weeks) collisions were provided for experiments in 2015 at the Relativistic Heavy Ion Collider (RHIC), with polarized proton beam in the Blue ring and Au/Al beam in the Yellow ring. The special features of the asymmetric run in 2015 will be introduced. The operation experience will be reviewed as well in the report.

  19. Chiral Diamine-catalyzed Asymmetric Aldol Reaction

    Institute of Scientific and Technical Information of China (English)

    LI Hui; XU Da-zhen; WU Lu-lu; WANG Yong-mei


    A highly efficient catalytic system composed of a simple and commercially available chiral primary diamine (1R,2R)-cyclohexane-1,2-diamine(6) and trifluoroacetic acid(TFA) was employed for asymmetric Aldol reaction in i-PrOH at room temperature.A loading of 10%(molar fraction) catalyst 6 with TFA as a cocatalyst could catalyze the Aldol reactions of various ketones or aldehydes with a series of aromatic aldehydes,furnishing Aldol products in moderate to high yields(up to >99%) with enantioselectivities of up to >99% and diastereoselectivities of up to 99:1.

  20. Nanotribology of Symmetric and Asymmetric Liquid Lubricants

    Directory of Open Access Journals (Sweden)

    Shinji Yamada


    Full Text Available When liquid molecules are confined in a narrow gap between smooth surfaces, their dynamic properties are completely different from those of the bulk. The molecular motions are highly restricted and the system exhibits solid-like responses when sheared slowly. This solidification behavior is very dependent on the molecular geometry (shape of liquids because the solidification is induced by the packing of molecules into ordered structures in confinement. This paper reviews the measurements of confined structures and friction of symmetric and asymmetric liquid lubricants using the surface forces apparatus. The results show subtle and complex friction mechanisms at the molecular scale.