Sample records for asymmetric transfer hydrogenation

  1. Synthesis of antidepressant duloxetine via asymmetric transfer hydrogenation

    Institute of Scientific and Technical Information of China (English)

    Shan Zhen He; Xue Ming Li; Jia Dai; Ming Yan


    Antidepressant duloxetine (1) was prepared via asymmetric transfer hydrogenation of 3-(dimethylamino)-1-(thiophen-2-yl)propan-1-one (3). The Ru(Ⅱ), Rh(Ⅲ) and Ir(Ⅲ) complexes of several chiral ligands were examined as the catalyst and(S,S)-N-tosyl-1,2-diphenyl ethylenediamine (TsDPEN)-Ru(Ⅱ) complex was found to provide good yield and excellent enantios-electivity.

  2. Asymmetric Transfer Hydrogenation of ω -Bromo Acetophenones in Aqueous Media

    Institute of Scientific and Technical Information of China (English)

    Wang Fei; Liu Hui; Cui Xin; Cun Linfeng; Zhu Jin; Deng Jingen; Jiang Yaozhong


    Optical active ω-bromophenylethanols are useful building blocks for synthesis of various pharmaceuticals such as α 1-, β 2-, and β 3- adrenergic receptor agonists, which are always obtained though a biotransformative pathway and using boron reagent with rigorous conditions [1]. To our knowledge, the metal-catalysed transfer hydrogenation is seldom applied in this reaction. Recently we have developed a water-soluble chiral Ru-complex and applied successfully in transfer hydrogenation of ω-bromo acetophenones in aqueous media [2], which can not be performed in homogeneous system with HCOOH/NEt3 as hydrogen donor[3] .In this paper, we will report that asymmetric transfer hydrogenation of ω-bromo acetophenones was successfully performed in aqueous media by employing hydrophobic Rh-amido complex (TsDPEN-Rh) as catalyst and HCOONa as hydrogen donor. Moreover, marked increasing of activity and high enantioselectivity (up to 98%) of ω-bromo acetophenone 1a was found in the presence of different micelles or vesicles. This method was also applied successfully in preparation of the important chiral medicinal intermediates, such as the precursor of salbutamol, 2b and fermoterol, 2c with high enantioselectivity.

  3. Recent Developments in the Area of Asymmetric Transfer Hydrogenation

    Directory of Open Access Journals (Sweden)

    Tim Walsgrove


    Full Text Available The use of an enantiomerically pure amino alcohol, coupled to a transfer hydrogenation process, in the asymmetric catalysis of the reduction of ketones to alcohols, is described. The process works well for unfunctionalised ketones, affording e.e.s of up to 98%, and excellent conversions. We have recently extended, for the first time in this application, the scope of the methodology to the reductions of a-heteroatom substituted substrates, through the use of the appropriate protecting groups on each atom.

  4. Asymmetric transfer hydrogenation of imines catalyzed by a polymer-immobilized chiral catalyst. (United States)

    Haraguchi, Naoki; Tsuru, Keiichi; Arakawa, Yukihiro; Itsuno, Shinichi


    The asymmetric transfer hydrogenation of imines was performed with the use of a polymer-immobilized chiral catalyst. The chiral catalyst, prepared from crosslinked polystyrene-immobilized chiral 1,2-diamine monosulfonamide, was effective in the asymmetric transfer hydrogenation of N-benzyl imines in CH(2)Cl(2) to give a chiral amine in high yield and good enantioselectivity. Furthermore, an amphiphilic polymeric catalyst prepared from crosslinked polystyrene containing sulfonated groups successfully catalyzed the asymmetric transfer hydrogenation of cyclic imines in water. Enantioenriched secondary amines with up to 94% ee were obtained by using a polymeric catalyst.

  5. Asymmetric transfer hydrogenation of prochiral ketone catalyzed over Fe-CS/SBA-15 catalyst

    Institute of Scientific and Technical Information of China (English)

    XUE Ping; WU Tao


    A heterogeneous chiral catalyst Fe(Ⅲ)-CS (chitosan)complex/mesoporous molecular sieve SBA-15 (Santa Barbara Amorphous) was prepared.The asymmetric transfer hydrogenations of prochiral acetophenone and 4-methyl-2-pentanone to corresponding chiral alcohols were carried out on Fe-CS/SBA-15 at atmosphere pressure using 2-propanol as hydrogen donor.Effects of Fe content in catalyst,reaction temperature,reaction time and promoter KOH concentration on the conversion of substrates and enantioselectivity were investigated.Fe-CS/SBA-15 with 2.2%mass fraction Fe exhibits considerable enantioselectivity and catalytic activity for the asymmetric transfer hydrogenations of aromatic ketone and aliphatic ketone.Under optimal reaction conditions:KOH concentration 0.03 mol/L,reaction temperature 70℃ and reaction time 4 h,enantiomer excess(ee)of (R)-1-phenylethanol and conversion of acetophenone can reach 87.4%and 27.7%,respectively.Under the above KOH concentration and reaction temperature and reaction time of 8 h,the ee of(R)-4-methyl-2-pentanol and conversion 4-methyl-2-pentanone amounted to 50.2%and 25.5%,respectively.

  6. Novel Chiral PNNP-Ru Complexes: Synthesis and Application in Asymmetric Transfer Hydrogenation of Ketones

    Institute of Scientific and Technical Information of China (English)

    CHENG Zhi-bo; YU Shen-luan; LI Yan-yun; DONG Zhen-rong; SUN Guo-song; HUANG Ke-lin; GAO Jing-xing


    The efficient catalytic systems generated in situ from RuCl2(PPh3)3 and chiral ligands N,N-bis[2-(di-otolylphosphino)-benzyl]cyclohexane-l,2-diamine(2) were employed for asymmetric transfer hydrogenation of aromatic ketones, giving the corresponding optically active alcohols with high activities(up to 99% conversion) and excellent enantioselectivities(up to 96% e.e.) under mild conditions. The chiral ruthenium(Ⅱ) complex (R,R)-3 has been prepared and characterized by NMR and X-ray crystallography.

  7. Asymmetric transfer hydrogenation of ketones catalyzed by nickel complex with new PNO-type ligands

    Institute of Scientific and Technical Information of China (English)

    Zhen Rong Dong; Yan Yun Li; Shen Luan Yu; Guo Song Sun; Jing Xing Gao


    The new polydentate mixed-N,P,O chiral ligands have been synthesized by the condensation of bis(o-formylphenyl)-phenylphosphane and R-phenylglycinol in CHCl3,and fully characterized by IR,NMR and EIMS spectra.These ligands were employed with a simple Ni complex Ni(PPh8)2Cl2 in situ as catalytic systems for asymmetric transfer hydrogenation of ketones,and the corresponding optical alcohols were obtained with up to 84% ee under mild conditions.

  8. Asymmetric Transfer Hydrogenation of Imines in Water by Varying the Ratio of Formic Acid to Triethylamine. (United States)

    Shende, Vaishali S; Deshpande, Sudhindra H; Shingote, Savita K; Joseph, Anu; Kelkar, Ashutosh A


    Asymmetric transfer hydrogenation (ATH) of imines has been performed with variation in formic acid (F) and triethylamine (T) molar ratios in water. The F/T ratio is shown to affect both the reduction rate and enantioselectivity, with the optimum ratio being 1.1 in the ATH of imines with the Rh-(1S,2S)-TsDPEN catalyst. Use of methanol as a cosolvent enhanced reduction activity. A variety of imine substrates have been reduced, affording high yields (94-98%) and good to excellent enantioselectivities (89-98%). In comparison with the common azeotropic F-T system, the reduction with 1.1/1 F/T is faster.

  9. 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.

  10. Synthesis of novel chiral N, P-containing multidentate ligands and their applications in asymmetric transfer hydrogenation

    Institute of Scientific and Technical Information of China (English)

    Shen Luan Yu; Yan Yun Li; Zhen Rong Dong; Juan Ni Zhang; Qi Li; Jing Xing Gao


    Novel chiral PN4-type multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis(o-formylphenyl)phenylphosphane and various chiral amino-sulfonamides. Their structures were fully characterized by IR, EI-MS and NMR. The catalytic systems, prepared in situ from the multidentate ligands and iridium(I) complexes, showed high activity in asymmetric transfer hydrogenation of propiophenone in 2-propanol solution, leading to corresponding optical alcohol with up to 75% ee.

  11. Asymmetric Transfer Hydrogenation of Prochiral Ketones in Aqueous Media with New Water-Soluble Chiral Vicinal Diamine as Ligand

    Institute of Scientific and Technical Information of China (English)

    ZHU Jin; MA Ya-Ping; LIU Hui; CHEN Li; CUI Xin; DENG Jin-Gen


    @@ As a consequence of the increasing demand for atom economy and environmental friendly methods, the water soluble ligands and their metal complexes are of great interest in catalytic synthesis because of simpler product sepa ration and the possibility of recycling. [1] Unique reactivity and selectivity are often observed in aqueous reactions. [2]Recently, we have developed a new water-soluble chiral vicinal diamine and synthesized its mono-N-tosylated derivative for the first time. The application of its mono-N-tosylated derivative in catalytic asymmetric transfer hydrogenation of prochiral ketones was examined in aqueous media. High activity (up to > 99 % conv. ) and good enatioselectivity ( up to 98% ee ) were achieved for most of prochiral aromatic ketones in organic solvent free system. [3

  12. 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.

  13. Opportunities Offered by Chiral η6-Arene/N-Arylsulfonyl-diamine-RuII Catalysts in the Asymmetric Transfer Hydrogenation of Ketones and Imines

    Directory of Open Access Journals (Sweden)

    Libor Červený


    Full Text Available Methods for the asymmetric transfer hydrogenation (ATH of ketones and imines are still being intensively studied and developed. Of foremost interest is the use of Noyori’s [RuCl(η6-arene(N-TsDPEN] complexes in the presence of a hydrogen donor (i-PrOH, formic acid. These complexes have found numerous practical applications and have been extensively modified. The resulting derivatives have been heterogenized, used in ATH in water or ionic liquids and even some attempts have been made to approach the properties of biocatalysts. Therefore, an appropriate modification of the catalyst that suits the specific requirements for the reaction conditions is very often readily available. The mechanism of the reaction has also been explored to a great extent. Model substrates, acetophenone (a ketone and 6,7-dimethoxy-1-methyl-3,4-dihydroisoquinoline (an imine, are both reduced by this Ru catalytic system with almost perfect selectivity. However, in each case the major product is a different enantiomer (S- for an alcohol, R- for an amine when the S,S-catalyst is used, which demanded an in-depth mechanistic investigation. Full-scale molecular modelling of this system enabled us to visualize the plausible 3D structures of the transition states, allowing the proposition of a viable explanation of previous experimental findings.

  14. Asymmetric Hydrogenation of 3-Substituted Pyridinium Salts

    NARCIS (Netherlands)

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


    The use of an equivalent amount of an organic base leads to high enantiomeric excess in the asymmetric hydrogenation of N-benzylated 3-substituted pyridinium salts into the corresponding piperidines. Indeed, in the presence of Et3N, a Rh-JosiPhos catalyst reduced a range of pyridinium salts with ee

  15. 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)


    Institute of Scientific and Technical Information of China (English)


    Hydrogen transfer is an important secondary reaction of catalytic cracking reactions, which affects product yield distribution and product quality. It is an exothermic reaction with low activation energy around 43.3 kJ/mol. Catalyst properties and operation parameters in catalytic cracking greatly influence the hydrogen transfer reaction. Satisfactory results are expected through careful selection of proper catalysts and operation conditions.

  17. 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.

  18. Asymmetric heat transfer from nanoparticles in lipid bilayers (United States)

    Potdar, Dipti; Sammalkorpi, Maria


    Here, we use molecular dynamics simulations to characterize the heat transfer properties of lipid bilayer - gold nanoparticle systems in which the nanoparticle acts as a heat source. The focus is on dipalmitoylphosphatidylcholine (DPPC) lipid bilayers and thiolated alcohol and alkyl functionalized nanoparticles as prototype hydrophilic and hydrophobic nanoparticles. We find hydrophilic nanoparticles which are partly in contact with the surrounding water environment are more efficient in transferring heat to the system than hydrophobic ones which reside surrounded by the membrane. This is because of the hydrogen bonding capability of the hydroxy pentanethiol and the more efficient heat conductivity through water than the lipid bilayer. Additionally, we find the heat conductance is strongly asymmetric and has a discontinuity between the bilayer leaflets. In total, the findings provide understanding on heat transport from localized heat sources in lipid bilayers and could bear significance, e.g., in engineering and controlling photoactivated triggering of liposomal systems.

  19. Rh-Catalyzed Asymmetric Hydrogenation of 1,2-Dicyanoalkenes. (United States)

    Li, Meina; Kong, Duanyang; Zi, Guofu; Hou, Guohua


    A highly efficient enantioselective hydrogenation of 1,2-dicyanoalkenes catalyzed by the complex of rhodium and f-spiroPhos has been developed. A series of 1,2-dicyanoalkenes were successfully hydrogenated to the corresponding chiral 1,2-dicyanoalkanes under mild conditions with excellent enantioselectivities (up to 98% ee). This methodology provides efficient access to the asymmetric synthesis of chiral diamines.

  20. Asymmetric Hydrogenation of Ketones-Design of Chiral Catalysts

    Institute of Scientific and Technical Information of China (English)

    Takeshi Ohkuma


    @@ 1Introduction Asymmetric hydrogenation of ketones is one of the most reliable methods for obtaining chiral secondary alcohols. This transformation is not only of academic interest, but also of industrial significance because of its simplicity, environmental friendliness, and economic viability. Chiral RuXY(binap)(1,2-diamine) complexes (BINAP = 2,2'-bis(diphenyl-phosphino)-1, 1'-binaphthyl,X = Y = C1 or X = H, Y = BH4) with[1] or without[2] a strong base catalyze rapid, highly productive asymmetric hydrogenation of various simple ketones in 2-propanol. This reaction, unlike conventional hydrogenation, proceeds selectively at a C = O bond leaving coexisting C = C linkages intact. A range of chiral alcohols are accessible in high enantiomeric purity from aromatic,heteroaromatic, olefinic, and amino ketones by this method[1,2]. However, no universal chiral catalysts exist due to the structural diversity of ketonic substrates. Thus, tert-alkyl ketones and 1-tetralones have remained difficult to be hydrogenated with high reactivity and enantioselectivity. We here report that this problem can be resolved by the use of BINAP/PICA-Ru (PICA = α-picolylamine)[3] or BINAP/1,4-diamine-Ru[4] complexes as catalysts.

  1. Highly enantioselective hydrogenation of N-aryl imines derived from acetophenones by using Ru-pybox complexes under hydrogenation or transfer hydrogenation conditions in isopropanol. (United States)

    Menéndez-Pedregal, Estefanía; Vaquero, Mónica; Lastra, Elena; Gamasa, Pilar; Pizzano, Antonio


    The asymmetric reduction of N-aryl imines derived from acetophenones by using Ru complexes bearing both a pybox (2,6-bis(oxazoline)pyridine) and a monodentate phosphite ligand has been described. The catalysts show good activity with a diverse range of substrates, and deliver the amine products in very high levels of enantioselectivity (up to 99 %) under both hydrogenation and transfer hydrogenation conditions in isopropanol. From deuteration studies, a very different labeling is observed under hydrogenation and transfer hydrogenation conditions, which demonstrates the different nature of the hydrogen source in both reactions.

  2. Recent advances in catalytic asymmetric hydrogenation:Renaissance of the monodentate phosphorus ligands

    Institute of Scientific and Technical Information of China (English)

    GUO Hongchao; DING Kuiling; DAI Lixin


    The history for the development of chiral phosphorus ligands in catalytic asymmetric hydrogenation is briefly highlighted. This review focuses on the recent advances in the synthesis of the monodentate phosphorus ligands and their applications in catalytic asymmetric hydrogenation. The examples highlighted in this article clearly demonstrated the importance and advantages of monodentate phosphorus ligands, which had been ignored for 30 a and experienced a renaissance at the very beginning of this millennium, particularly in the area of asymmetric hydrogenation.

  3. Hydrogen Bonds in Excited State Proton Transfer (United States)

    Horke, D. A.; Watts, H. M.; Smith, A. D.; Jager, E.; Springate, E.; Alexander, O.; Cacho, C.; Chapman, R. T.; Minns, R. S.


    Hydrogen bonding interactions between biological chromophores and their surrounding protein and solvent environment significantly affect the photochemical pathways of the chromophore and its biological function. A common first step in the dynamics of these systems is excited state proton transfer between the noncovalently bound molecules, which stabilizes the system against dissociation and principally alters relaxation pathways. Despite such fundamental importance, studying excited state proton transfer across a hydrogen bond has proven difficult, leaving uncertainties about the mechanism. Through time-resolved photoelectron imaging measurements, we demonstrate how the addition of a single hydrogen bond and the opening of an excited state proton transfer channel dramatically changes the outcome of a photochemical reaction, from rapid dissociation in the isolated chromophore to efficient stabilization and ground state recovery in the hydrogen bonded case, and uncover the mechanism of excited state proton transfer at a hydrogen bond, which follows sequential hydrogen and charge transfer processes.

  4. Phase-transfer-catalysed asymmetric synthesis of tetrasubstituted allenes (United States)

    Hashimoto, Takuya; Sakata, Kazuki; Tamakuni, Fumiko; Dutton, Mark J.; Maruoka, Keiji


    Allenes are molecules based on three carbons connected by two cumulated carbon-carbon double bonds. Given their axially chiral nature and unique reactivity, substituted allenes have a variety of applications in organic chemistry as key synthetic intermediates and directly as part of biologically active compounds. Although the demands for these motivated many endeavours to make axially chiral, substituted allenes by exercising asymmetric catalysis, the catalytic asymmetric synthesis of fully substituted ones (tetrasubstituted allenes) remained largely an unsolved issue. The fundamental obstacle to solving this conundrum is the lack of a simple synthetic transformation that provides tetrasubstituted allenes in the action of catalysis. We report herein a strategy to overcome this issue by the use of a phase-transfer-catalysed asymmetric functionalization of 1-alkylallene-1,3-dicarboxylates with N-arylsulfonyl imines and benzylic and allylic bromides.

  5. Heat-transfer data for hydrogen (United States)

    Mc Carthy, J. R.; Miller, W. S.; Okuda, A. S.; Seader, J. D.


    Information is given regarding experimental heat-transfer data compiled for the turbulent flow of hydrogen within straight, electrically heated, round cross section tubes. Tube materials, test conditions, parameters studied, and generalized conclusions are presented.

  6. Modeling of vehicular hydrogen storage transfer processes

    Energy Technology Data Exchange (ETDEWEB)

    Viola, J.; Ventner, R.D. [Toronto Univ., ON (Canada). Dept. of Mechanical and Industrial Engineering; Bose, T.; Benard, P. [Quebec Univ., Trois-Rivieres, PQ (Canada)


    The acceptance of hydrogen as an alternate fuel for powering vehicles depends on several factors, such as the performance properties of hydrogen fuels, the behaviour of the vehicle in terms of power response, and the handling of the fuel during the transfer operation to the vehicle. This paper presents a study which examined the transfer of fuel and compared the fueling processes of several hydrogen storage methods on a vehicle. The study involved a computer-simulation of different hydrogen storage systems to compare the characteristics of the various transfer processes. The thermodynamics of hydrogen transfer from a defined initial condition to its final state was studied. Tabulations of energy requirements, temperature and pressure variations, and limitations concerning the transfer rate were provided. The fueling procedure was simulated using dynamic models, and the components from the initial to the final equilibrium state within the vehicle were characterized. The fluctuations in the system during the physical transfer operations were illustrated. Some of the safety risks include passive risks from toxic and low temperature or cryogenic effects, and explosion and combustion. The authors used fuzzy analysis of survey results to examine safety, which is more subjective in nature than the other properties modeled. An introduction to fuzzy logic was presented, followed by a description of the method used. 2 refs., 7 figs.

  7. Recycling asymmetric hydrogenation catalysts by their immobilisation onto ion-exchange resins. (United States)

    Barbaro, Pierluigi; Bianchini, Claudio; Giambastiani, Giuliano; Oberhauser, Werner; Bonzi, Laura Morassi; Rossi, Filippo; Dal Santo, Vladimiro


    New systems based on cationic chiral phosphine-rhodium complexes anchored to a commercial cation-exchange gel-type resin showed high efficiency and easy recycling in the asymmetric hydrogenation of prochiral olefins.

  8. Synthesis and application of chiral N,N′-dialkylated cyclohexanediamine for asymmetric hydrogenation of aryl ketones

    Institute of Scientific and Technical Information of China (English)

    Meng Lin Ma; Chuan Hong Ren; Ya Jing Lv; Hua Chen; Xian Jun Li


    Chiral N,N′-dialkylated cyclohexanediamine derived ligands have been synthesized and used in the asymmetric hydrogenation of aryl ketones. Optically active alcohols with up to 90% enantiomeric excess were obtained in high yields.

  9. Asymmetric Hydrogenation of α-Hydroxy Ketones: A Reaction Sensitive toward Electronic Effect of Substrates

    Institute of Scientific and Technical Information of China (English)

    XU Hui; MENG Qing-Hua; ZHANG Zhao-Guo


    An efficient asymmetric hydrogenation of a-hydroxy ketones was reported with the catalyst prepared from [RuCl2(benzene)]2 and SunPhos,chiral terminal 1,2-diols were obtained in up to 99% ee.This Ru-catalyzed asymmetric hydrogenation reaction of a-hydroxy ketones represents a new route for the synthesis of chiral terminal 1,2-diols.

  10. 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 ruth

  11. Synthesis of Versatile Building Blocks through Asymmetric Hydrogenation of Functionalized Itaconic Acid Mono-Esters

    NARCIS (Netherlands)

    Hekking, Koen F.W.; Lefort, Laurent; Vries, André H.M. de; Delft, Floris L. van; Schoemaker, Hans E.; Vries, Johannes G. de; Rutjes, Floris P.J.T.


    The rhodium-catalyzed asymmetric hydrogenation of several β-substituted itaconic acid mono-esters, using a library of monodentate phosphoramidite and phosphite ligands is described. Two β-alkyl-substituted substrates were readily hydrogenated by the rhodium complex Rh(COD)2BF4 in combination with (S

  12. 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....

  13. Radiative transfer effects in primordial hydrogen recombination

    CERN Document Server

    Ali-Haïmoud, Yacine; Hirata, Christopher M


    The calculation of a highly accurate cosmological recombination history has been the object of particular attention recently, as it constitutes the major theoretical uncertainty when predicting the angular power spectrum of Cosmic Microwave Background anisotropies. Lyman transitions, in particular the Lyman-alpha line, have long been recognized as one of the bottlenecks of recombination, due to their very low escape probabilities. The Sobolev approximation does not describe radiative transfer in the vicinity of Lyman lines to a sufficient degree of accuracy, and several corrections have already been computed in other works. In this paper, the impact of some previously ignored radiative transfer effects is calculated. First, the effect of Thomson scattering in the vicinity of the Lyman-alpha line is evaluated, using a full redistribution kernel incorporated into a radiative transfer code. The effect of feedback of distortions generated by the optically thick deuterium Lyman-alpha line blueward of the hydrogen ...

  14. Asymmetric Catalytic Hydrogenation Using Rhodium Diphosphinites Derived From D-glucose and D-mannitol

    Institute of Scientific and Technical Information of China (English)


    Three diphosphinites were synthesized for preparing rhodium-diphosphinite complexes. The complexes were used for asymmetric catalytic hydrogenation of amino acid precursor a -acetamidocinnamic acid and its methyl ester. With all complexes, D-amino acid is the most abundant product.

  15. Asymmetric hydrogenation with highly active IndolPhos-Rh catalysts: kinetics and reaction mechanism

    NARCIS (Netherlands)

    Wassenaar, J.; Kuil, M.; Lutz, M.; Spek, A.L.; Reek, J.N.H.


    The mechanism of the Indol- Phos–Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows a

  16. Asymmetric hydrogenation with highly active IndolPhos-Rh catalysts: kinetics and reaction mechanism

    NARCIS (Netherlands)

    Wassenaar, J.; Kuil, M.; Lutz, M.; Spek, A.L.; Reek, J.N.H.


    The mechanism of the IndolPhos-Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an

  17. Monodentate phosphoramidites : A breakthrough in rhodium-catalysed asymmetric hydrogenation of olefins

    NARCIS (Netherlands)

    Berg, Michel van den; Minnaard, Adriaan J.; Haak, Robert M.; Leeman, Michel; Schudde, Ebe P.; Meetsma, Auke; de Vries, Andre H.M.; Maljaars, C. Elizabeth P.; Willans, Charlotte E.; Hyett, David; Boogers, Jeroen A.F.; Henderickx, Hubertus; Feringa, Ben L.


    Monodentate phosphoramidites based on BINOL or substituted BINOL are excellent ligands for the rhodium-catalysed asymmetric hydrogenation of olefins. Very high enantioselectivities were obtained with MonoPhos (7a) the simplest member of this class, a ligand that is prepared in a single step from BIN

  18. Air-water transfer of hydrogen sulfide

    DEFF Research Database (Denmark)

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


    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...... differences in KLaH2S at pH values between 4.5 and 8.0 became larger as the turbulence level increased, whereas those at pH between 4.5 and 7.0 did not statistically show any change. At constant pH, KLaH2S/KLaO2 was observed not to be dependent on the turbulence range studied. KLaH2S/KLaO2 ratio was 0...

  19. Isonitrile iron(II) complexes with chiral N2P2 macrocycles in the enantioselective transfer hydrogenation of ketones. (United States)

    Bigler, Raphael; Mezzetti, Antonio


    Bis(isonitrile) iron(II) complexes bearing a C2-symmetric N2P2 macrocyclic ligand, which are easily prepared from the corresponding bis(acetonitrile) analogue, catalyze the asymmetric transfer hydrogenation (ATH) of a broad scope of ketones in excellent yields (up to 98%) and with high enantioselectivity (up to 91% ee).

  20. Phosphonic acid functionalized asymmetric phthalocyanines: synthesis, modification of indium tin oxide, and charge transfer. (United States)

    Polaske, Nathan W; Lin, Hsiao-Chu; Tang, Anna; Mayukh, Mayunk; Oquendo, Luis E; Green, John T; Ratcliff, Erin L; Armstrong, Neal R; Saavedra, S Scott; McGrath, Dominic V


    Metalated and free-base A(3)B-type asymmetric phthalocyanines (Pcs) bearing, in the asymmetric quadrant, a flexible alkyl linker of varying chain lengths terminating in a phosphonic acid (PA) group have been synthesized. Two parallel series of asymmetric Pc derivatives bearing aryloxy and arylthio substituents are reported, and their synthesis and characterization through NMR, combustion analysis, and MALDI-MS are described. We also demonstrate the modification of indium tin oxide (ITO) substrates using the PA functionalized asymmetric Pc derivatives and monitoring their electrochemistry. The PA functionalized asymmetric Pcs were anchored to the ITO surface through chemisorption and their electrochemical properties characterized using cyclic voltammetry to investigate the effects of PA structure on the thermodynamics and kinetics of charge transfer. Ionization energies of the modified ITO surfaces were measured using ultraviolet photoemission spectroscopy.

  1. Phosphonic Acid Functionalized Asymmetric Phthalocyanines: Synthesis, Modification of Indium Tin Oxide (ITO), and Charge Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Polaske, Nathan W.; Lin, Hsiao-Chu; Tang, Anna; Mayukh, Mayank; Oquendo, Luis E.; Green, John; Ratcliff, Erin L.; Armstrong, Neal R.; Saavedra, S. Scott; McGrath, Dominic V.


    Metalated and free-base A₃B-type asymmetric phthalocyanines (Pcs) bearing, in the asymmetric quadrant, a flexible alkyl linker of varying chain lengths terminating in a phosphonic acid (PA) group have been synthesized. Two parallel series of asymmetric Pc derivatives bearing aryloxy and arylthio substituents are reported, and their synthesis and characterization through NMR, combustion analysis, and MALDI-MS are described. We also demonstrate the modification of indium tin oxide (ITO) substrates using the PA functionalized asymmetric Pc derivatives and monitoring their electrochemistry. The PA functionalized asymmetric Pcs were anchored to the ITO surface through chemisorption and their electrochemical properties characterized using cyclic voltammetry to investigate the effects of PA structure on the thermodynamics and kinetics of charge transfer. Ionization energies of the modified ITO surfaces were measured using ultraviolet photoemission spectroscopy.

  2. The Combinatorial Approach to Asymmetric Hydrogenation: More Miles out of Monophos

    Institute of Scientific and Technical Information of China (English)

    Johannes G. de Vries


    @@ 1Introduction In custom manufacturing time-to-market is of overriding importance. Thus, asymmetric hydrogenation will be applied only if an appropriate catalyst can be found in a very short period of time. For this reason we have build up a full-scale capability for High Throughput Experimentation, encompassing several robot systems. As ligand synthesis was the last remaining barrier we have explored, together with the University of Groningen, the use of simple monodentate ligands, such as MonoPhosTM. These ligands can be synthesised in two chemical steps, from BINOL, PCl3 and an amine.Surprisingly, very high enantioselectivities can be obtained in the asymmetric hydrogenation of α-and β-dehydro-amino acids and esters, aromatic enamides, itaconic acid and ester[1]. See Scheme 1 and 2(at page 830).

  3. Synthesis of Novel C2-Symmetrical Bidentate Phosphoramidite Ligands for Rh-catalyzed Asymmetric Hydrogenation of β-(Acylamino)acrylates

    Institute of Scientific and Technical Information of China (English)

    Qing Heng ZENG; Xiang Ping HU; Xin Miao LIANG; Zhuo ZHENG


    Two new C2-symmetrical bidentate phosphoramidite ligands were synthesized and employed in the Rh-catalyzed asymmetric hydrogenation of β-(acylamino)acrylates, up to 89% ee with full conversions was obtained.

  4. Asymmetric hydrogenation on chirally modified Pt: origin of hydrogen in the N-H-O interaction between cinchonidine and ketone. (United States)

    Maeda, Nobutaka; Hungerbühler, Konrad; Baiker, Alfons


    An understanding of the chiral site-substrate interaction is a necessary prerequisite for the rational design and development of efficient heterogeneous asymmetric catalysts. For the enantioselective hydrogenation of α-ketoesters on cinchona-modified platinum, it has earlier been proposed that the crucial interaction is an N-H-O type hydrogen bonding between the quinuclidine N atom of cinchonidine and the α-carbonyl O atom of the substrate. The involved hydrogen atom has been proposed to originate either from protonation (in protic solvent) or from dissociatively adsorbed hydrogen (in aprotic solvent), but experimental evidence for the latter was lacking so far. In this study, in situ attenuated total reflection infrared spectroscopy combined with modulation excitation spectroscopy and phase sensitive detection provides clear evidence that in aprotic media, hydrogen dissociated on Pt is involved in the N-H-O interaction between the chiral modifier, cinchonidine, and the ketone. In the absence of Pt (pure alumina support), no such interaction occurs, indicating the crucial role of dissociated hydrogen in the formation of the diastereomeric transition complex.

  5. Efficient C2-Symmetric Chiral Schiff Bases for Lanthanide-catalyzed Asymmetric Hydrogenation of Acetophenone

    Institute of Scientific and Technical Information of China (English)

    Peng Fei YAN; Wen Bin SUN; Guang Ming LI; Chun Hong NIE; Zheng Yu YUE


    An array of C2-symmetric chiral Schiff bases of substituted salicylaldehyde (1R, 2R)-1,2-cyclohexanediamine and (R)-(+)-2, 2'-diamino-1, 1'-binaphthalene, incorporated with lanthanide complexes, have been applied as catalysts for asymmetric hydrogenation of acetophenone for the first time. Highly enantioselective product with 90% enantiomeric excess (e.e.) was obtained when the catalyst, hybridized by the bulky electron-donating 3, 5-di-tert-butyl substituted Schiff base (2) and SmCl3·4THF, was employed.

  6. Asymmetric cyclopropanation of chalcones using chiral phase-transfer catalysts



    The first phase-transfer catalyzed cyclopropanation reaction of chalcones using bromomalonates as the nucleophiles in a Michael Initiated Ring Closing reaction (MIRC) was developed. Key to success was the use of a free OH-containing cinchona alkaloid ammonium salt catalyst and carefully optimized liquid/liquid reaction conditions. The reaction performed well for electron neutral and electron deficient chalcones giving the products in yields up to 98% and with enantiomeric ratios up to 91:9.

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

    DEFF Research Database (Denmark)

    Kermani, Nasrin Arjomand; Rokni, Masoud


    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 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...... 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...

  8. 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...

  9. 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.


    Institute of Scientific and Technical Information of China (English)


    The optical α-amino acids were synthesized under room temperature by alkylation of N-(diphenyl methylene) glycine t-butyl ester under polymer-supported phase transfer conditions using polymer-supported cinchonine (or quinine) alkaloids as chiral phase transfer catalysts and dichloromethane as solvent, followed by hydrolysis of the above intermediates introduced to the final products-optical α-amino acids. This is a new method for the asymmetric synthesis of α-amino acids. The influences of catalyst,temperature, substrates, and organic solvents on the chemical yield and optical purities of products were studied.

  11. 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.

  12. Specific Heat Properties of Proton Transfer in Hydrogen Bonded Systems

    Institute of Scientific and Technical Information of China (English)

    庞小峰; 封原平


    The thermodynamic properties of proton transport along hydrogen-bonded systems at finite temperatures have been studied by our model. We first derive the dynamic equations of the proton transport and find the solutions and the free energy of the systems. Finally, we obtain the specific heats of the hydrogen bonded systems, resulting from the motion of the soliton, by using transfer integral way. The theoretical value is basically consistent with the experimental data.

  13. Rh-Catalyzed Asymmetric Hydrogenation of α-Substituted Vinyl Sulfones: An Efficient Approach to Chiral Sulfones. (United States)

    Shi, Liyang; Wei, Biao; Yin, Xuguang; Xue, Peng; Lv, Hui; Zhang, Xumu


    Rh/(S)-(+)-DTBM-Segphos complex catalyzed asymmetric hydrogenation of α-substituted vinyl sulfones has been achieved, furnishing the desired products in high yields and excellent enantioselectivities (>90% yield, up to 99% ee). This method provided an efficient approach to α-substituted chiral sulfones under mild conditions and has potential applications in organic synthesis.

  14. Kinetic investigation on the hydrogen transfer from dihydropyridines to hydrazyls

    Energy Technology Data Exchange (ETDEWEB)

    Abou-Elenien, G.; Rieser, J.; Ismail, N.; Wallenfels, K.


    The results of a kinetic study on the hydrogen transfer between different dihydropyridines and mono-, bis- and trishydrazyls of the tricyanobenzene series are described. The reactions have been found to obey in all cases a second-order law. The influences of solvent medium, redox-potentials of the reactants and temperature on the rates of reactions have been investigated.

  15. Biocatalytic oxidation of benzyl alcohol to benzaldehyde via hydrogen transfer

    NARCIS (Netherlands)

    Orbegozo, Thomas; Lavandera, Iván; Fabian, Walter M.F.; Mautner, Barbara; Vries, Johannes G. de; Kroutil, Wolfgang


    Various types of biocatalysts like oxidases, alcohol dehydrogenases, and microbial cells were tested for the oxidation of benzyl alcohol. Oxidases in combination with molecular oxygen led to low conversion. Alcohol dehydrogenases and microbial cells were tested in a hydrogen transfer reaction employ

  16. Bidentates versus monodentates in asymmetric hydrogenation catalysis: synergic effects on rate and allosteric effects on enantioselectivity. (United States)

    Norman, David W; Carraz, Charles A; Hyett, David J; Pringle, Paul G; Sweeney, Joseph B; Orpen, A Guy; Phetmung, Hirrahataya; Wingad, Richard L


    C 1-Symmetric phosphino/phosphonite ligands are prepared by the reactions of Ph 2P(CH 2) 2P(NMe 2) 2 with ( S)-1,1'-bi-2-naphthol (to give L A ) or ( S)-10,10'-bi-9-phenanthrol (to give L B ). Racemic 10,10'-bi-9-phenanthrol is synthesized in three steps from phenanthrene in 44% overall yield. The complexes [PdCl 2( L A,B )] ( 1a, b), [PtCl 2( L A,B )] ( 2a, b), [Rh(cod)( L A,B )]BF 4 ( 3a, b) and [Rh( L A,B ) 2]BF 4 ( 4a, b) are reported and the crystal structure of 1a has been determined. A (31)P NMR study shows that M, a 1:1 mixture of the monodentates, PMePh 2 and methyl monophosphonite L 1a (based on ( S)-1,1 '-bi-2-naphthol), reacts with 1 equiv of [Rh(cod) 2]BF 4 to give the heteroligand complex [Rh(cod)(PMePh 2)( L 1a )]BF 4 ( 5) and homoligand complexes [Rh(cod)(PMePh 2) 2]BF 4 ( 6) and [Rh(cod)( L 1a ) 2]BF 4 ( 7) in the ratio 2:1:1. The same mixture of 5- 7 is obtained upon mixing the isolated homoligand complexes 6 and 7 although the equilibrium is only established rapidly in the presence of an excess of PMePh 2. The predominant species 5 is a monodentate ligand complex analogue of the chelate 3a. When the mixture of 5- 7 is exposed to 5 atm H 2 for 1 h (the conditions used for catalyst preactivation in the asymmetric hydrogenation studies), the products are identified as the solvento species [Rh(PMePh 2)( L 1a )(S) 2]BF 4 ( 5'), [Rh(S) 2(PMePh 2) 2]BF 4 ( 6') and [Rh(S) 2( L 1a ) 2]BF 4 ( 7') and are formed in the same 2:1:1 ratio. The reaction of M with 0.5 equiv of [Rh(cod) 2]BF 4 gives exclusively the heteroligand complex cis-[Rh(PMePh 2) 2( L 1a ) 2]BF 4 ( 8), an analogue of 4a. The asymmetric hydrogenation of dehydroamino acid derivatives catalyzed by 3a, b is reported, and the enantioselectivities are compared with those obtained with (a) chelate catalysts derived from analogous diphosphonite ligands L 2a and L 2b , (b) catalysts based on methyl monophosphonites L 1a and L 1b , and (c) catalysts derived from mixture M. For the cinnamate and

  17. Determination of forced convective heat transfer coefficients for subsonic flows over heated asymmetric NANA 4412 airfoil (United States)

    Dag, Yusuf

    Forced convection over traditional surfaces such as flat plate, cylinder and sphere have been well researched and documented. Data on forced convection over airfoil surfaces, however, remain very scanty in literature. High altitude vehicles that employ airfoils as lifting surfaces often suffer leading edge ice accretions which have tremendous negative consequences on the lifting capabilities and stability of the vehicle. One of the ways of mitigating the effect of ice accretion involves judicious leading edge convective cooling technique which in turn depends on the accuracy of convective heat transfer coefficient used in the analysis. In this study empirical investigation of convective heat transfer measurements on asymmetric airfoil is presented at different angle of attacks ranging from 0° to 20° under subsonic flow regime. The top and bottom surface temperatures are measured at given points using Senflex hot film sensors (Tao System Inc.) and used to determine heat transfer characteristics of the airfoils. The model surfaces are subjected to constant heat fluxes using KP Kapton flexible heating pads. The monitored temperature data are then utilized to determine the heat convection coefficients modelled empirically as the Nusselt Number on the surface of the airfoil. The experimental work is conducted in an open circuit-Eiffel type wind tunnel, powered by a 37 kW electrical motor that is able to generate subsonic air velocities up to around 41 m/s in the 24 square-inch test section. The heat transfer experiments have been carried out under constant heat flux supply to the asymmetric airfoil. The convective heat transfer coefficients are determined from measured surface temperature and free stream temperature and investigated in the form of Nusselt number. The variation of Nusselt number is shown with Reynolds number at various angles of attacks. It is concluded that Nusselt number increases with increasing Reynolds number and increase in angle of attack from 0

  18. 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.

  19. Heat Transfer Characteristics in an Asymmetrical Solid-Liquid System by Molecular Dynamics Simulations (United States)

    Feng, Yuan; Liang, Xingang


    Solid-liquid systems widely exist in micro- and nanodevices, and it is necessary to study the heat transfer mechanism through solid-liquid interfaces. An asymmetrical sandwich structure of a solid-liquid system consisting of liquid argon and artificial solid walls that have the same FCC structure with argon but a different atomic masses is composed. Heat transfer characteristics are investigated by the molecular dynamics method. The interaction strength between a liquid and solid plays an essential role in heat transport at solid-liquid interfaces, and the thermal resistance length is inversely proportional to it. The mass arrangement of artificial solid walls also has a significant effect on heat transport as well. A maximum heat flux comes up due to the mismatch in phonon spectra with the increasing atomic mass of one solid wall. The asymmetrical liquid density profiles are obtained with various mass differences between solid walls. Especially, a thermal rectification effect is observed and the magnitude is inextricably bound up with asymmetry.

  20. Rh-Catalyzed Asymmetric Hydrogenation of a-Enol Ester Phosphonates with 1-Phenylethylamine-Derived Phosphine- Phosphoramidite Ligands

    Institute of Scientific and Technical Information of China (English)


    HU Juan, WANG Dao-yong, ZHENG Zhuo, HU Xiang-ping J. Mol. Catal. (China) 2012, 26(6), 487 ~492 Chiral phosphine-phosphoramidite ligand, ( So, S,, )-2b, was found to be highly efficient in the Rh-catalyzed asymmetric hydrogenation of various α-enol ester phosphonates, in which excellent enantioselectivities (up to 〉99% ee) and high catalyticactivity ( S/C up to 5000) were achieved.

  1. Development of invar joint for hydrogen transfer line in JSNS (United States)

    Teshigawara, M.; Harada, M.; Ooi, M.; Kai, T.; Maekawa, F.; Futakawa, M.


    A plan of 2nd moderator fabrication in JSNS is under way. In terms of low thermal expansion, invar joints, such as Invar-Al and Invar-SS316L joints, were developed by friction welding method as a component of hydrogen transfer line. Mechanical tests such as tensile tests, were carried out at room and cold (77 K) temperature conditions. Especially, Invar-SS316L joint gave high tensile strength (yield strength: ca. 20% higher and ultimate strength: ca. 2.5 times higher) and large strain at 77 K, and fractured not at bonding interface but at base metal of invar. In case of Invar-Al joint, it also gave high yield strength, but fracture was occurred at bonding interface. However, these joints will be available for component of hydrogen transfer line.

  2. Charge density analysis of two proton transfer complexes: Understanding hydrogen bonding and determination of in-crystal dipole moments

    Indian Academy of Sciences (India)

    Reji Thomas; Shrinwantu Pal; Ayan Datta; Mariusz K Marchewka; Henryk Ratajczak; Swapan K Pati; G U Kulkarni


    An experimental charge density study has been carried out on proton-transfer complexes exhibiting nonlinear optical (NLO) properties-melaminium tartrate monohydrate and L-asparaginium picrate employing high-resolution X-ray diffraction at 100 K. Both the complexes crystallize in non-centric space group P21 and the structures exhibit interesting patterns of N-H…O and O-H…O hydrogen bonding. Experimental determination of the dipole moment () for the asymmetric unit reveals that for both the crystals, there is a large cooperative enhancement in the crystalline arising essentially due to hydrogen bond mediated charge transfer between the melaminium ion and the L-tartrate in one case, between the Lasparaginium ion and the picrate in the other complex. We have additionally performed theoretical calculations at the density functional theory (DFT) level to understand the origin of enhancement of the dipole moments in the two systems.

  3. Mixed convective heat and mass transfer analysis for peristaltic transport in an asymmetric channel with Soret and Dufour effects

    Institute of Scientific and Technical Information of China (English)

    F M Abbasi; A Alsaedi; T Hayat


    The present investigation addresses the simultaneous effects of heat and mass transfer in the mixed convection peristaltic flow of viscous fluid in an asymmetric channel. The channel walls exhibit the convective boundary conditions. In addition, the effects due to Soret and Dufour are taken into consideration. Resulting problems are solved for the series solutions. Numerical values of heat and mass transfer rates are displayed and studied. Results indicate that the concentration and temperature of the fluid increase whereas the mass transfer rate at the wall decreases with increase of the mass transfer Biot number. Furthermore, it is observed that the temperature decreases with the increase of the heat transfer Biot number.

  4. Hydrated alizarin complexes: hydrogen bonding and proton transfer. (United States)

    Huh, Hyun; Cho, Sung Haeng; Heo, Jiyoung; Kim, Nam Joon; Kim, Seong Keun


    We investigated the hydrogen bonding structures and proton transfer for the hydration complexes of alizarin (Az) produced in a supersonic jet using fluorescence excitation (FE), dispersed laser induced fluorescence (LIF), visible-visible hole burning (HB), and fluorescence detected infrared (FDIR) spectroscopy. The FDIR spectrum of bare Az with two O-H groups exhibits two vibrational bands at 3092 and 3579 cm(-1), which, respectively, correspond to the stretching vibration of O1-H1 that forms a strong intramolecular hydrogen bond with the C9=O9 carbonyl group and the stretching vibration of O2-H2 that is weakly hydrogen-bonded to O1-H1. For the 1:1 hydration complex Az(H(2)O)(1), we identified three conformers. In the most stable conformer, the water molecule forms hydrogen bonds with the O1-H1 and O2-H2 groups of Az as a proton donor and proton acceptor, respectively. In the other conformers, the water binds to the C10=O10 group in two nearly isoenergetic configurations. In contrast to the sharp vibronic peaks in the FE spectra of Az and Az(H(2)O)(1), only broad, structureless absorption was observed for Az(H(2)O)(n) (n≥ 2), indicating a facile decay process, possibly due to proton transfer in the electronic excited state. The FDIR spectrum with the wavelength of the probe laser fixed at the broad band exhibited a broad vibrational band near the O2-H2 stretching vibration frequency of the most stable conformer of Az(H(2)O)(1). With the help of theoretical calculations, we suggest that the broad vibrational band may represent the occurrence of proton transfer by tunnelling in the electronic ground state of Az(H(2)O)(n) (n≥ 2) upon excitation of the O2-H2 vibration.

  5. Multidimensional modelling to investigate interspecies hydrogen transfer in anaerobic biofilms. (United States)

    Batstone, D J; Picioreanu, C; van Loosdrecht, M C M


    Anaerobic digestion is a multistep process, mediated by a functionally and phylogenetically diverse microbial population. One of the crucial steps is oxidation of organic acids, with electron transfer via hydrogen or formate from acetogenic bacteria to methanogens. This syntrophic microbiological process is strongly restricted by a thermodynamic limitation on the allowable hydrogen or formate concentration. In order to study this process in more detail, we developed an individual-based biofilm model which enables to describe the processes at a microbial resolution. The biochemical model is the ADM1, implemented in a multidimensional domain. With this model, we evaluated three important issues for the syntrophic relationship: (i) Is there a fundamental difference in using hydrogen or formate as electron carrier? (ii) Does a thermodynamic-based inhibition function produced substantially different results from an empirical function? and; (iii) Does the physical co-location of acetogens and methanogens follow directly from a general model. Hydrogen or formate as electron carrier had no substantial impact on model results. Standard inhibition functions or thermodynamic inhibition function gave similar results at larger substrate field grid sizes (> 10 microm), but at smaller grid sizes, the thermodynamic-based function reduced the number of cells with long interspecies distances (> 2.5 microm). Therefore, a very fine grid resolution is needed to reflect differences between the thermodynamic function, and a more generic inhibition form. The co-location of syntrophic bacteria was well predicted without a need to assume a microbiological based mechanism (e.g., through chemotaxis) of biofilm formation.

  6. Inner hydrogen atom transfer in benzo-fused low symmetrical metal-free tetraazaporphyrin and phthalocyanine analogues: density functional theory studies. (United States)

    Qi, Dongdong; Zhang, Yuexing; Cai, Xue; Jiang, Jianzhuang; Bai, Ming


    Density functional theory (DFT) calculations were carried out to study the inner hydrogen atom transfer in low symmetrical metal-free tetrapyrrole analogues ranging from tetraazaporphyrin H(2)TAP (A(0)B(0)C(0)D(0)) to naphthalocyanine H(2)Nc (A(2)B(2)C(2)D(2)) via phthalocyanine H(2)Pc (A(1)B(1)C(1)D(1)). All the transition paths of sixteen different compounds (A(0)B(0)C(0)D(0)-A(2)B(2)C(2)D(2) and A(0)B(0)C(m)D(n), m rings onto the TAP skeleton have significant effect on the potential energy barrier of the inner hydrogen atom transfer. Introducing fused benzene rings onto the hydrogen-releasing pyrrole rings can increase the transitivity of inner hydrogen atom and thus lower the transfer barrier of this inner hydrogen atom while fusing benzene rings onto the hydrogen-accepting pyrrole rings will increase the hydrogen transfer barrier to this pyrrole ring. The transient cis-isomer intermediate with hydrogen atoms joined to the two adjacent pyrrole rings with less fused benzene rings is much stable than the others. It is also found that the benzene rings fused directly onto pyrrole rings have more effect on the inner hydrogen atom transfer than the outer benzene rings fused onto the periphery of isoindole rings. The present work, representing the first effort towards systematically understanding the effect of ring enlargement through asymmetrical peripheral fusion of benzene ring(s) onto the TAP skeleton on the inner hydrogen transfer of tetrapyrrole derivatives, will be helpful in clarifying the N-H tautomerization phenomenon and detecting the cis-porphyrin isomer in bio-systems.

  7. Theoretical Studies on the Hydrogen Bond Transfer and Proton Transfer between Anamorphoses of the Dihydrated Glycine Complex

    Institute of Scientific and Technical Information of China (English)

    WANG Ke-Cheng; MENG Xiang-Jun; SHI Jin; LI Bing-Huan


    The conversion between anamorphoses of the dihydrated glycine complex was studied by means of B3LYP/6-31++G**. It was found that proton transfer was accompanied by hydrogen bond transfer in the process of conversion between different kinds of anamorphoses. With proton transfer, the electrostatic action was notably increased and the hydrogen-bonding action was evidently strengthened when the dihydrated neutral glycine complex converts into dihydrated zwitterionic glycine complex. The activation energy required for hydrogen bond transfer between dihydrated neutral glycine complexes is very low (6.32 kJ·mol-1); however, the hydrogen bond transfer between dihydrated zwitterionic glycine complexes is rather difficult with the required activation energy of 13.52 kJ·mol-1 due to the relatively strong electrostatic action. The activation energy required by proton transfer is at least 27.33 kJ·mol-1, higher than that needed for hydrogen bond transfer. The activation energy for either hydrogen bond transfer or proton transfer is in the bond-energy scope of medium-strong hydrogen bond, so the four kinds of anamorphoses of the dihydrated glycine complex could convert mutually.

  8. Alkane desaturation by concerted double hydrogen atom transfer to benzyne. (United States)

    Niu, Dawen; Willoughby, Patrick H; Woods, Brian P; Baire, Beeraiah; Hoye, Thomas R


    The removal of two vicinal hydrogen atoms from an alkane to produce an alkene is a challenge for synthetic chemists. In nature, desaturases and acetylenases are adept at achieving this essential oxidative functionalization reaction, for example during the biosynthesis of unsaturated fatty acids, eicosanoids, gibberellins and carotenoids. Alkane-to-alkene conversion almost always involves one or more chemical intermediates in a multistep reaction pathway; these may be either isolable species (such as alcohols or alkyl halides) or reactive intermediates (such as carbocations, alkyl radicals, or σ-alkyl-metal species). Here we report a desaturation reaction of simple, unactivated alkanes that is mechanistically unique. We show that benzynes are capable of the concerted removal of two vicinal hydrogen atoms from a hydrocarbon. The discovery of this exothermic, net redox process was enabled by the simple thermal generation of reactive benzyne intermediates through the hexadehydro-Diels-Alder cycloisomerization reaction of triyne substrates. We are not aware of any single-step, bimolecular reaction in which two hydrogen atoms are simultaneously transferred from a saturated alkane. Computational studies indicate a preferred geometry with eclipsed vicinal C-H bonds in the alkane donor.

  9. Hydrogen bonding asymmetric star-shape derivative of bile acid leads to supramolecular fibrillar aggregates that wrap into micrometer spheres. (United States)

    Myllymäki, Teemu T T; Nonappa; Yang, Hongjun; Liljeström, Ville; Kostiainen, Mauri A; Malho, Jani-Markus; Zhu, X X; Ikkala, Olli


    We report that star-shaped molecules with cholic acid cores asymmetrically grafted by low molecular weight polymers with hydrogen bonding end-groups undergo aggregation to nanofibers, which subsequently wrap into micrometer spherical aggregates with low density cores. Therein the facially amphiphilic cholic acid (CA) is functionalized by four flexible allyl glycidyl ether (AGE) side chains, which are terminated with hydrogen bonding 2-ureido-4[1H]pyrimidinone (UPy) end-groups as connected by hexyl spacers, denoted as CA(AGE6-C6H12-UPy)4. This wedge-shaped molecule is expected to allow the formation of a rich variety of solvent-dependent structures due to the complex interplay of interactions, enabled by its polar/nonpolar surface-active structure, the hydrophobicity of the CA in aqueous medium, and the possibility to control hydrogen bonding between UPy molecules by solvent selection. In DMSO, the surfactant-like CA(AGE6-C6H12-UPy)4 self-assembles into nanometer scale micelles, as expected due to its nonpolar CA apexes, solubilized AGE6-C6H12-UPy chains, and suppressed mutual hydrogen bonds between the UPys. Dialysis in water leads to nanofibers with lateral dimensions of 20-50 nm. This is explained by promoted aggregation as the hydrogen bonds between UPy molecules start to become activated, the reduced solvent dispersibility of the AGE-chains, and the hydrophobicity of CA. Finally, in pure water the nanofibers wrap into micrometer spheres having low density cores. In this case, strong complementary hydrogen bonds between UPy molecules of different molecules can form, thus promoting lateral interactions between the nanofibers, as allowed by the hydrophobic hexyl spacers. The wrapping is illustrated by transmission electron microscopy tomographic 3D reconstructions. More generally, we foresee hierarchically structured matter bridging the length scales from molecular to micrometer scale by sequentially triggering supramolecular interactions.

  10. Science Letters: Hydrogen transfer reduction of ketones using formic acid as a hydrogen donor under hydrothermal conditions

    Institute of Scientific and Technical Information of China (English)

    Zheng SHEN; Fang-ming JIN; Ya-lei ZHANG; Bing WU; Jiang-lin CAO


    The hydrothermal experiments with ketones and formic acid showed that the hydrogen transfer reduction of ketones can be conducted using formic acid as a hydride donor in the presence of NaOH at 300℃. The yield of alcohols was considerably higher at a much lower ratio of hydrogen source to ketones than the traditional Meerwein-Ponndorf-Verley (MPV) reduction,reaching 60% for isopropanol from acetone and 70% for lactic acid from pyruvic acid. Water molecules may act as a catalyst in the hydrogen transfer reduction of ketones under hydrothermal conditions.

  11. Intermolecula transfer and elimination of molecular hydrogen in thermal reactions of unsaturated organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Suria, Sabartanty [Iowa State Univ., Ames, IA (United States)


    Two reactions which are important to coal liquefaction include intermolecular transfer and the elimination of two hydrogen atoms. We have designed several model reactions to probe the viability of several hydrogen transfer and elimination pathways. This report described studies on these reactions using organic model compounds.

  12. 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).

  13. Incorporation of hygromycin resistance in Brassica nigra and its transfer to B. napus through asymmetric protoplast fusion. (United States)

    Sacristán, M D; Gerdemann-Knörck, M; Schieder, O


    With the idea to develop a selection system for asymmetric somatic hybrids between oilseed rape (Brassica napus) and black mustard (B. nigra), the marker gene hygromycin resistance was introduced in this last species by protoplast transformation with the disarmed Agrobacterium tumefaciens strain C58 pGV 3850 HPT. The B. nigra lines used for transformation had been previously selected for resistance to two important rape pathogens (Phoma lingam, Plasmodiophora brassicae). Asymmetric somatic hybrids were obtained through fusion of X-ray irradiated (mitotically inactivated) B. nigra protoplasts from transformed lines as donor with intact protoplasts of B. napus, using the hygromycin resistance as selection marker for fusion products. The somatic hybrids hitherto obtained expressed both hygromycin phosphotransferase and nopaline synthase genes. Previous experience with other plant species had demonstrated that besides the T-DNA, other genes of the donor genome can be co-transferred. In this way, the produced hybrids constitute a valuable material for studying the possibility to transfer agronomically relevant characters - in our case, diseases resistances - through asymmetric protoplast fusion.

  14. Bifunctional Asymmetric Catalysis with Hydrogen Chloride: Enantioselective Ring-Opening of Aziridines Catalyzed by a Phosphinothiourea. (United States)

    Mita, Tsuyoshi; Jacobsen, Eric N


    Ring-opening of aziridines with hydrogen chloride to form β-chloroamine derivatives is catalyzed by a chiral phosphinothiourea derivative in high yields and with high enantioselectivities. On the basis of (31)P NMR studies, activation of HCl appears to proceed via quantitative protonation of the catalyst to afford a phosphonium chloride complex.

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

    NARCIS (Netherlands)

    Kiryutin, A.S.; Yurkovskaya, A.V.; Kaptein, R.; 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,

  16. Highly enantioselective synthesis of non-natural aliphatic α-amino acids via asymmetric hydrogenation. (United States)

    Ji, Jianjian; Chen, Caiyou; Cai, Jiayu; Wang, Xinrui; Zhang, Kai; Shi, Liyang; Lv, Hui; Zhang, Xumu


    By employing a rhodium-Duanphos complex as the catalyst, β-alkyl (Z)-N-acetyldehydroamino esters were smoothly hydrogenated in a highly efficient and enantioselective way. Excellent enantioselectivities together with excellent yields were achieved for a series of substrates. An efficient approach for the synthesis of the intermediate of the orally administered anti-diabetic drugs Alogliptin and Linagliptin in the DPP-4 inhibitor class was also developed.

  17. 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

  18. The asymmetric alkylation of dimethylhydrazones; intermolecular chirality transfer using sparteine as chiral ligand. (United States)

    McSweeney, Christina M; Foley, Vera M; McGlacken, Gerard P


    The asymmetric alkylation of ketones represents a fundamental transformation in organic chemistry. Chiral auxiliaries have been used almost exclusively for this transformation. Herein we describe a strategy for the generation of enantiomerically enriched α-alkylated ketones up to an er of 83 : 17, using a chiral ligand protocol.

  19. Schwinger variational calculation of ionization of hydrogen atoms for large momentum transfers

    Indian Academy of Sciences (India)

    K Chakrabarti


    Schwinger variational principle is used here to study large momentum transfer cases of electron and positron impact ionization of atomic hydrogen from the ground state at intermediate and moderately high energies. The results appear somewhat better compared to other theories.

  20. Preliminary Study on Hydrogen Permeation and Stability of BaCe0.90Y0.10O3-δ Membrane under Asymmetric Atm osphere

    Institute of Scientific and Technical Information of China (English)


    @@High-temperature proton conductors (HTPC) have been extensively studied since I wahara et al?1? reported protonic conduction in SrCeO3-based oxid es. Later, the BaCeO3-based oxides, such as BaCe0.90Yb0.10O3- d (BCYb10) and BaCe0.90Y0.10-O3-d (BCY10), we re fou nd to show higher conductivity?2?. High electronic and protonic conducti vity makes BCY10 a potential membrane for hydrogen separation?3?. Thin f ilms with high density, most probably made by sequential coating on porous subst rates, are imperative in order to promote hydrogen permeation flux?4?. T his makes it more necessary for such membranes to be kept stable and unspoilt un der asymmetric hydrogen-permeation atmosphere at elevated temperatures. In this paper, the stability and hydrogen permeation ability of BCY10 membrane are stud ied by XRD, SEM, energy dispersive X-ray (EDX) analysis, H2-TPR process and hydrogen permeation experiment. The results showed that hydrogen cannot permeate through the BCY10 membrane without surface modification, and its surface cannot keep a uniform perovskite structure in the asymmetric atmosphere.

  1. Selective Hydrogen Transfer Reaction in FCC Process:Characterization and Application

    Institute of Scientific and Technical Information of China (English)

    Chen Beiyan; He Mingyuan; Da Zhijian


    The product distribution and gasoline quality of FCC process, especially the olefin content,heavily depends on the catalyst performance in terms of selective/non-selective hydrogen transfer reaction selectivity. A reliable experimental protocol has been established by using n-dodecane as a probe molecule to characterize the selective hydrogen transfer ability of catalytic materials. The results obtained have been correlated with the performance of the practical catalysts.

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

    NARCIS (Netherlands)

    Millar, 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".

  3. Bipolar spin-filtering effect in B- or N-doped zigzag graphene nanoribbons with asymmetric edge hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Li-hua; Zhang, Zi-zhen; Zhao, Jian-Guo [School of Physics & Electronic Science and Institute of Applied Chemistry, Shanxi Datong University, Datong 037009 (China); Ding, Bing-jun [State Key Laboratory for Mechanical Behavior of Materials, Xi' an Jiaotong University, Shannxi 710049 (China); Guo, Yong, E-mail: [School of Physics & Electronic Science and Institute of Applied Chemistry, Shanxi Datong University, Datong 037009 (China); Jin, Chun, E-mail: [School of Physics & Electronic Science and Institute of Applied Chemistry, Shanxi Datong University, Datong 037009 (China)


    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. - Highlights: • We have investigated the spin-dependent transport properties of the H2–5(6)ZGNR–H devices with B/N doping in both ZGNR electrodes. • A perfect bipolar spin-filtering effect can be obtained in 5(6)ZGNR-based hetero-structures with P and AP magnetic configurations. • The graphene-based diode can be attained by manipulating the doping positions of B or N atoms in both electrodes.

  4. Applicability of heat transfer equations to hydrogen combustion


    Shudo, Toshio; Suzuki, Hiroyuki


    Previous research by the authors showed that hydrogen combustion exhibits a higher cooling loss to the combustion chamber wall of an internal combustion engine compared to hydrocarbon combustion because of its higher burning velocity and shorter quenching distance. The high cooling loss means that reduction of the cooling loss is essential to establish a high thermal efficiency in hydrogen combustion engines. This research analyzed the applicability of equations to describe the h...

  5. 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.)

  6. Magnetohydrodynamic peristaltic flow of a hyperbolic tangent fluid in a vertical asymmetric channel with heat transfer

    Institute of Scientific and Technical Information of China (English)

    Sohail Nadeem; Safia Akram


    In the present paper we discuss the magnetohydrodynamic (MHD) peristaltic flow of a hyperbolic tangent fluid model in a vertical asymmetric channel under a zero Reynolds number and long wavelength approximation. Exact solution of the temperature equation in the absence of dissipation term has been computed and the analytical expression for stream function and axial pressure gradient are established. The flow is analyzed in a wave frame of reference moving with the velocity of wave. The expression for pressure rise has been computed numerically. The physical features of pertinent parameters are analyzed by plotting graphs and discussed in detail.

  7. A simple iridicycle catalyst for efficient transfer hydrogenation of N-heterocycles in water. (United States)

    Talwar, Dinesh; Li, Ho Yin; Durham, Emma; Xiao, Jianliang


    A cyclometalated iridium complex is shown to catalyse the transfer hydrogenation of various nitrogen heterocycles, including but not limited to quinolines, isoquinolines, indoles and pyridinium salts, in an aqueous solution of HCO2H/HCO2Na under mild conditions. The catalyst shows excellent functional-group compatibility and high turnover number (up to 7500), with catalyst loadings as low as 0.01 mol % being feasible. Mechanistic investigation of the quinoline reduction suggests that the transfer hydrogenation proceeds via both 1,2- and 1,4-addition pathways, with the catalytic turnover being limited by the step of hydride transfer.

  8. Hydroxylation of benzene with hydrogen peroxide under phase-transfer conditions

    Energy Technology Data Exchange (ETDEWEB)

    Karakhanov, E.A.; Narin, S.Yu.; Filippova, T.Yu.; Dedov, A.G.


    The authors developed a method for the selective hydroxylation of benzene to phenol with hydrogen peroxide in a two-phase water-benzene system in the presence of ions of transition metals and phase-transfer catalysts. As phase-transfer catalysts they used cetyltrimethylammonium bromide, tetrabutyl-ammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, benzyltriethylammonium chloride, dibenzo-18-crown-6, benzo-15-crown-5, N-cetylpyridinium bromide, potassium didodecylsebacinate ..cap alpha..-sulfonate, and polyethylene glycols of various molecular weight. They were able to find the optimal conditions for the selective hydroxylation of benzene with hydrogen peroxide under phase-transfer catalysis conditions.

  9. Hydrogen-bonded proton transfer in the protonated guanine-cytosine (GC+H)+ base pair. (United States)

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


    The single proton transfer at the different sites of the Watson-Crick (WC) guanine-cytosine (GC) DNA base pair are studied here using density functional methods. The conventional protonated structures, transition state (TS) and proton-transferred product (PT) structures of every relevant species are optimized. Each transition state and proton-transferred product structure has been compared with the corresponding conventional protonated structure to demonstrate the process of proton transfer and the change of geometrical structures. The relative energies of the protonated tautomers and the proton-transfer energy profiles in gas and solvent are analyzed. The proton-transferred product structure G(+H(+))-H(+)C(N3)(-H(+))(PT) has the lowest relative energy for which only two hydrogen bonds exist. Almost all 14 isomers of the protonated GC base pair involve hydrogen-bonded proton transfer following the three pathways, with the exception of structure G-H(+)C(O2). When the positive charge is primarily "located" on the guanine moiety (H(+)G-C, G-H(+)C(C4), and G-H(+)C(C6)), the H(1) proton transfers from the N(1) site of guanine to the N(3) site of cytosine. The structures G-H(+)C(C5) and G-H(+)C(C4) involve H(4a) proton transfer from the N(4) of cytosine to the O(6) site of guanine. H(2a) proton transfer from the N(2) site of guanine to the O(2) site of cytosine is found only for the structure G-H(+)C(C4). The structures to which a proton is added on the six-centered sites adjoining the hydrogen bonds are more prone to proton transfer in the gas phase, whereas a proton added on the minor groove and the sites adjoining the hydrogen bonds is favorable to the proton transfer in energy in the aqueous phase.

  10. 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)

  11. Tunable Dendritic Ligands of Chiral 1,2-Diamine and Their Application in Asymmetric Transfer Hydrogenation

    Institute of Scientific and Technical Information of China (English)

    LIU,Wei-Guo; CUI,Xin; CUN,Lin-Feng; WU,Jun; ZHU,Jin; DENG,Jin-Gen


    @@ Dendrimers are perfect monodisperse macromolecules with a regular and highly branched three-dimensional architecture, so their unique physical and chemical properties are noticed and utilized more and more.[1] The dendrimer architecture can offer a means of better controlling the disposition of the catalytic species in soluble polymer-based catalysts and such novel catalysts of nano-scale size may aid the recycling of catalysts simply by supra-filtration or solvent precipitation methods.

  12. The role of hydrogen bonding in excited state intramolecular charge transfer. (United States)

    Chipem, Francis A S; Mishra, Anasuya; Krishnamoorthy, G


    Intramolecular charge transfer (ICT) that occurs upon photoexcitation of molecules is a vital process in nature and it has ample applications in chemistry and biology. The ICT process of the excited molecules is affected by several environmental factors including polarity, viscosity and hydrogen bonding. The effect of polarity and viscosity on the ICT processes is well understood. But, despite the fact that hydrogen bonding significantly influences the ICT process, the specific role of hydrogen bonding in the formation and stabilization of the ICT state is not unambiguously established. Some literature reports predicted that the hydrogen bonding of the solvent with a donor promotes the formation of a twisted intramolecular charge transfer (TICT) state. Some other reports stated that it inhibits the formation of the TICT state. Alternatively, it was proposed that the hydrogen bonding of the solvent with an acceptor favors the TICT state. It is also observed that a dynamic equilibrium is established between the free and the hydrogen bonded ICT states. This perspective focuses on the specific role played by hydrogen bonding of the solvent with the donor and the acceptor, and by proton transfer in the ICT process. The utility of such influence in molecular recognition and anion sensing is discussed with a few recent literature examples in the end.

  13. Heat and mass transfer in a square microchannel with asymmetric heating

    NARCIS (Netherlands)

    Male, van P.; Croon, de M.H.J.M.; Tiggelaar, R.M.; Berg, van den A.; Schouten, J.C.


    This paper describes the heat and mass transfer in a square microchannel that is heated from one side. This microchannel represents a reaction channel in a microreactor that is used to study the kinetics of the catalytic partial oxidation of methane. The microchannel is contained in a silicon wafer

  14. 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...... of model molecular potentials, and with reference to the excess proton conductivity in aqueous solution....

  15. An analytical comparison of convective heat transfer correlations in supercritical hydrogen (United States)

    Dziedzic, William M.; Jones, Stuart C.; Gould, Dana C.; Petley, Dennis H.


    Four correlations that cover the ranges of liquid to gas for turbulent flow convection of hydrogen are compared with CFD analysis over a range of expected design conditions for active cooling of hypersonic aircraft. Analysis of hydrogen cooling in a typical cooling panel shows how predicted design performance varies with the correlation utilized. The CFD heat transfer coefficient results for a heat spike differed significantly from all four correlations. An acceptable heat transfer coefficient can be calculated at the heat spike location by overlooking the coefficient at the spike and averaging the coefficient before and after the spike.

  16. Study of filament performance in heat transfer and hydrogen dissociation in diamond chemical vapor deposition

    Institute of Scientific and Technical Information of China (English)


    Hot-filament chemical vapor deposition (HFCVD) is a promising method for commercial production of diamond films.Filament performance in heat transfer and hydrogen decomposition in reactive environment was investigated. Power consumption by the filament in vacuum, helium and 2% CH4/H2 was experimentally determined in temperature range 1300℃-2200℃. Filament heat transfer mechanism in C-H reactive environment was calculated and analyzed. The result shows that due to surface carburization and slight carbon deposition, radiation in stead of hydrogen dissociation, becomes the largest contributor to power consumption. Filament-surface dissociation of H2 was observed at temperatures below 1873K, demonstrating the feasibility of diamond growth at low filament temperatures. The effective activation energies of hydrogen dissociation on several clean refractory filaments were derived from power consumption data in literatures. They are all lower than that of thermal dissociation of hydrogen, revealing the nature of catalytic dissociation of hydrogen on filament surface. Observation of substrate temperature suggested a weakerrole of atomic hydrogen recombination in heating substrates in C-H environment than in pure hydrogen.

  17. Peristaltic transport of MHD Williamson fluid in an inclined asymmetric channel through porous medium with heat transfer

    Institute of Scientific and Technical Information of China (English)

    K. Ramesh; M. Devakar


    The intention of this investigation is to study the effects of heat transfer and inclined magnetic field on the peristaltic flow of Williamson fluid in an asymmetric channel through porous medium. The governing two-dimensional equations are simplified under the assumption of long wavelength approximation. The simplified equations are solved for the stream function, temperature, and axial pressure gradient by using a regular perturbation method. The expression for pressure rise is computed numerically. The profiles of velocity, pressure gradient, temperature, heat transfer coefficient and stream function are sketched and interpreted for various embedded parameters and also the behavior of stream function for various wave forms is discussed through graphs. It is observed that the peristaltic velocity increases from porous medium to non-porous medium, the magnetic effects have increasing effect on the temperature, and the size of the trapped bolus decreases with the increasing of magnetic effects while the trend is reversed with the increasing of Darcy number. Moreover, limiting solutions of our problem are in close agreement with the corresponding results of the Newtonian fluid model.

  18. The Complex of Crosslinked Chitosan with 4'-formal Benzo-15-crown-5 and Palladium Used as Catalyst for Asymmetric Hydrogenation of α-phenylethanone

    Institute of Scientific and Technical Information of China (English)

    YI Ying; WANG Yuting; WAN Lili; ZHANG Xueyong; MA Shulan


    The crosslinked chitosan was grafted by 4'-formal benzo-15-crown-5 to obtaine crosslinked chitosan with 4'-formal benzo-15-crown-5(CCTS-N=CH-B-15-C-5). Then it was loaded with palldium chloride to gain the heterogeneous catalyst, which was easily isolated from the reaction system. The influences of the Pd content of the catalyst, solvent, and temperature on asymmetric hydrogenation of α-phenylethanone have been studied. The catalyst has been found to catalyze the hydrogenation of α-phenylethanone into the chiral alcohol,α-phenyl ethanol under the mild condition. The optical yield of (R)-l-phenylethanol could be obtained as 97.1% under the following conditions: temperature, 30 ℃; solvent, ethanol; Pd content, 1.43 mmol/g; substrate concentration, 0.02 g/mL due to the cooperative effect of crown ether and chitosan polymer. The stability of this catalyst was also studied at the same time. This chiral natural crosslinked chitosan-palladium complex catalyst could be reused without appreciable change in optical catalytic activity, which will be useful for designing crosslinked-chitosan-based adsorption for metal ions for asymmetric hydrogenation.

  19. Altering intra- to inter-molecular hydrogen bonding by dimethylsulfoxide: A TDDFT study of charge transfer for coumarin 343 (United States)

    Liu, Xiaochun; Yin, Hang; Li, Hui; Shi, Ying


    DFT and TDDFT methods were carried out to investigate the influences of intramolecular and intermolecular hydrogen bonding on excited state charge transfer for coumarin 343 (C343). Intramolecular hydrogen bonding is formed between carboxylic acid group and carbonyl group in C343 monomer. However, in dimethylsulfoxide (DMSO) solution, DMSO 'opens up' the intramolecular hydrogen bonding and forms solute-solvent intermolecular hydrogen bonded C343-DMSO complex. Analysis of frontier molecular orbitals reveals that intramolecular charge transfer (ICT) occurs in the first excited state both for C343 monomer and complex. The results of optimized geometric structures indicate that the intramolecular hydrogen bonding interaction is strengthened while the intermolecular hydrogen bonding is weakened in excited state, which is confirmed again by monitoring the shifts of characteristic peaks of infrared spectra. We demonstrated that DMSO solvent can not only break the intramolecular hydrogen bonding to form intermolecular hydrogen bonding with C343 but also alter the mechanism of excited state hydrogen bonding strengthening.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ogloblin, A. A. [National Research Center Kurchatov Institute (Russian Federation); Zhang, H. Q.; Lin, C. J.; Jia, H. M. [China Institute of Atomic Energy (China); Khlebnikov, S. V. [Khlopin Radium Institute (Russian Federation); Kuzmin, E. A.; Danilov, A. N.; Demyanova, A. S. [National Research Center Kurchatov Institute (Russian Federation); Trzaska, W. H. [University of Jyväskylä, Department of Physics (Finland); Xu, X. X. [China Institute of Atomic Energy (China); Yang, F. [National Research Center Kurchatov Institute (Russian Federation); Sargsyan, V. V., E-mail:; Adamian, G. G.; Antonenko, N. V. [Joint Institute for Nuclear Research (Russian Federation); Scheid, W. [Institüt für Theoretische Physik der Justus-Liebig-Universität (Germany)


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

  1. Conductivity properties of proton transfer and influence of temperature on it in hydrogen-bonded systems

    Institute of Scientific and Technical Information of China (English)

    PANGXiao-feng; YUJia-feng


    We study and calculate the mobility and oonductivity of proton transfer and influence of temperature on it by pang's dynamic model in hydrogen bonded systems, which ooincide with experiments. We further study the mechanism of magnetization of ciguid water in the basis of this model.

  2. 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.

  3. Conductivity properties of proton transfer and influence of temperature on it in hydrogen-bonded systems

    Institute of Scientific and Technical Information of China (English)

    PANG Xiao-feng; YU Jia-feng


    We study and calculate the mobility and conductivity of proton transfer and influence of temperature on it by pang's dynamic model in hydrogen bonded systems, which coincide with experiments. We further study the mechanism of magnetization of ciguid water in the basis of this model.

  4. 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...

  5. 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) Wiley

  6. 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.

  7. 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.

  8. Heat transfer analysis of metal hydrides in metal-hydrogen secondary batteries (United States)

    Onischak, M.; Dharia, D.; Gidaspow, D.


    The heat transfer between a metal-hydrogen secondary battery and a hydrogen-storing metal hydride was studied. Temperature profiles of the endothermic metal hydrides and the metal-hydrogen battery were obtained during discharging of the batteries assuming an adiabatic system. Two hydride materials were considered in two physical arrangements within the battery system. In one case the hydride is positioned in a thin annular region about the battery stack; in the other the hydride is held in a tube down the center of the stack. The results show that for a typical 20 ampere-hour battery system with lanthanum pentanickel hydride as the hydrogen reservoir the system could perform successfully.

  9. Impact of turbulent phase noise on frequency transfer with asymmetric two-way ground-satellite coherent optical links (United States)

    Robert, Clélia; Conan, Jean-Marc; Wolf, Peter


    Bidirectional ground-satellite laser links suffer from turbulence-induced scintillation and phase distortion. We study how turbulence impacts on coherent detection capacity and on the associated phase noise that restricts clock transfer precision. We evaluate the capacity to obtain a two-way cancellation of atmospheric effects despite the asymmetry between up and down link that limits the link reciprocity. For ground-satellite links, the asymmetry is induced by point-ahead angle and possibly the use, for the ground terminal, of different transceiver diameters, in reception and emission. The quantitative analysis is obtained thanks to refined end- to-end simulations under realistic turbulence and wind conditions as well as satellite cinematic. These temporally resolved simulations allow characterizing the coherent detection in terms of time series of heterodyne efficiency for different system parameters. We show that Tip/Tilt correction on ground is mandatory at reception for the down link and as a pre-compensation of the up link. Good correlation between up and down phase noise is obtained even with asymmetric apertures of the ground transceiver and in spite of pointing ahead angle. The reduction to less than 1 rad2 of the two-way differential phase noise is very promising for clock comparisons.

  10. 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.

  11. Dvr1 transfers left-right asymmetric signals from Kupffer's vesicle to lateral plate mesoderm in zebrafish. (United States)

    Peterson, Annita G; Wang, Xinghao; Yost, H Joseph


    An early step in establishing left-right (LR) symmetry in zebrafish is the generation of asymmetric fluid flow by Kupffer's vesicle (KV). As a result of fluid flow, a signal is generated and propagated from the KV to the left lateral plate mesoderm, activating a transcriptional response of Nodal expression in the left lateral plate mesoderm (LPM). The mechanisms and molecules that aid in this transfer of information from the KV to the left LPM are still not clear. Here we provide several lines of evidence demonstrating a role for a member of the TGFβ family member, Dvr1, a zebrafish Vg1 ortholog. Dvr1 is expressed bilaterally between the KV and the LPM. Knockdown of Dvr1 by morpholino causes dramatically reduced or absent expression of southpaw (spaw, a Nodal homolog), in LPM, and corresponding loss of downstream Lefty (lft1 and lft) expression, and aberrant brain and heart LR patterning. Dvr1 morphant embryos have normal KV morphology and function, normal expression of southpaw (spaw) and charon (cha) in the peri-KV region and normal expression of a variety of LPM markers in LPM. Additionally, Dvr1 knockdown does not alter the capability of LPM to respond to signals that initiate and propagate spaw expression. Co-injection experiments in Xenopus and zebrafish indicate that Dvr1 and Spaw can enhance each other's ability to activate the Nodal response pathway and co-immunoprecipitation experiments reveal differential relationships among activators and inhibitors in this pathway. These results indicate that Dvr1 is responsible for enabling the transfer of a left-right signal from KV to the LPM.

  12. Heat transfer in a porous saturated wavy channel with asymmetric convective boundary conditions

    Institute of Scientific and Technical Information of China (English)

    Q Hussain; S Asghar; T Hayat; A Alsaedi


    The viscous flow in a wavy channel with convective boundary conditions is investigated. The channel is filled with a porous viscous fluid. Two cases of equal and different external convection coefficients on the walls are taken into account. Effect of viscous dissipation is also considered. The governing equations are derived employing long wavelength and low Reynolds number approximations. Exact closed form solutions are obtained for the simplified equations. Important physical features for peristaltic flow caused by the wavy wave are pumping, trapping and heat transfer rate at the channel walls. These are discussed one by one in depth and detail through graphical illustrations. Special attention has been given to the effects of convective boundary conditions. The results show that for Bi1≠Bi2, there exists a critical value of Brinkman number Brc at which the temperatures of both the walls become equal. And, for Bi1>Bi2 and Br>Brc, the temperature of the cold wall exceeds the temperature of hot wall.

  13. Transfer Hydrogenation of C= C Double Bonds Catalyzed by Ruthenium Amido-Complexes:Scopes, Limitation and Enantioselectivity

    Institute of Scientific and Technical Information of China (English)

    XUE,Dong; CHENG,Ying-Chun; CUI,Xin; WANG,Qi-Wei; ZHU,Jin; DENG,Jin-Gen


    @@ The reduction of C = C double bonds is one of the most fundamental synthetic transformations and plays a key role in the manufacturing of a wide variety of bulk and fine chemicals. Hydrogenation of olefinic substrates can be achieved readily with molecular hydrogen in many cases, but transfer hydrogenation methods using suitable donor molecules such as formic acid or alcohols are receiving increasing attention as possible synthetic alternatives because it requires no special equipment and avoids the handling of potentially hazardous gaseous hydrogen.

  14. Elimination of spin diffusion effects in saturation transfer experiments: application to hydrogen exchange in proteins. (United States)

    Jensen, Malene Ringkjøbing; Kristensen, Søren M; Led, Jens J


    The NMR saturation transfer experiment is widely used to characterize exchange processes in proteins that take place on the ms-s timescale. However, spin diffusion effects are inherently associated with the saturation transfer experiment and may overshadow the effect of the exchange processes of interest. As shown here, the effects from spin diffusion and exchange processes can be separated by varying the field strength of the saturation pulse, thereby allowing correct exchange rates to be obtained. The method is demonstrated using the hydrogen exchange process in the protein Escherichia coli thioredoxin as an example.

  15. Rate constants for 1,5- and 1,6-hydrogen atom transfer reactions of mono-, di-, and tri-aryl-substituted donors, models for hydrogen atom transfers in polyunsaturated fatty acid radicals. (United States)

    DeZutter, Christopher B; Horner, John H; Newcomb, Martin


    Rate constants for 1,5- and 1,6-hydrogen atom transfer reactions in models of polyunsaturated fatty acid radicals were measured via laser flash photolysis methods. Photolyses of PTOC (pyridine-2-thioneoxycarbonyl) ester derivatives of carboxylic acids gave primary alkyl radicals that reacted by 1,5-hydrogen transfer from mono-, di-, and tri-aryl-substituted positions or 1,6-hydrogen transfer from di- and tri-aryl-substituted positions to give UV-detectable products. Rate constants for reactions in acetonitrile at room temperature ranged from 1 x 10(4) to 4 x 10(6) s(-1). The activation energies for a matched pair of 1,5- and 1,6-hydrogen atom transfers giving tri-aryl-substituted radicals were approximately equal, as were the primary kinetic isotope effects, but the 1,5-hydrogen atom transfer reaction was 1 order of magnitude faster at room temperature than the 1,6-hydrogen atom transfer reaction due to a less favorable entropy of activation for the 1,6-transfer reaction. Solvent effects on the rate constants for the 1,5-hydrogen atom transfer reaction of the 2-[2-(diphenylmethyl)phenyl]ethyl radical at ambient temperature were as large as a factor of 2 with the reaction increasing in rate in lower polarity solvents. Hybrid density functional theory computations for the 1,5- and 1,6-hydrogen atom transfers of the tri-aryl-substituted donors were in qualitative agreement with the experimental results.

  16. 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.

  17. Iron-Catalyzed Regioselective Transfer Hydrogenative Couplings of Unactivated Aldehydes with Simple Alkenes. (United States)

    Zheng, Yan-Long; Liu, Yan-Yao; Wu, Yi-Mei; Wang, Yin-Xia; Lin, Yu-Tong; Ye, Mengchun


    An FeBr3 -catalyzed reductive coupling of various aldehydes with alkenes that proceeds through a direct hydride transfer pathway has been developed. With (i) PrOH as the hydrogen donor under mild conditions, previously challenging coupling reactions of unactivated alkyl and aryl aldehydes with simple alkenes, such as styrene derivatives and α-olefins, proceeded smoothly to furnish a diverse range of functionalized alcohols with complete linear regioselectivity.

  18. Forced flow heat transfer from a round wire in a vertically- mounted pipe to supercritical hydrogen (United States)

    Horie, Y.; Shiotsu, M.; Shirai, Y.; Higa, D.; Shigeta, H.; Tatsumoto, H.; Naruo, Y.; Nonaka, S.; Kobayashi, H.; Inatani, Y.


    Forced flow heat transfer of hydrogen from a round wire in a vertically-mounted pipe was measured at pressure of 1.5 MPa and temperature of 21 K by applying electrical current to give an exponential heat input (Q=Q0exp(t/τ),τ=10 s) to the round wire. Two round wire heaters, which were made of Pt-Co alloy, with a diameter of 1.2 mm and lengths of 54.5 and 120 mm were set on the central axis of a flow channel made of FRP with inner diameter of 5.7 and 8.0 mm, respectively. Supercritical hydrogen flowed upward in the channel. Flow velocities were varied from 1 to 12.5 m/s. The heat transfer coefficients of supercritical hydrogen were compared with the conventional correlation presented by Shiotsu et al. It was confirmed that the heat transfer coefficients for a round wire were expressed well by the correlation using the hydraulic equivalent diameter.

  19. Theoretical Studies of the Role of Vibrational Excitation on the Dynamics of the Hydrogen-Transfer Reaction of F(^2P) + HCl → FH + Cl({^2}P) (United States)

    Ray, Sara E.; Vissers, Gé W. M.; McCoy, Anne B.


    Hydrogen-transfer reactions are probed through vibrational excitation of the HCl bond in the pre-reactive F\\cdotsHCl complex. Such open-shell species provide a challenge for quantum dynamical calculations due to the need to take into account multiple potential energy surfaces to accurately describe the system.A three-dimensional, fully-coupled potential energy surface has been constructed based on electronic energies calculated at the multireference configuration interaction+Davidson correction (MRCI+Q) level of theory with an aug-cc-pVnZ (n=2,3,4) basis. Spin orbit calculations have also been included. Here we present the results of time-dependent quantum wave packet calculations on the asymmetric hydrogen-transfer reaction of F(^2P) + HCl. In these calculations, the reaction is initiated by vibrationally exciting the HCl stretching motion in the pre-reactive F\\cdotsHCl complex. The wave packet is propagated on the coupled potential energy surfaces. Product state distributions were calculated for reactions initiated in the first three vibrationally excited states of HCl, v=1-3. M. P. Deskevich, M. Y. Hayes, K. Takahashi, R. T. Skodje, and D. J. Nesbitt J. Chem. Phys. 124 (22) 224303 (2006) M. P. Deskevich and D. J. Nesbitt private communication(2007)

  20. Synthesis of iridium and rhodium complexes with new chiral phosphine-NHC ligands based on 1,1'-binaphthyl framework and their application in asymmetric hydrogenation. (United States)

    Gu, Peng; Zhang, Jun; Xu, Qin; Shi, Min


    The first series of chiral phosphine-imidazole carbene ligands based on a 1,1'-binaphthyl framework were synthesized from (R)-2-amine-2'-(diphenylphosphino)-1,1'-binaphthyl (1) in a four-step pathway. After deprotonation of these phosphine-imidazolium salts with LiO(t)Bu, and subsequent complexation with [Ir(COD)Cl]2 and anion exchange with NaBArF, phosphine-carbene chelated iridium complexes (R)-6a and (R)-6b were obtained. Their structures have been characterized by NMR and X-ray diffraction analysis. The NHC-phosphine rhodium complex (R)-6c has been also obtained by a similar synthetic method. These iridium complexes have been applied to catalyze the asymmetric hydrogenation of alkenes to give the corresponding products in moderate to excellent conversion (up to 99%) and moderate enantioselectivities under mild conditions (up to 61% ee).

  1. Numerical and experimental analysis of heat transfer in injector plate of hydrogen peroxide hybrid rocket motor (United States)

    Cai, Guobiao; Li, Chengen; Tian, Hui


    This paper is aimed to analyze heat transfer in injector plate of hydrogen peroxide hybrid rocket motor by two-dimensional axisymmetric numerical simulations and full-scale firing tests. Long-time working, which is an advantage of hybrid rocket motor over conventional solid rocket motor, puts forward new challenges for thermal protection. Thermal environments of full-scale hybrid rocket motors designed for long-time firing tests are studied through steady-state coupled numerical simulations of flow field and heat transfer in chamber head. The motor adopts 98% hydrogen peroxide (98HP) oxidizer and hydroxyl-terminated poly-butadiene (HTPB) based fuel as the propellants. Simulation results reveal that flowing liquid 98HP in head oxidizer chamber could cool the injector plate of the motor. The cooling of 98HP is similar to the regenerative cooling in liquid rocket engines. However, the temperature of the 98HP in periphery portion of the head oxidizer chamber is higher than its boiling point. In order to prevent the liquid 98HP from unexpected decomposition, a thermal protection method for chamber head utilizing silica-phenolics annular insulating board is proposed. The simulation results show that the annular insulating board could effectively decrease the temperature of the 98HP in head oxidizer chamber. Besides, the thermal protection method for long-time working hydrogen peroxide hybrid rocket motor is verified through full-scale firing tests. The ablation of the insulating board in oxygen-rich environment is also analyzed.

  2. Intermolecular hydrogen bonds: From temperature-driven proton transfer in molecular crystals to denaturation of DNA

    Indian Academy of Sciences (India)

    Mark Johnson


    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 physical and chemical properties and are thought to play a fundamental role in processes like enzymatic catalysis. By combining elastic and inelastic neutron scattering results with ab initio, lattice dynamics and molecular dynamics simulations, low frequency lattice modes are identified which modulate the potential energy surface of the hydrogen bond proton and drive proton transfer. The second example concerns base-pair opening in DNA which is the fundamental physical process underlying biological processes like denaturation and transcription. We have used an emprical force field and a large scale, all-atom phonon calculation to gain insight into the base-pair opening modes and the apparent `energy gap' between the accepted frequencies for these modes (∼ 100 cm-1 or ∼ 140 K) and the temperature of the biological processes (room temperature to 100° C) [3]. Inelastic neutron scattering spectra on aligned, highly crystalline DNA samples, produced at the ILL, provide the reference data for evaluating the precision of these simulation results.

  3. 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.

  4. Film boiling heat transfer from a wire to upward flow of liquid hydrogen and liquid nitrogen (United States)

    Shiotsu, M.; Shirai, Y.; Horie, Y.; Shigeta, H.; Higa, D.; Tatsumoto, H.; Hata, K.; Kobayashi, H.; Nonaka, S.; Naruo, Y.; Inatani, Y.


    Film boiling heat transfer coefficients in liquid hydrogen were measured for the heater surface superheats to 300 K under pressures from 0.4 to 1.1 MPa, liquid subcoolings to 11 K and flow velocities to 8 m/s. Two test wires were both 1.2 mm in diameter, 120 mm and 200 mm in lengths and were made of PtCo alloy. The test wires were located on the center of 8 mm and 5 mm diameter conduits of FRP (Fiber Reinforced Plastics). Furthermore film boiling heat transfer coefficients in liquid nitrogen were measured only for the 200 mm long wire. The film boiling heat transfer coefficients are higher for higher pressure, higher subcooling, and higher flow velocity. The experimental data were compared with a conventional equation for forced flow film boiling in a wide channel. The data for the 8 mm diameter conduit were about 1.7 times and those for the 5 mm conduit were about 1.9 times higher than the predicted values by the equation. A new equation was presented modifying the conventional equation based on the liquid hydrogen and liquid nitrogen data. The experimental data were expressed well by the equation.

  5. Charge Transfer Dynamics in Semiconductor Quantum Dots Relevant to Solar Hydrogen Production (United States)

    Krauss, Todd

    Artificial conversion of sunlight to chemical fuels has attracted attention for several decades as a potential source of clean, renewable energy. For example, in light-driven proton reduction to molecular hydrogen, a light-absorbing molecule (the photosensitizer) rapidly transfers a photoexcited electron to a catalyst for reducing protons. We recently found that CdSe quantum dots (QDs) and simple aqueous Ni2+ salts in the presence of a sacrificial electron donor form a highly efficient, active, and robust system for photochemical reduction of protons to molecular hydrogen. To understand why this system has such extraordinary catalytic behavior, ultrafast transient absorption (TA) spectroscopy studies of electron transfer (ET) processes from the QDs to the Ni catalysts were performed. CdSe QDs transfer photoexcited electrons to a Ni-dihydrolipoic acid (Ni-DHLA) catalyst complex extremely fast and with high efficiency. Even under high fluence, the relative fraction of TA signal due to ET remains well over 80%, and depopulation from exciton-exciton annihilation is minimal (6%). We also found that increasing QD size and/or shelling the core CdSe QDs with a shell of CdS slowed the ET rate, in agreement with the relative efficiency of photochemical H2 generation. The extremely fast ET provides a fundamental explanation for the exceptional photocatalytic H2 activity of the CdSe QD/Ni-DHLA system and guides new directions for further improvements.

  6. 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.

  7. On Combined Effects of Heat Transfer and Chemical Reaction for the Flow through an Asymmetric Channel with Orthogonally Deformable Porous Walls

    Directory of Open Access Journals (Sweden)

    Syed Tauseef Mohyud-Din


    Full Text Available The combined effects of heat transfer and chemical reaction are studied for the flow through a semi-infinite asymmetric channel with orthogonally deformable porous walls. The similarity transforms have been used to reduce the conservation laws to a corresponding system of nonlinear ordinary differential equations. The resulting equations are solved, both analytically and numerically, by using Homotopy Analysis Method (HAM and the fourth-order Runge-Kutta (RK-4 method, respectively. The convergence of the analytical solution is assured through the so-called total squared residual error analysis. The optimal values of auxiliary parameters are obtained by minimizing the total squared residual error.

  8. 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.

  9. 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.

  10. Properties of Proton Transfer in Hydrogen-Bonded Systems at Finite Temperature

    Institute of Scientific and Technical Information of China (English)

    PANG Xiao-Feng


    The properties of proton transfer along hydrogen-bonded molecular systems are studied at finite temperature. The dynamic equations of the proton transport along the systems are obtained by using a completely quantummechanics method. From the dynamic equations and its soliton solutions we find out specific heat arising from the motionof solitons in the systems with finite temperature and the critical temperature of the soliton in the protein molecules,which is about 318 K. This shows that we can continuously study some biological phenomena in the living systems bythis model.

  11. Synthesis of novel chiral tetraaza ligands and their application in enantioselective transfer hydrogenation of ketones

    Institute of Scientific and Technical Information of China (English)

    Shen Luan Yu; Yan Yun Li; Zhen Rong Dong; Jing Xing Gao


    Novel chiral tetraaza ligands (R)-N,N'-bis[2-(piperidin-l-yl)benzylidene]propane-1,2-diamine 6 and (S)-N-[2-(piperidin-1-yl)benzylidene]-3-{ [2-(piperidin-1-yl)benzylidene]amino}-alanine sodium salt 7 have been synthesized and fully characterized by NMR,IR,MS and CD spectra.The catalytic property of the ligands was investigated in Ir-catalyzed enantioselective transfer hydrogenation of ketones.The corresponding optical active alcohols were obtained with high yields and moderate ees under mild reaction conditions.

  12. Resonant electron transfer in slow collisions of protons with Rydberg hydrogen atoms

    Energy Technology Data Exchange (ETDEWEB)

    Janev, R.K.; Joachain, C.J.; Nedeljkovic, N.N.


    The resonant charge-transfer reaction of protons on highly excited hydrogen atoms is considered by taking into account both the tunneling (under-barrier) and the over-barrier (classically allowed) electron transitions. It is demonstrated that in a wide range of variation of the reduced ve- locity v = vn, the classical transition mechanism is predominant. Cross-section calculations for principal quantum numbers n between 10 and 50 are presented. The results for 45< or =n< or =50 are compared with the available experimental data and with other theoretical calculations.

  13. 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...... of two closest water molecules to and from the reaction complex as crucial steps. The water molecules induce a "gated" shift of the proton from the donor to the acceptor in the double-well potential with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor...... and acceptor. The short-range and long-range proton transfer as "structural diffusion" of Zundel complexes is also considered. The theoretical formalism is illustrated with the use of Morse, exponential, and harmonic molecular potentials. This approach is extended to proton transfer in strongly hydrogen...

  14. Hydrogen bonding: a channel for protons to transfer through acid-base pairs. (United States)

    Wu, Liang; Huang, Chuanhui; Woo, Jung-Je; Wu, Dan; Yun, Sung-Hyun; Seo, Seok-Jun; Xu, Tongwen; Moon, Seung-Hyeon


    Different from H(3)O(+) transport as in the vehicle mechanism, protons find another channel to transfer through the poorly hydrophilic interlayers in a hydrated multiphase membrane. This membrane was prepared from poly(phthalazinone ether sulfone kentone) (SPPESK) and H(+)-form perfluorosulfonic resin (FSP), and poorly hydrophilic electrostatically interacted acid-base pairs constitute the interlayer between two hydrophilic phases (FSP and SPPESK). By hydrogen bonds forming and breaking between acid-base pairs and water molecules, protons transport directly through these poorly hydrophilic zones. The multiphase membrane, due to this unique transfer mechanism, exhibits better electrochemical performances during fuel cell tests than those of pure FSP and Nafion-112 membranes: 0.09-0.12 S cm(-1) of proton conductivity at 25 degrees C and 990 mW cm(-2) of the maximum power density at a current density of 2600 mA cm(-2) and a cell voltage of 0.38 V.

  15. Synthesis of New Ligand 1,2-Bis { di[( R ,R) -1,3,2-oxzaphosphlidine ] phosphino} ethane with C2 -symmetric Axis and Application in Rh-catalyzed Asymmetric Hydrogenation

    Institute of Scientific and Technical Information of China (English)

    GONG Da-chun; ZHOU Hua; WEI Ping; OUYANG Ping-kai


    New ligand 1,2-bis{ di[(R,R)-1,3,2-oxzaphosphlidine ] phosphino } ethane [ (R, R)-BDOPPEs 1, 2, 3 and 4 ] with C2-symmetric axis and bearing nitrogen and oxygen were synthesized from readily available optically active amino alcohols. Rh complexes with these ligands were highly enantioselective catalysts for asymmetric hydrogenation of N-benzoyldehydroamino acid derivatives and α-functionalized ketones in 99% e. e. and 98% e. e. , respectively.This new class of (R,R)-BDOPPEs 1, 2, 3 and 4 gave much more effectivity and enantionselectivity than their corresponding non-C2-asymmetric aminophosphine phosphinite.

  16. Spectroscopy and energy transfer of molecular transients: Hydrogen isocyanide and the ketenyl radical (United States)

    Wilhelm, Michael J.

    Energy transfer from molecular species has been a long standing topic of profound interest to the chemical physics community. It is worth noting however, that to date, most studies have preferentially focused on chemically stable molecular species. While the literature does contain numerous examples of energy transfer of small radical or chemically unstable species, there have been extremely few studies which have actually probed highly vibrationally excited species. This apparent lack of attention should not be confused with a lack of interest. On the contrary, given the prevalence of vibrationally excited radicals in complex chemical systems such as planetary atmospheres and combustion, it is highly desirable to gain a complete understanding of the energetic deactivation processes of these delicate species. More often than not, the limiting factor which prevents examination of such species is a lack of spectroscopic information which is necessary for the identification as well as modeling of the corresponding species. In this thesis, we explore the use of time-resolved Fourier transform infrared emission spectroscopy, coupled with ab initio quantum chemical calculations, as a means of characterizing the vibrationally excited energy transfer dynamics from hydrogen isocyanide (HNC) as well as the ketenyl (HCCO) radical. It has been determined that each of these radical species can be generated in appreciable relative concentrations and with excess internal energy, following the 193 nm photolysis of specific stable molecular precursors. Through variation of the associated inert atomic collider species, and repeated spectral fitting analysis, it becomes feasible to obtain a measure the time-resolved average internal energy (as a function of the collider species), and hence a measure of the vibrational energy transfer efficiency of each radical species. It is observed that both HNC and HCCO exhibit enhanced vibrational energy transfer, for all average internal

  17. Theoretical Design of Thermosyphon for Process Heat Transfer from NGNP to Hydrogen Plant

    Energy Technology Data Exchange (ETDEWEB)

    Piyush Sabharwall; Mike Patterson; Fred Gunnerson


    The Next Generation Nuclear Plant (NGNP) will most likely produce electricity and process heat, with both being considered for hydrogen production. To capture nuclear process heat, and transport it to a distant industrial facility requires a high temperature system of heat exchangers, pumps and/or compressors. The heat transfer system is particularly challenging not only due to the elevated temperatures (up to ~ 1300K) and industrial scale power transport (=50 MW), but also due to a potentially large separation distance between the nuclear and industrial plants (100+m) dictated by safety and licensing mandates. The work reported here is the preliminary analysis of two-phase thermosyphon heat transfer performance with alkali metals. A thermosyphon is a device for transporting heat from one point to another with quite extraordinary properties. In contrast to single-phased forced convective heat transfer via ‘pumping a fluid’, a thermosyphon (also called a wickless heat pipe) transfers heat through the vaporization / condensing process. The condensate is further returned to the hot source by gravity, i.e. without any requirement of pumps or compressors. With this mode of heat transfer, the thermosyphon has the capability to transport heat at high rates over appreciable distances, virtually isothermally and without any requirement for external pumping devices. Two-phase heat transfer by a thermosyphon has the advantage of high enthalpy transport that includes the sensible heat of the liquid, the latent heat of vaporization, and vapor superheat. In contrast, single-phase forced convection transports only the sensible heat of the fluid. Additionally, vapor-phase velocities within a thermosyphon are much greater than single-phase liquid velocities within a forced convective loop. Thermosyphon performance can be limited by the sonic limit (choking) or vapor flow and/or by condensate entrainment. Proper thermosyphon requires analysis of both.

  18. Phenyl-ring rotational disorder in the two-dimensional hydrogen-bonded structure of the 1:1 proton-transfer salt of the diazo-dye precursor 4-(phenyldiazenyl)aniline (aniline yellow) with L-tartaric acid. (United States)

    Smith, Graham; Wermuth, Urs D; Young, David J


    In the structure of the 1:1 proton-transfer compound from the reaction of L-tartaric acid with the azo-dye precursor aniline yellow [4-(phenyldiazenyl)aniline], namely 4-(phenyldiazenyl)anilinium (2R,3R)-3-carboxy-2,3-dihydroxypropanoate, C(12)H(12)N(3)(+) x C(4)H(5)O(6)(-), the asymmetric unit contains two independent 4-(phenyldiazenyl)anilinium cations and two hydrogen L-tartrate anions. The structure is unusual in that all four phenyl rings of the two cations have identical rotational disorder with equal occupancy of the conformations. The two hydrogen L-tartrate anions form independent but similar chains through head-to-tail carboxyl-carboxylate O-H...O hydrogen bonds [graph set C(7)], which are then extended into a two-dimensional hydrogen-bonded sheet structure through hydroxy O-H...O hydrogen-bonded links. The anilinium groups of the 4-(phenyldiazenyl)anilinium cations are incorporated into the sheets and also provide internal hydrogen-bonded extensions, while their aromatic tails are layered in the structure without significant association except for weak pi-pi interactions [minimum ring centroid separation = 3.844 (3) A]. The hydrogen L-tartrate residues of both anions exhibit the common short intramolecular hydroxy-carboxylate O-H...O hydrogen bonds. This work provides a solution to the unusual disorder problem inherent in the structure of this salt, as well as giving another example of the utility of the hydrogen tartrate anion in the generation of sheet substructures in molecular assembly processes.

  19. Liquid-Phase Catalytic Transfer Hydrogenation of Furfural over Homogeneous Lewis Acid-Ru/C Catalysts. (United States)

    Panagiotopoulou, Paraskevi; Martin, Nickolas; Vlachos, Dionisios G


    The catalytic performance of homogeneous Lewis acid catalysts and their interaction with Ru/C catalyst are studied in the catalytic transfer hydrogenation of furfural by using 2-propanol as a solvent and hydrogen donor. We find that Lewis acid catalysts hydrogenate the furfural to furfuryl alcohol, which is then etherified with 2-propanol. The catalytic activity is correlated with an empirical scale of Lewis acid strength and exhibits a volcano behavior. Lanthanides are the most active, with DyCl3 giving complete furfural conversion and a 97 % yield of furfuryl alcohol at 180 °C after 3 h. The combination of Lewis acid and Ru/C catalysts results in synergy for the stronger Lewis acid catalysts, with a significant increase in the furfural conversion and methyl furan yield. Optimum results are obtained by using Ru/C combined with VCl3 , AlCl3 , SnCl4 , YbCl3 , and RuCl3 . Our results indicate that the combination of Lewis acid/metal catalysts is a general strategy for performing tandem reactions in the upgrade of furans.

  20. Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene (United States)

    Papadakis, Raffaello; Li, Hu; Bergman, Joakim; Lundstedt, Anna; Jorner, Kjell; Ayub, Rabia; Haldar, Soumyajyoti; Jahn, Burkhard O.; Denisova, Aleksandra; Zietz, Burkhard; Lindh, Roland; Sanyal, Biplab; Grennberg, Helena; Leifer, Klaus; Ottosson, Henrik


    The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S0), becomes exergonic in the first triplet state (T1). This is in line with Baird's rule, which tells that benzene is antiaromatic and destabilized in its T1 state and also in its first singlet excited state (S1), opposite to S0, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T1-state benzene is excellent at H-atom abstraction, while cyclooctatetraene, aromatic in the T1 and S1 states according to Baird's rule, is unreactive. Remarkably, also CVD-graphene on SiO2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions. PMID:27708336

  1. Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene. (United States)

    Papadakis, Raffaello; Li, Hu; Bergman, Joakim; Lundstedt, Anna; Jorner, Kjell; Ayub, Rabia; Haldar, Soumyajyoti; Jahn, Burkhard O; Denisova, Aleksandra; Zietz, Burkhard; Lindh, Roland; Sanyal, Biplab; Grennberg, Helena; Leifer, Klaus; Ottosson, Henrik


    The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S0), becomes exergonic in the first triplet state (T1). This is in line with Baird's rule, which tells that benzene is antiaromatic and destabilized in its T1 state and also in its first singlet excited state (S1), opposite to S0, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T1-state benzene is excellent at H-atom abstraction, while cyclooctatetraene, aromatic in the T1 and S1 states according to Baird's rule, is unreactive. Remarkably, also CVD-graphene on SiO2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions.

  2. Photochemical Hydrogen Abstraction and Electron Transfer Reactions of Tetrachlorobenzoquinone with Pyrimidine Nucleobases

    Institute of Scientific and Technical Information of China (English)

    Kun-hui Liu; Li-dan Wu; Xiao-ran Zou; Wen Yang; Qian Du; Hong-mei Su


    Pentachlorophenol,a widespread environmental pollutant that is possibly carcinogenic to humans,is metabolically oxidized to tetrachloroquinone (TCBQ) which can result in DNA damage.We have investigated the photochemical reaction dynamics of TCBQ with two pyrimidine type nucleobases (thymine and uracil) upon UVA (355 nm) excitation using the technique of nanosecond time-resolved laser flash photolysis.It has been found that 355 nm excitation populates TCBQ molecules to their triplet state 3TCBQ*,which are highly reactive towards thymine or uracil and undergo two parallel reactions,the hydrogen abstraction and electron transfer,leading to the observed photoproducts of TCBQH.and TCBQ.- in transient absorption spectra.The concomitantly produced nucleobase radicals and radical cations are expected to induce a series of oxidative or strand cleavage damage to DNA afterwards.By characterizing the photochemical hydrogen abstraction and electron transfer reactions,our results provide potentially important molecular reaction mechanisms for understanding the carcinogenic effects of pentachlorophenol and its metabolites TCBQ.

  3. Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene (United States)

    Papadakis, Raffaello; Li, Hu; Bergman, Joakim; Lundstedt, Anna; Jorner, Kjell; Ayub, Rabia; Haldar, Soumyajyoti; Jahn, Burkhard O.; Denisova, Aleksandra; Zietz, Burkhard; Lindh, Roland; Sanyal, Biplab; Grennberg, Helena; Leifer, Klaus; Ottosson, Henrik


    The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S0), becomes exergonic in the first triplet state (T1). This is in line with Baird's rule, which tells that benzene is antiaromatic and destabilized in its T1 state and also in its first singlet excited state (S1), opposite to S0, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T1-state benzene is excellent at H-atom abstraction, while cyclooctatetraene, aromatic in the T1 and S1 states according to Baird's rule, is unreactive. Remarkably, also CVD-graphene on SiO2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions.

  4. High enantioselectivity in the asymmetric hydrogenation of ketones by a supported Pt nanocatalyst on a mesoporous modified MCM-41 support

    Institute of Scientific and Technical Information of China (English)

    Susmit Basu


    Catalysts containing metal nanotubes were prepared by the adsorption of platinum metal nano‐tubes onto functionalized and modified silica surfaces (MCM‐41 and fumed silica). (3‐Chloropro‐pyl)trimethoxysilane and cinchonidine were used for functionalization and modification, respec‐tively. Potassium chloroplatinate was used as the metal precursor to impregnate platinum metal nanotubes on the pretreated functionalized and modified silica surfaces. The solid catalysts were characterized by ESEM, TEM, EDAX, and XPS. The MCM‐41 supported platinum nanotube catalyst showed>98%to~100%enantioselectivity towards the hydrogenation of a range of pharmaceuti‐cally important chemicals such as methyl pyruvate, ethyl pyruvate, and acetophenone with nearly full conversion.

  5. Optimal control of fuel overpressure in a polymer electrolyte membrane fuel cell with hydrogen transfer leak during load change (United States)

    Ebadighajari, Alireza; DeVaal, Jake; Golnaraghi, Farid


    Formation of membrane pinholes is a common defect in fuel cells, inflicting more cost and making less durable cells. This work focuses on mitigating this issue, and offers a continuous online treatment instead of attempting to dynamically model the hydrogen transfer leak rate. This is achieved by controlling the differential pressure between the anode and cathode compartments at the inlet side of the fuel cell stack, known as the fuel overpressure. The model predictive control approach is used to attain the objectives in a Ballard 9-cell Mk1100 polymer electrolyte membrane fuel cell (PEMFC) with inclusion of hydrogen transfer leak. Furthermore, the pneumatic modeling technique is used to model the entire anode side of a fuel cell station. The hydrogen transfer leak is embedded in the model in a novel way, and is considered as a disturbance during the controller design. Experimental results for different sizes of hydrogen transfer leaks are provided to show the benefits of fuel overpressure control system in alleviating the effects of membrane pinholes, which in turn increases membrane longevity, and reduces hydrogen emissions in the eventual presence of transfer leaks. Moreover, the model predictive controller provides an optimal control input while satisfying the problem constraints.

  6. Dependence of (35)Cl NQR on hydrogen bonding and temperature in dichlorophenol-aniline charge transfer complexes. (United States)

    Ramananda, D; Ramesh, K P; Uchil, J


    The hydrogen-bonded charge transfer complexes of aniline with pi-acceptors (or proton donors) such as 2,5-, 2,6-, 3,4- and 3,5-dichlorophenol were prepared. The (35)Cl nuclear quadrupole resonance (NQR) frequencies of these charge transfer complexes in the temperature range 77-300 K were measured to ascertain the existence or otherwise of a phase transition upon complex formation. Further, the NQR frequency and asymmetry parameter of the electric field gradient at the site of quadrupole nucleus were used to estimate the chemical bond parameters, namely ionic bond, double bond character of the carbon-chlorine(C--Cl) bond and the percentage charge transfer between the donor-acceptor components in charge transfer complexes. The effect of hydrogen bonding and temperature on the charge transfer process is analysed.

  7. 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


    -(1-naphthyl)ethylamine, ((R)-NEA), as the modifier. On the nonmodified surface, introduction of H2 at a background pressure of ∼1 × 10–6 mbar leads to the rapid break-up of TFAP dimer structures followed by the gradual removal of all TFAP-related images. During the latter step, some monomers display an extra...... 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...

  8. 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

  9. The hydrogen sulfide releasing compounds ATB-346 and diallyl trisulfide attenuate streptozotocin-induced cognitive impairment, neuroinflammation, and oxidative stress in rats: involvement of asymmetric dimethylarginine. (United States)

    Mostafa, Dalia K; El Azhary, Nesrine M; Nasra, Rasha A


    Hydrogen sulfide (H2S) has attracted interest as a gaseous mediator involved in diverse processes in the nervous system, particularly with respect to learning and memory. However, its therapeutic potential in Alzheimer disease (AD) is not fully explored. Therefore, the effects of H2S-releasing compounds against AD-like behavioural and biochemical abnormalities were investigated. Memory deficit was induced by intracerberoventicular injection of streptozotocin (STZ, 3 mg·kg(-1)). Animals were randomly assigned into 5 groups (12 rats each): normal control, STZ treated, and 3 drug-treated groups receiving naproxen, H2S-releasing naproxen (ATB-346), and diallyl trisulfide in 20, 32, 40 mg·kg(-1)·day(-1), respectively. Memory function was assessed by passive avoidance and T-maze tasks. After 21 days, hippocampal IL-6, malondialdehyde, reduced glutathione (GSH), asymmetric dimethylarginine (ADMA), and acetylcholinestrase activity were determined. ATB-346 and diallyl trisulfide ameliorated behavioural performance and reduced malondialdehyde, ADMA, and acetylcholinestrase activity while increasing GSH. This study demonstrates the beneficial effects of H2S release in STZ-induced memory impairment by modulation of neuroinflammation, oxidative stress, and cholinergic function. It also delineates the implication of ADMA to the cognitive impairment induced by STZ. These findings draw the attention to H2S-releasing compounds as new candidates for treating neurodegenerative disorders that have prominent oxidative and inflammatory components such as AD.

  10. Study of coupled heat and mass transfer during absorption of hydrogen in MmNi4·6Al0·4 based hydrogen storage device

    Indian Academy of Sciences (India)

    P Muthukumar; Manvendra M Umekar


    A two-dimensional numerical analysis of coupled heat and mass transfer processes in a cylindrical metal hydride reactor containing MmNi4·6Al0·4 is presented. To understand the hydrogen absorption mechanism the governing equations for energy, momentum and mass conservation and reaction kinetic equations are solved simultaneously using the finite volume method (FVM). 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 be negligible. The results obtained from the computer simulation showed good agreement with the available experimental data. At the supply conditions of 30 bar and 298 K, MmNi4·6Al0·4 stores about 1·28 wt%, which is very close to the experimental value of 1·3 wt%. Overall high heat transfer coefficients are found to reduce the absorption time significantly.

  11. 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.

  12. Transfer hydrogenation catalysis in cells as a new approach to anticancer drug design. (United States)

    Soldevila-Barreda, Joan J; Romero-Canelón, Isolda; Habtemariam, Abraha; Sadler, Peter J


    Organometallic complexes are effective hydrogenation catalysts for organic reactions. For example, Noyori-type ruthenium complexes catalyse reduction of ketones by transfer of hydride from formate. Here we show that such catalytic reactions can be achieved in cancer cells, offering a new strategy for the design of safe metal-based anticancer drugs. The activity of ruthenium(II) sulfonamido ethyleneamine complexes towards human ovarian cancer cells is enhanced by up to 50 × in the presence of low non-toxic doses of formate. The extent of conversion of coenzyme NAD(+) to NADH in cells is dependent on formate concentration. This novel reductive stress mechanism of cell death does not involve apoptosis or perturbation of mitochondrial membrane potentials. In contrast, iridium cyclopentadienyl catalysts cause cancer cell death by oxidative stress. Organometallic complexes therefore have an extraordinary ability to modulate the redox status of cancer cells.

  13. 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

  14. Doing the Limbo with a Low Barrier: Hydrogen Bonding and Proton Transfer in Hydroxyformylfulvene (United States)

    Vealey, Zachary; Nemchick, Deacon; Vaccaro, Patrick


    Model compounds continue to play crucial roles for elucidating the ubiquitous phenomena of hydrogen bonding and proton transfer, often yielding invaluable insights into kindred processes taking place in substantially larger species. The symmetric double-minimum topography that characterizes the potential-energy landscape for an important subset of these systems allows unambiguous signatures of molecular dynamics (in the form of tunneling-induced bifurcations) to be extracted directly from spectral measurements. As a relatively unexplored member of this class, 6-hydroxy-2-formylfulvene (HFF) contains an intramolecular O-H···O interaction that has participating atoms from the hydroxylic (donor) and ketonic (acceptor) moieties closely spaced in a quasi-linear configuration. This unusual arrangement suggests proton transduction to occur with minimal encumbrance, possibly leading to a pronounced dislocation of the shuttling hydron commensurate with the concepts of low-barrier hydrogen bonding (which are distinguished by great strength, short distance, and vanishingly small potential barriers). A variety of spectroscopic probes built primarily upon the techniques of laser-induced fluorescence and dispersed fluorescence have been enlisted to acquire the first vibronically resolved information reported for the ground [tilde{X}1A1] and lowest-lying singlet excited [tilde{A}1B{2} (π*π)] electronic manifolds of HFF entrained in a cold supersonic free-jet expansion. These experimental findings will be discussed and compared to those obtained for related proton-transfer systems, with complimentary quantum-chemical calculations serving to unravel the unique bonding motifs and reactive pathways inherent to HFF.

  15. Effects of mass transfer and hydrogen pressure on the fixed-bed pyrolysis of sunflower bagasse

    Energy Technology Data Exchange (ETDEWEB)

    Putun, E.; Kockar, O.M.; Gercel, F. [Anadolu Univ., Eskisehir (Turkey)] [and others


    There are a number of waste and biomass sources being considered as potential sources of fuels and chemical feedstocks. The economics for biomass pyrolysis are generally considered to be most favourable for (1) plants which grow abundantly and require little cultivation in and lands and (2) wastes available in relatively large quantities from agricultural plants, for example, sunflower and hazel nuts. For the former, one such group of plants is Euphorbiaceae which are characterised by their ability to produce a milky latex, an emulsion of about 30% w/w terpenoids in water. One species in the family, Euphorbia Rigida from Southwestern Anatolia, Turkey is cultivated in close proximity to the sunflower growing regions and their oil extraction plants. The Turkish sunflower oil industry generates 800,000 tons of extraction residue (bagasse) per annum. Thus, both sunflower wastes and latex-producing plants are being considered as feedstocks for a future thermochemical demonstration unit in Turkey. Pyrolysis at relatively high hydrogen pressures (hydropyrolysis) has not been widely investigated for biomass. A potential advantage of hydropyrolysis is the ability to upgrade tar vapours over hydroprocessing catalysts. Fixed-bed pyrolysis and hydropyrolysis experiments have been conducted on sunflower bagasse to assess the effects of mass transfer and hydrogen pressure on oil yield and quality.

  16. Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions. (United States)

    Zheng, Haiyan; Li, Kuo; Cody, George D; Tulk, Christopher A; Dong, Xiao; Gao, Guoying; Molaison, Jamie J; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-Kwang


    Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst.

  17. 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.

  18. Peristaltic Flow and Heat Transfer of a Conducting Phan-Thien-Tanner Fluid in an Asymmetric Channel - Application to Chyme Movement in Small Intestine (United States)

    Vajravelu, K.; Sreenadh, S.; Dhananjaya, S.; Lakshminarayana, P.


    In this paper, the influence of heat transfer on the peristaltic flow of a conducting Phan-Thien-Tanner fluid in an asymmetric channel with porous medium is studied. The coupled nonlinear governing differential equations are solved by a perturbation technique. The expressions for the temperature field, the stream function, the axial velocity, and the pressure gradient are obtained. The effects of the various physical parameters such as the magnetic parameter M, the permeability parameter σ, the Brinkman number Br and the Weissenberg number We on the pumping phenomenon are analyzed through graphs and the results are discussed in detail. It is observed that the velocity and the pressure are decreased with increasing the magnetic parameter M whereas the effect of the parameter M on the temperature field is quite the opposite.

  19. 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...... to the clinically used photosensitizer temoporfin, was used as a model drug, and two types of large liposomes were studied as a potential model acceptor phase. Efficiency of separation of small donor from large acceptor liposomes by AF4 was evaluated in dependence on the injected lipid mass using two different......-line absorbance measurements was found feasible for the chosen model drug, but careful (re-) evaluation of turbidity effects is crucial for other drug and carrier combinations....

  20. Transfer of bacterial blight resistance from Oryza meyeriana to O.Sativa asymmetric somatic hybridization

    Institute of Scientific and Technical Information of China (English)

    ZHU Yongsheng; CHEN Baotang; YU Shunwu; ZHANG Duanpin; ZHANG Xueqin; YAN Qiusheng


    Asymmetric somatic hybrid plants were produced between cultivated rice (Oryza sativa L.) and wild species [O. Meyeriana (Zoll. etMor, exSteud.)] with high resistance to rice bacterial blight. X-ray-irradiated protoplasts of the wild species were used as donor and chemically fused with iodoacetamide-inactivated protoplasts of rice cv. 02428to produce hybrids. Seventy-two plants were regenerated from 623 calli based on metabolic complementation. The morphological characters of the plants closely resembled that of the rice. Simple sequence repeats were employed to identify their hybridity. Cytological analysis of root-tips revealed that their chromosome number varied in the range of 27-38. The somatic hybrids were inoculated with strains of Xanthamonas oryzae pv. Oryzae at adult growth stage and demonstrated the resistance to bacterial blight introgression from the O. Meyeriana.

  1. Metal-Free Hydrogen Atom Transfer from Water: Expeditious Hydrogenation of N-Heterocycles Mediated by Diboronic Acid. (United States)

    Xia, Yun-Tao; Sun, Xiao-Tao; Zhang, Ling; Luo, Kai; Wu, Lei


    A hydrogenation of N-heterocycles mediated by diboronic acid with water as the hydrogen atom source is reported. A variety of N-heterocycles can be hydrogenated with medium to excellent yields within 10 min. Complete deuterium incorporation from stoichiometric D2 O onto substrates further exemplifies the H/D atom sources. Mechanism studies reveal that the reduction proceeds with initial 1,2-addition, in which diboronic acid synergistically activates substrates and water via a six-membered ring transition state.

  2. Do Spin State and Spin Density Affect Hydrogen Atom Transfer Reactivity? (United States)

    Saouma, Caroline T; Mayer, James M


    The prevalence of hydrogen atom transfer (HAT) reactions in chemical and biological systems has prompted much interest in establishing and understanding the underlying factors that enable this reactivity. Arguments have been advanced that the electronic spin state of the abstractor and/or the spin-density at the abstracting atom are critical for HAT reactivity. This is consistent with the intuition derived from introductory organic chemistry courses. Herein we present an alternative view on the role of spin state and spin-density in HAT reactions. After a brief introduction, the second section introduces a new and simple fundamental kinetic analysis, which shows that unpaired spin cannot be the dominant effect. The third section examines published computational studies of HAT reactions, which indicates that the spin state affects these reactions indirectly, primarily via changes in driving force. The essay concludes with a broader view of HAT reactivity, including indirect effects of spin and other properties on reactivity. It is suggested that some of the controversy in this area may arise from the diversity of HAT reactions and their overlap with proton-coupled electron transfer (PCET) reactions.

  3. Proton transfer in hydrogen-bonded network of phenol molecules: intracluster formation of water. (United States)

    Lengyel, Jozef; Gorejová, Radka; Herman, Zdeněk; Fárník, Michal


    Electron ionization and time-of-flight mass spectrometry was used to investigate the phenol clusters (PhOH)n of different size from single molecule to large clusters: in coexpansion with He, the dimers n = 2 are mostly generated; in Ar, large species of n ≥ 10 also occur. Besides [(PhOH)n](+•) cluster ion series, hydrated phenol cluster ions [(PhOH)n·xH2O](+•) with up to x = 3 water molecules and dehydrated phenol clusters [(PhOH)n-H2O](+•) were observed. The hydrated phenol series exhibits minima and maxima that are interpreted as evidence for proton transfer between the hydrogen bonded cluster ions of cyclic structures. The proton transfer leads to a water generation within the clusters, and subsequent elimination of the diphenyl ether molecule(s) from the cluster yields the hydrated phenol cluster ions. Alternatively, a water molecule release yields a series of dehydrated phenols, among which the diphenyl ether ion [PhOPh](+•) (n = 2) constitutes the maximum.

  4. 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.

  5. NQR application to the study of hydrogen dynamics in hydrogen-bonded molecular dimers (United States)

    Asaji, Tetsuo


    The temperature dependences of 1H NMR as well as 35Cl NQR spin-lattice relaxation times T 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 B and the activation energy V/ k 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 1 on the low-temperature side of the T 1 minimum. The NQR T 1 measurements was revealed to be a good probe for the hydrogen transfer dynamics.

  6. 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.

  7. Asymmetric Transfer Hydrogenation to Synthesize R-(-)-Baclofen%不对称氢转移合成R-(-)-Baclofen

    Institute of Scientific and Technical Information of China (English)

    许波洪; 张跃



  8. 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.

  9. Improved performance in coprocessing through fundamental and mechanistic studies in hydrogen transfer and catalysis. Quarterly report, March 27, 1990--June 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.

  10. Resonant charge transfer of hydrogen Rydberg atoms incident at a Cu(100) projected band-gap surface

    CERN Document Server

    Gibbard, J A; Kohlhoff, M; Rennick, C J; So, E; Ford, M; Softley, T P


    The charge transfer (ionization) of hydrogen Rydberg atoms (principal quantum number $n=25-34$) incident at a Cu(100) surface is investigated. Unlike fully metallic surfaces, where the Rydberg electron energy is degenerate with the conduction band of the metal, the Cu(100) surface has a projected bandgap at these energies, and only discrete image states are available through which charge transfer can take place. Resonant enhancement of charge transfer is observed at hydrogen principal quantum numbers for which the Rydberg energy matches the energy of one of the image states. The integrated surface ionization signals show clear periodicity as the energies of states with increasing $n$ come in and out of resonance with the image states. The velocity dependence of the surface ionization dynamics is also investigated. Decreased velocity of the incident H atom leads to a greater mean distance of ionization and a lower field required to extract the ion. The surface-ionization profiles (signal versus applied field) ...

  11. Cu/MgAl(2)O(4) as bifunctional catalyst for aldol condensation of 5-hydroxymethylfurfural and selective transfer hydrogenation. (United States)

    Pupovac, Kristina; Palkovits, Regina


    Copper supported on mesoporous magnesium aluminate has been prepared as noble-metal-free solid catalyst for aldol condensation of 5-hydroxymethylfurfural with acetone, followed by hydrogenation of the aldol condensation products. The investigated mesoporous spinels possess high activity as solid-base catalysts. Magnesium aluminate exhibits superior activity compared to zinc and cobalt-based aluminates, reaching full conversion and up to 81 % yield of the 1:1 aldol product. The high activity can be correlated to a higher concentration of basic surface sites on magnesium aluminate. Applying continuous regeneration, the catalysts can be recycled without loss of activity. Focusing on the subsequent hydrogenation of aldol condensation products, Cu/MgAl2 O4 allows a selective hydrogenation and CO bond cleavage, delivering 3-hydroxybutyl-5-methylfuran as the main product with up to 84 % selectivity avoiding ring saturation. Analysis of the hydrogenation activity reveals that the reaction proceeds in the following order: CC>CO>CO cleavage>ring hydrogenation. Comparable activity and selectivity can be also achieved utilizing 2-propanol as solvent in the transfer hydrogenation, providing the possibility for partial recycling of acetone and optimization of the hydrogen management.

  12. Asymmetric Learning Transfer between Imagined Viewer- and Object-Rotations: Evidence of a Hierarchical Organization of Spatial Reference Frames (United States)

    Pellizzer, Giuseppe; Ba, Maryse Badan; Zanello, Adriano; Merlo, Marco C. G.


    Neural resources subserving spatial processing in either egocentric or allocentric reference frames are, at least partly, dissociated. However, it is unclear whether these two types of representations are independent or whether they interact. We investigated this question using a learning transfer paradigm. The experiment and material were…

  13. 糖基含磷配体在不对称氢化反应中的应用%Application of Sugar-Based Phosphorus Ligands in Asymmetric Hydrogenation

    Institute of Scientific and Technical Information of China (English)

    崔朋雷; 刘卉敏; 果秀敏; 张冬暖; 王彦恩; 王春


    There is a very important application for the asymmetric hydrogenation in the actual industrial production. Sugar is chiral natural product which widely exists in the nature. More and more attention was paid to the research of the chiral sugar's synthesis and application. Sugar derivatives, as chiral ligands, were widely used in asymmetric reactions and the relative research became a very active area in organic chemistry. The recent progress of sugar-based phosphorus-containing ligands that used in asymmetric hydrogenation is reviewed.%不对称氢化反应在实际工业生产中有非常重要的应用.糖类是广泛存在于自然界的手性天然产物,手性糖类化合物的合成与应用研究日益受到人们的关注,以糖类衍生物作为手性配体用于不对称反应已成为有机化学中非常活跃的研究领域.综述了糖基含磷配体用于不对称氢化反应的最新研究进展.

  14. A systematic investigation of quaternary ammonium ions as asymmetric phase-transfer catalysts. Application of quantitative structure activity/selectivity relationships. (United States)

    Denmark, Scott E; Gould, Nathan D; Wolf, Larry M


    Although the synthetic utility of asymmetric phase-transfer catalysis continues to expand, the number of proven catalyst types and design criteria remains limited. At the origin of this scarcity is a lack in understanding of how catalyst structural features affect the rate and enantioselectivity of phase transfer catalyzed reactions. Described in this paper is the development of quantitative structure-activity relationships (QSAR) and -selectivity relationships (QSSR) for the alkylation of a protected glycine imine with libraries of quaternary ammonium ion catalysts. Catalyst descriptors including ammonium ion accessibility, interfacial adsorption affinity, and partition coefficient were found to correlate meaningfully with catalyst activity. The physical nature of the descriptors was rationalized through differing contributions of the interfacial and extraction mechanisms to the reaction under study. The variation in the observed enantioselectivity was rationalized employing a comparative molecular field analysis (CoMFA) using both the steric and electrostatic fields of the catalysts. A qualitative analysis of the developed model reveals preferred regions for catalyst binding to afford both configurations of the alkylated product.

  15. Influence of induced magnetic field and heat transfer on the peristaltic motion of a Jeffrey fluid in an asymmetric channel: Closed form solutions

    Energy Technology Data Exchange (ETDEWEB)

    Akram, Safia, E-mail: [Department of Humanities and Basic Sciences, Military College of Signals, National University of Sciences and Technology, Rawalpindi 46000 (Pakistan); Department of Mathematics, Quaid-i-Azam University 45320, Islamabad 44000 (Pakistan); Nadeem, S. [Department of Mathematics, Quaid-i-Azam University 45320, Islamabad 44000 (Pakistan)


    We discuss the peristaltic motion of a two dimensional Jeffrey fluid in an asymmetric channel under the effects of induced magnetic field and heat transfer. The problem is simplified by using long wave length and low Reynolds approximations. Exact and closed form Adomian solutions are presented. Expressions for the velocity, stream function, magnetic force function, temperature, pressure gradient and pressure rise are computed. The results of pertinent parameters are discussed. Finally, the trapping phenomena for different wave shapes are discussed. It is observed that the pressure rise for sinusoidal wave is less than trapezoidal wave and greater than triangular in a Jeffrey fluid. - Highlights: Black-Right-Pointing-Pointer The effects of induced magnetic field and heat transfer in peristaltic motion of a two dimensional Jeffrey fluid are discussed. Black-Right-Pointing-Pointer In this paper exact and closed form Adomian solutions are presented. Black-Right-Pointing-Pointer Different wave shapes are considered to observe the behavior of pressure rise and trapping phenomena.

  16. Mechanistic Insights into Homogeneous and Heterogeneous Asymmetric Iron Catalysis (United States)

    Sonnenberg, Jessica

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

  17. 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.

  18. Cryogenic Tests of 30 m Flexible Hybrid Energy Transfer Line with Liquid Hydrogen and Superconducting MgB2 Cable (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.

    Recently we reported about first in the world test of 10 m hybrid energy transfer line with liquid hydrogen and MgB2 superconducting cable. In this paper we present the new development of our second hybrid energy transfer line with 30 m length. The flexible 30 m hydrogen cryostat has three sections with different types of thermal insulation in each section: simple vacuum superinsulation, vacuum superinsulation with liquid nitrogen shield and active evaporating cryostatting (AEC) system. We performed thermo-hydraulic tests of the cryostat to compare three thermo-insulating methods. The tests were performed at temperatures from 20 to 26 K, hydrogen flow from 100 to 450 g/s and pressure from 0.25 to 0.5 MPa. It was found that AEC thermal insulation practically eliminated completely heat transfer from room temperature to liquid hydrogen in the 10 m section. AEC thermal insulation method can be used for long superconducting power cables. High voltage current leads were developed as well. The current leads and superconducting MgB2 cable have been passed high voltage DC test up to 50 kV DC. Critical current of the cable at ∼21 K was ∼3500 A. The 30 m hybrid energy system developed is able to deliver up to 135 MW of chemical and electrical power in total.

  19. 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

  20. Simulations of galaxy formation with radiative transfer: Hydrogen reionisation and radiative feedback

    CERN Document Server

    Petkova, Margarita


    We carry out hydrodynamical simulations of galaxy formation that simultaneously follow radiative transfer of hydrogen-ionising photons, based on the optically-thin variable Eddinton tensor approximation as implemented in the {\\small GADGET} code. We consider only star-forming galaxies as sources and examine to what extent they can yield a reasonable reionisation history and thermal state of the intergalactic medium at redshifts around $z\\sim 3$. This serves as an important benchmark for our self-consistent methodology to simulate galaxy formation and reionisation, and for future improvements through accounting of other sources and other wavelength ranges. We find that star formation alone is sufficient for reionising the Universe by redshift $z\\sim6$. For a suitable choice of the escape fraction and the heating efficiency, our models are approximately able to account at the same time for the one-point function and the power spectrum of the Lyman-$\\alpha$ forest. The radiation field has an important impact on ...

  1. Contra-thermodynamic behavior in intermolecular hydrogen transfer of alkylperoxy radicals. (United States)

    Pfaendtner, Jim; Broadbelt, Linda J


    Quantum chemical investigation of bimolecular hydrogen transfer involving alkylperoxy radicals, a key reaction family in the free-radical oxidation of hydrocarbons, was performed to establish structure-reactivity relationships. Eight different reactions were investigated featuring four different alkane substrates (methane, ethane, propane and isobutane) and two different alkylperoxy radicals (methylperoxy and iso-propylperoxy). Including forward and reverse pairs, sixteen different activation energies and enthalpies of reaction were used to formulate structure-reactivity relationships to describe this chemistry. We observed that the enthalpy of formation of loosely bound intermediate states has a strong inverse correlation with the overall heat of reaction and that this results in unique contra-thermodynamic behavior such that more exothermic reactions have higher activation barriers. A new structure-reactivity relationship was proposed that fits the calculated data extremely well: E(A)=E(o)+alphaDeltaH(rxn) where alpha=-0.10 for DeltaH(rxn)0 and E(o)=3.05 kcal mol(-1).

  2. Charge-Transfer Induced High Efficient Hydrogen Evolution of MoS2/graphene Cocatalyst (United States)

    Li, Honglin; Yu, Ke; Li, Chao; Tang, Zheng; Guo, Bangjun; Lei, Xiang; Fu, Hao; Zhu, Ziqiang


    The MoS2 and reduced graphite oxide (rGO) composite has attracted intensive attention due to its favorable performance as hydrogen evolution reaction (HER) catalyst, but still lacking is the theoretical understanding from a dynamic perspective regarding to the influence of electron transfer, as well as the connection between conductivity and the promoted HER performance. Based on the first-principles calculations, we here clearly reveal how an excess of negative charge density affects the variation of Gibbs free energy (ΔG) and the corresponding HER behavior. It is demonstrated that the electron plays a crucial role in the HER routine. To verify the theoretical analyses, the MoS2 and reduced graphite oxide (rGO) composite with well defined 3-dimensional configuration was synthesized via a facile one-step approach for the first time. The experimental data show that the HER performance have a direct link to the conductivity. These findings pave the way for a further developing of 2-dimension based composites for HER applications.

  3. 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.

  4. Investigation of heat transfer performance of high efficient heat exchange component with asymmetric grooved tube%非对称横槽管高效换热元件传热性能研究

    Institute of Scientific and Technical Information of China (English)

    付崇彬; 李炳熙; 韩怀志


    Based on the k-ε model,numerical simulation of flow and heat transfer mechanism of helium in asymmetric grooved tube type was presented in this article. The overall heat transfer performance of the symmetric and asymmetric grooved tube was compared. Meanwhile,the Central Composition Design (CCD) is proceed to optimize the three basic structural parameters (groove pitch,groove wide,groove height) in asymmetric grooved tube. The heat transfer performance affected by various constructions in asymmetric grooved tube was investigated; where the inner mechanism was preliminary discussed. The result show that,the heat transfer performance in asymmetric grooved tube is superior than traditional symmetric grooved tube,the optimal parameters are al2. l-b8-e0. 6.%基于k-ε模型,针对一种非对称横槽管换热元件,对高温高压工况下管内氦气的流动与传热进行了数值模拟研究.比较了非对称横槽管与对称横槽管的综合传热性能.同时,应用“中心复合设计”(CCD)方法对非对称横槽管的三个基本结构参数(槽间距a、槽宽6、槽深e)进行了优化设计,考察了不同结构对非对称横槽管传热性能的影响,并对其内部机理进行了初步的探讨.结果表明,非对称横槽管传热性能优于传统的对称型横槽管,最优结构参数为a12-b8-e0.6.

  5. Asymmetric autocatalysis induced by meteoritic amino acids with hydrogen isotope chirality† †This article is part of a ChemComm ‘Catalysis in Organic Synthesis’ web-theme issue showcasing high quality research in organic chemistry. Please see our website ( to access the other papers in this issue. ‡ ‡Electronic supplementary information (ESI) available: Procedures for the asymmetric autocatalysis in the presence of 1 and 2, the preparation of enantiomers of 1 and 2, and the determination of the enantiomeric purity of 1 and 2. See DOI: 10.1039/b908754k Click here for additional data file. (United States)

    Kawasaki, Tsuneomi; Shimizu, Masako; Nishiyama, Daisuke; Ito, Masateru; Ozawa, Hitomi


    Achiral meteoritic amino acids, glycine and α-methylalanine, with hydrogen isotope (D/H) chirality, acted as the source of chirality in asymmetric autocatalysis with amplification of ee to afford highly enantioenriched 5-pyrimidyl alkanols. PMID:19597604

  6. Ruthenium and osmium complexes of hemilabile chiral monophosphinite ligands derived from 1D-pinitol or 1D-chiro-inositol as catalysts for asymmetric hydrogenation reactions. (United States)

    Slade, Angela T; Lensink, Cornelis; Falshaw, Andrew; Clark, George R; Wright, L James


    The monophosphinite ligands, 1D-1,2;5,6-di-O-cyclopentylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P1), 1D-1,2;5,6-di-O-isopropylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P2), 1D-1,2;5,6-di-O-cyclohexylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P3), and 1D-1,2;5,6-di-O-cyclopentylidene-3-O-ethyl-4-O-diphenylphosphino-chiro-inositol (D-P4), can be conveniently prepared from the chiral natural products 1D-pinitol or 1D-chiro-inositol. On treatment of toluene solutions of RuCl2(PPh3)3 with two mole equivalents of the ligands D-PY (Y = 1-4) the complexes RuCl2(D-P1)2 (1), RuCl2(D-P2)2 (4), RuCl2(D-P3)2 (5), or RuCl2(D-P4)2 (6), respectively, are formed. Similarly, treatment of OsCl2(PPh3)3 with D-P1 gives OsCl2(D-P1)2 (7). The single crystal X-ray structure determination of 1 reveals that each D-P1 ligand coordinates to ruthenium through phosphorus and the oxygen atom of the methoxyl group. Treatment of 1 with excess LiBr or LiI results in metathesis of the chloride ligands and RuBr2(D-P1)2 (2) or RuI2(D-P1)2 (3), respectively, are formed. Exposure of a solution of 1 to carbon monoxide results in the very rapid formation of RuCl2(CO)2(D-P1)2 (8), thereby demonstrating the ease with which the oxygen donors are displaced from the metal and hence the hemilabile nature of the two bidentate D-P1 ligands in 1. Preliminary studies indicate that 1-7 act as catalysts for the asymmetric hydrogenation reactions of acetophenone and 3-quinuclidinone to give the corresponding alcohols in generally high conversions but low enantiomeric excesses.

  7. Efficient estimators for quantum instanton evaluation of the kinetic isotope effects: application to the intramolecular hydrogen transfer in pentadiene. (United States)

    Vanícek, Jirí; Miller, William H


    The quantum instanton approximation is used to compute kinetic isotope effects for intramolecular hydrogen transfer in cis-1,3-pentadiene. Due to the importance of skeleton motions, this system with 13 atoms is a simple prototype for hydrogen transfer in enzymatic reactions. The calculation is carried out using thermodynamic integration with respect to the mass of the isotopes and a path integral Monte Carlo evaluation of relevant thermodynamic quantities. Efficient "virial" estimators are derived for the logarithmic derivatives of the partition function and the delta-delta correlation functions. These estimators require significantly fewer Monte Carlo samples since their statistical error does not increase with the number of discrete time slices in the path integral. The calculation treats all 39 degrees of freedom quantum mechanically and uses an empirical valence bond potential based on a molecular mechanics force field.

  8. Formation, Isolation and Characterization of a New Ruthenium Complex in Reaction of Acetone Masked Terminal Alkynone with Transfer Hydrogenation Catalyst

    Institute of Scientific and Technical Information of China (English)

    郭敏捷; 李到; 孙延辉; 成江; 张兆国


    Reaction of [1S,2S-(Ts-diphen)Ru(Ⅱ)(p-cymene)] (1S,2S-Ts-diphen= 1S,2S-N-tosyl-1,2-diphenylethylenediamine) and 2-hydroxy-2-methyl-non-3-yn-5-one under transfer hydrogenation condition gave a ruthenium complex bearing a 2,5-dihydrofuran moiety. The complex was characterized and a possible mechanism for the formation of the complex was proposed.

  9. 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.

  10. Neutral transition metal hydrides as acids in hydrogen bonding and proton transfer: media polarity and specific solvation effects. (United States)

    Levina, Vladislava A; Filippov, Oleg A; Gutsul, Evgenii I; Belkova, Natalia V; Epstein, Lina M; Lledos, Agusti; Shubina, Elena S


    Structural, spectroscopic, and electronic features of weak hydrogen-bonded complexes of CpM(CO)(3)H (M = Mo (1a), W (1b)) hydrides with organic bases (phosphine oxides R(3)PO (R = n-C(8)H(17), NMe(2)), amines NMe(3), NEt(3), and pyridine) are determined experimentally (variable temperature IR) and computationally (DFT/M05). The intermediacy of these complexes in reversible proton transfer is shown, and the thermodynamic parameters (DeltaH degrees , DeltaS degrees ) of each reaction step are determined in hexane. Assignment of the product ion pair structure is made with the help of the frequency calculations. The solvent effects were studied experimentally using IR spectroscopy in CH(2)Cl(2), THF, and CH(3)CN and computationally using conductor-like polarizable continuum model (CPCM) calculations. This complementary approach reveals the particular importance of specific solvation for the hydrogen-bond formation step. The strength of the hydrogen bond between hydrides 1 and the model bases is similar to that of the M-H...X hydrogen bond between 1 and THF (X = O) or CH(3)CN (X = N) or between CH(2)Cl(2) and the same bases. The latter competitive weak interactions lower the activities of both the hydrides and the bases in the proton transfer reaction. In this way, these secondary effects shift the proton transfer equilibrium and lead to the counterintuitive hampering of proton transfer upon solvent change from hexane to moderately polar CH(2)Cl(2) or THF.

  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. Asymmetric Synthesis and Binding Study of New Long-Chain HPA-12 Analogues as Potent Ligands of the Ceramide Transfer Protein CERT. (United States)

    Ďuriš, Andrej; Daïch, Adam; Santos, Cécile; Fleury, Laurence; Ausseil, Frédéric; Rodriguez, Frédéric; Ballereau, Stéphanie; Génisson, Yves; Berkeš, Dušan


    A series of 12 analogues of the Cer transfer protein (CERT) antagonist HPA-12 with long aliphatic chains were prepared as their (1R,3S)-syn and (1R,3R)-anti stereoisomers from pivotal chiral oxoamino acids. The enantioselective access to these intermediates as well as their ensuing transformation relied on a practical crystallization-induced asymmetric transformation (CIAT) process. Sonogashira coupling followed by triple bond reduction and thiophene ring hydrodesulfurization (HDS) into the corresponding alkane moieties was then implemented to complete the synthetic routes delivering the targeted HPA-12 analogues in concise 4- to 6-step reaction sequences. Ten compounds were evaluated regarding their ability to bind to the CERT START domain by using the recently developed time-resolved FRET-based homogeneous (HTR-FRET) binding assay. The introduction of a lipophilic appendage on the phenyl moiety led to an overall 10- to 1000-fold enhancement of the protein binding, with the highest effect being observed for a n-hexyl residue in the meta position. The importance of the phenyl ring for the activity was indicated by the reduced potency of the 3-deoxyphytoceramide aliphatic analogues. The 1,3-syn stereoisomers were systematically more potent than their 1,3-anti analogues. In silico studies were used to rationalized these trends, leading to a model of protein recognition coherent with the stronger binding of (1R,3S)-syn HPAs.

  13. Kinetic solvent effects on the reactions of the cumyloxyl radical with tertiary amides. Control over the hydrogen atom transfer reactivity and selectivity through solvent polarity and hydrogen bonding. (United States)

    Salamone, Michela; Mangiacapra, Livia; Bietti, Massimo


    A laser flash photolysis study on the role of solvent effects on hydrogen atom transfer (HAT) from the C-H bonds of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-formylpyrrolidine (FPRD), and N-acetylpyrrolidine (APRD) to the cumyloxyl radical (CumO(•)) was carried out. From large to very large increases in the HAT rate constant (kH) were measured on going from MeOH and TFE to isooctane (kH(isooctane)/kH(MeOH) = 5-12; kH(isooctane)/kH(TFE) > 80). This behavior was explained in terms of the increase in the extent of charge separation in the amides determined by polar solvents through solvent-amide dipole-dipole interactions and hydrogen bonding, where the latter interactions appear to play a major role with strong HBD solvents such as TFE. These interactions increase the electron deficiency of the amide C-H bonds, deactivating these bonds toward HAT to an electrophilic radical such as CumO(•), indicating that changes in solvent polarity and hydrogen bonding can provide a convenient method for deactivation of the C-H bond of amides toward HAT. With DMF, a solvent-induced change in HAT selectivity was observed, suggesting that solvent effects can be successfully employed to control the reaction selectivity in HAT-based procedures for the functionalization of C-H bonds.

  14. 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.

  15. Transient Heat Transfer from a Wire Inserted into a Vertically Mounted Pipe to Forced Flow Liquid Hydrogen (United States)

    Tatsumoto, Hideki; Shirai, Yasuyuki; Shiotsu, Masahiro; Naruo, Yoshihiro; Kobayashi, Hiroaki; Inatani, Yoshifumi

    The transient heat transfer from a Pt-Co wire heater inserted into a vertically mounted pipe, through which forced flow subcooled liquid hydrogen was passed, is measured by increasing the exponential heat input with various time periods at a pressure of 0.7 MPa and an inlet temperature of 21 K. The flow velocities range from 0.8 to 5.5 m/s. For shorter periods, the non-boiling heat transfer becomes higher than that given by the Dittus-Boelter equation due to the transient conductive heat transfer contribution. In addition, the transient critical heat flux (CHF) becomes higher than the steady-state CHF. The effect of the flow velocity and period on the transient CHF heat flux is also clarified.

  16. Film Boiling Heat Transfer from a Round Wire to Liquid Hydrogen Flowing Upward in a Concentric Annulus (United States)

    Shiotsu, M.; Shirai, Y.; Oura, Y.; Horie, Y.; Yoneda, K.; Tatsumoto, H.; Hata, K.; Kobayashi, H.; Naruo, Y.; Inatani, Y.

    Hydrogen film boiling heat transfer coefficients were measured for the heater surface superheats up to 400 K under pressures from 400 to 1100 kPa, liquid subcoolings from 0 to 11 K and flow velocities up to 7 m/s. The test wire used was 1.2 mm in diameter and 120 mm in length made of PtCo (0.5 wt.%) alloy, which was located at the center of 8 mm diameter conduit made of FRP (Fiber Reinforced Plastics). The heat transfer coefficients were higher for higher pressure, higher subcooling and higher flow velocity. The heat transfer coefficients were about 1.6 times higher than those predicted by Shiotsu-Hama equation for forced flow film boiling in a wide channel. Discussions were made on the mechanism of difference between them.

  17. Catalytic transfer hydrogenation for stabilization of bio-oil oxygenates: reduction of p-cresol and furfural over bimetallic Ni-Cu catalysts using isopropanol (United States)

    Transfer hydrogenation and hydrodeoxygenation of model bio-oil compounds (p-cresol and furfural) and bio-oils derived from biomass via traditional pyrolysis and tail-gas reactive pyrolysis (TGRP) were conducted. Mild batch reaction conditions were employed, using isopropanol as a hydrogen donor over...

  18. 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.

  19. Hydrogen-atom transfer reactions from ortho-alkoxy-substituted phenols: an experimental approach. (United States)

    Amorati, Riccardo; Menichetti, Stefano; Mileo, Elisabetta; Pedulli, Gian Franco; Viglianisi, Caterina


    The role of intramolecular hydrogen bonding (HB) on the bond-dissociation enthalpy (BDE) of the phenolic O-H and on the kinetics of H-atom transfer to peroxyl radicals (k(inh)) of several 2-alkoxyphenols was experimentally quantified by the EPR equilibration technique and by inhibited autoxidation studies. These compounds can be regarded as useful models for studying the H-atom abstraction from 2-OR phenols, such as many lignans, reduced coenzyme Q and curcumin. The effects of the various substituents on the BDE(O-H) of 2-methoxy, 2-methoxy-4-methyl, 2,4-dimethoxyphenols versus phenol were measured in benzene solution as -1.8; -3.7; -5.4 kcal mol(-1), respectively. In the case of polymethoxyphenols, significant deviations from the BDE(O-H) values predicted by the additive effects of the substituents were found. The logarithms of the k(inh) constants in cumene were inversely related to the BDE(O-H) values, obeying a linear Evans-Polanyi plot with the same slope of other substituted phenols and a y-axis intercept slightly smaller than that of 2,6-dimethyl phenols. In the cases of phenols having the 2-OR substituent included in a five-membered condensed ring (i.e, compounds 9-11), both conformational isomers in which the OH group points toward or away from the oxygen in position 2 were detected by FTIR spectroscopy and the intramolecular HB strength was thus estimated. The contribution to the BDE(O-H) of the ortho-OR substituent in 9, corrected for intramolecular HB formation, was calculated as -5.6 kcal mol(-1). The similar behaviour of cyclic and non-cyclic ortho-alkoxy derivatives clearly showed that the preferred conformation of the OMe group in ortho-methoxyphenoxyl radicals is that in which the methyl group points away from the phenoxyl oxygen, in contrast to the geometries predicted by DFT calculations.

  20. Asymmetric Organocatalytic Reactions of α,β-Unsaturated Cyclic Ketones

    Directory of Open Access Journals (Sweden)

    Giuseppe Bartoli


    Full Text Available The 1,4-conjugate addition of nucleophiles to α,β-unsaturated carbonyl compounds represents one fundamental bond-forming reaction in organic synthesis. The development of effective organocatalysts for the enantioselective conjugate addition of malonate, nitroalkane and other carbon and heteroatom nucleophiles to cycloenones constitutes an important research field and has been explored in recent years. At the same time, asymmetric Diels-Alder reactions have been developed and often a mechanism has been demonstrated to be a double addition rather than synchronous. This review aims to cover literature up to the end of 2010, describing all the different organocatalytic asymmetric 1,4-conjugate additions even if they are listed as transfer hydrogenation, cycloadditions or desymmetrization of aromatic compounds.

  1. 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.

  2. Elastic, charge transfer, and related transport cross sections for proton impact of atomic hydrogen for astrophysical and laboratory plasma modeling (United States)

    Schultz, D. R.; Ovchinnikov, S. Yu; Stancil, P. C.; Zaman, T.


    Updating and extending previous work (Krstić and Schultz 1999 J. Phys. B: At. Mol. Opt. Phys. 32 3458 and other references) comprehensive calculations were performed for elastic scattering and charge transfer in proton—atomic hydrogen collisions. The results, obtained for 1301 collision energies in the center-of-mass energy range of 10-4-104 eV, are provided for integral and differential cross sections relevant to transport modeling in astrophysical and other plasma environments, and are made available through a website. Use of the data is demonstrated through a Monte Carlo transport simulation of solar wind proton propagation through atomic hydrogen gas representing a simple model of the solar wind interaction with heliospheric neutrals.

  3. Photoinduced electron transfer pathways in hydrogen-evolving reduced graphene oxide-boosted hybrid nano-bio catalyst. (United States)

    Wang, Peng; Dimitrijevic, Nada M; Chang, Angela Y; Schaller, Richard D; Liu, Yuzi; Rajh, Tijana; Rozhkova, Elena A


    Photocatalytic production of clean hydrogen fuels using water and sunlight has attracted remarkable attention due to the increasing global energy demand. Natural and synthetic dyes can be utilized to sensitize semiconductors for solar energy transformation using visible light. In this study, reduced graphene oxide (rGO) and a membrane protein bacteriorhodopsin (bR) were employed as building modules to harness visible light by a Pt/TiO2 nanocatalyst. Introduction of the rGO boosts the nano-bio catalyst performance that results in hydrogen production rates of approximately 11.24 mmol of H2 (μmol protein)(-1) h(-1). Photoelectrochemical measurements show a 9-fold increase in photocurrent density when TiO2 electrodes were modified with rGO and bR. Electron paramagnetic resonance and transient absorption spectroscopy demonstrate an interfacial charge transfer from the photoexcited rGO to the semiconductor under visible light.

  4. 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.

  5. 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

  6. Large tunneling effect on the hydrogen transfer in bis(μ-oxo)dicopper enzyme: a theoretical study. (United States)

    Park, Kisoo; Pak, Youngshang; Kim, Yongho


    Type-III copper-containing enzymes have dicopper centers in their active sites and exhibit a novel capacity for activating aliphatic C-H bonds in various substrates by taking molecular oxygen. Dicopper enzyme models developed by Tolman and co-workers reveal exceptionally large kinetic isotope effects (KIEs) for the hydrogen transfer process, indicating a significant tunneling effect. In this work, we demonstrate that variational transition state theory allows accurate prediction of the KIEs and Arrhenius parameters for such model systems. This includes multidimensional tunneling based on state-of-the-art quantum-mechanical calculations of the minimum-energy path (MEP). The computational model of bis(μ-oxo)dicopper enzyme consists of 70 atoms, resulting in a 204-dimensional potential energy surface. The calculated values of E(a)(H) - E(a)(D), A(H)/A(D), and the KIE at 233 K are -1.86 kcal/mol, 0.51, and 28.1, respectively, for the isopropyl ligand system. These values agree very well with experimental values within the limits of experimental error. For the representative tunneling path (RTP) at 233 K, the pre- and post-tunneling configurations are 3.3 kcal/mol below the adiabatic energy maximum, where the hydrogen travels 0.54 Å by tunneling. We found that tunneling is very efficient for hydrogen transfer and that the RTP is very different from the MEP. It is mainly heavy atoms that move as the reaction proceeds from the reactant complex to the pretunneling configuration, and the hydrogen atom suddenly hops at that point.

  7. Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid (United States)

    Rury, Aaron S.; Sorenson, Shayne; Dawlaty, Jahan M.


    Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm-1 oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.

  8. Film Boiling Heat Transfer Properties of Liquid Hydrogen in Natural Convection (United States)

    Horie, Y.; Shirai, Y.; Shiotsu, M.; Matsuzawa, T.; Yoneda, K.; Shigeta, H.; Tatsumoto, H.; Hata, K.; Naruo, Y.; Kobayashi, H.; Inatani, Y.

    Film boiling heat transfer properties of LH2 for various pressures and subcooling conditions were measured by applying electric current to give an exponential heat input to a PtCo wire with a diameter of 1.2 mm submerged in LH2. The heated wire was set to be horizontal to the ground. The heat transfer coefficient in the film boiling region was higher for higher pressure and higher subcooling. The experimental results are compared with the equation of pool film boiling heat transfer. It is confirmed that the pool film boiling heat transfer coefficients in LH2 can be expressed by this equation.

  9. Forced convection heat transfer from a wire inserted into a vertically-mounted pipe to liquid hydrogen flowing upward (United States)

    Tatsumoto, H.; Shirai, Y.; Shiotsu, M.; Naruo, Y.; Kobayashi, H.; Inatani, Y.


    Forced convection heat transfer from a PtCo wire with a length of 120 mm and a diameter of 1.2 mm that was inserted into a vertically-mounted pipe with a diameter of 8.0 mm to liquid hydrogen flowing upward was measured with a quasi-steady increase of a heat generation rate for wide ranges of flow rate under saturated conditions. The pressures were varied from 0.4 MPa to 1.1 MPa. The non-boiling heat transfer characteristic agrees with that predicted by Dittus-Boelter correlation. The critical heat fluxes are higher for higher flow rates and lower pressures. Effect of Weber number on the CHF was clarified and a CHF correlation that can describe the experimental data is derived based on our correlation for a pipe.

  10. Antioxidant Activity/Capacity Measurement. 2. Hydrogen Atom Transfer (HAT)-Based, Mixed-Mode (Electron Transfer (ET)/HAT), and Lipid Peroxidation Assays. (United States)

    Apak, Reşat; Özyürek, Mustafa; Güçlü, Kubilay; Çapanoğlu, Esra


    Measuring the antioxidant activity/capacity levels of food extracts and biological fluids is useful for determining the nutritional value of foodstuffs and for the diagnosis, treatment, and follow-up of numerous oxidative stress-related diseases. Biologically, antioxidants play their health-beneficial roles via transferring a hydrogen (H) atom or an electron (e(-)) to reactive species, thereby deactivating them. Antioxidant activity assays imitate this action; that is, antioxidants are measured by their H atom transfer (HAT) or e(-) transfer (ET) to probe molecules. Antioxidant activity/capacity can be monitored by a wide variety of assays with different mechanisms, including HAT, ET, and mixed-mode (ET/HAT) assays, generally without distinct boundaries between them. Understanding the principal mechanisms, advantages, and disadvantages of the measurement assays is important for proper selection of method for valid evaluation of antioxidant properties in desired applications. This work provides a general and up-to-date overview of HAT-based, mixed-mode (ET/HAT), and lipid peroxidation assays available for measuring antioxidant activity/capacity and the chemistry behind them, including a critical evaluation of their advantages and drawbacks.

  11. 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.

  12. Synthesis of metal-hydrazone complexes and vapochromic behavior of their hydrogen-bonded proton-transfer assemblies. (United States)

    Kobayashi, Atsushi; Dosen, Masa-aki; Chang, Mee; Nakajima, Kiyohiko; Noro, Shin-ichiro; Kato, Masako


    We synthesized and investigated a new series of metal-hydrazone complexes, including deprotonated [MX(mtbhp)] and protonated forms [MX(Hmtbhp)](ClO(4)) (M = Pd(2+), Pt(2+); X = Cl(-), Br(-); Hmtbhp = 2-(2-(2-(methylthio)benzylidene)hydrazinyl)pyridine) and hydrogen-bonded proton-transfer (HBPT) assemblies containing [PdBr(mtbhp)] and bromanilic acid (H(2)BA). The mtbhp hydrazone ligand acts as a tridentate SNN ligand and provides a high proton affinity. UV-vis spectroscopy revealed that these metal-hydrazone complexes follow a reversible protonation-deprotonation reaction ([MX(mtbhp)] + H(+) ⇋ [MX(Hmtbhp)](+)), resulting in a remarkable color change from red to yellow. Reactions between proton acceptor [PdBr(mtbhp)] (A) and proton donor H(2)BA (D) afforded four types of HBPT assemblies with different D/A ratios: for D/A = 1:1, {[PdBr(Hmtbhp)](HBA)·Acetone} and {[PdBr(Hmtbhp)](HBA)·2(1,4-dioxane)}; for D/A = 1:2, [PdBr(Hmtbhp)](2)(BA); and for D/A = 3:2, {[PdBr(Hmtbhp)](2)(HBA)(2)(H(2)BA)·2Acetonitrile}. The proton donor gave at least one proton to the acceptor to form the hydrogen bonded A···D pair of [PdBr(Hmtbhp)](+)···HBA(-). The strength of the hydrogen bond in the pair depends on the kind of molecule bound to the free monoanionic bromanilate OH group. Low-temperature IR spectra (T < 150 K) showed that the hydrogen bond distance between [PdBr(Hmtbhp)](+) and bromanilate was short enough (ca. 2.58 Å) to induce proton migration in the [PdBr(Hmtbhp)](2)(BA) assembly in the solid state. The hydrogen bonds formed not only between [PdBr(Hmtbhp)](+) and HBA(-) but also between HBA(-) and neutral H(2)BA molecules in the {[PdBr(Hmtbhp)](2)(HBA)(2)(H(2)BA)·2Acetonitrile} assembly. The H(2)BA-based flexible hydrogen bond network and strong acidic host structure result in an interesting vapor adsorption ability and vapochromic behavior in this assembly because the vapor-induced rearrangement of the hydrogen bond network, accompanied by changes in

  13. Protein hydrogen exchange measured at single-residue resolution by electron transfer dissociation mass spectrometry

    DEFF Research Database (Denmark)

    Rand, Kasper D; Zehl, Martin; Jensen, Ole Nørregaard


    Because of unparalleled sensitivity and tolerance to protein size, mass spectrometry (MS) has become a popular method for measuring the solution hydrogen (1H/2H) exchange (HX) of biologically relevant protein states. While incorporated deuterium can be localized to different regions by pepsin...... the HX of individual amide linkages in the amyloidogenic protein beta2-microglobulin. A comparison of the deuterium levels of 60 individual backbone amides of beta2-microglobulin measured by HX-ETD-MS analysis to the corresponding values measured by NMR spectroscopy shows an excellent correlation......-phase hydrogen (1H/2H) migration (i.e., hydrogen scrambling). This article demonstrates that ETD can be implemented in a mass spectrometric method to monitor the conformational dynamics of proteins in solution at single-residue resolution....

  14. Experimental study on enhancing convective heat transfer at outer asymmetrical finned tubes%非对称翅片管式换热器管外对流传热强化实验研究

    Institute of Scientific and Technical Information of China (English)

    王云雷; 何光艳; 张保生


    提出一种新型非对称翅片管式换热器,通过不同工况的实验,研究其传热过程和传热效果,并通过计算传热系数比较其与环状翅片管管束和光管管束的传热性能。结果表明:非对称翅片管对流体的扰动强于环状翅片管和光管;相同参数条件下,非对称翅片管换热器的换热效果优于环状翅片管和光管式换热器;采取相同面积的换热面,非对称翅片管换热器比环状翅片管换热器更加紧凑。%A new kind of asymmetrical finned tube heat exchanger was designed.The heat transfer process and effect of the asymmetrical finned tube were experimentally studied under four working conditions.Mo-reover,its heat transfer performance was compared with that of the ring-fin tube and smooth tube,through the heat transfer coefficient calculation.The results show that,this asymmetrical finned tube does stronger disturbance to the flow than the ring-fin tube and smooth tube,it has better heat transfer effect than the other two tubes,and with the same heating surface area,it is more compact than the ring-fin tube.

  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. 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 dy

  17. Anti-oxidant activity of 6-gingerol as a hydroxyl radical scavenger by hydrogen atom transfer, radical addition and electron transfer mechanisms

    Indian Academy of Sciences (India)



    Mechanisms of anti-oxidant action of 6-gingerol as a hydroxyl radical scavenger have been investigated using the transition state theory within the framework of density functional theory. Hydrogen abstraction by a hydroxyl radical from the different sites of 6-gingerol and addition of the former to the different sites ofthe latter were studied. Electron transfer from 6-gingerol to a hydroxyl radical was also studied. Solvent effect in aqueous media was treated using the integral equation formalism of the polarizable continuum model (IEFPCM). Reaction rate constants in aqueous media were generally found to be larger than those in gas phase. The tunneling contributions to rate constants were found to be appreciable. Our results show that 6-gingerol is an excellent anti-oxidant and would scavenge hydroxyl radicals efficiently.

  18. 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.

  19. Ultrafast forward and backward electron transfer dynamics of coumarin 337 in hydrogen-bonded anilines as studied with femtosecond UV-pump/IR-probe spectroscopy. (United States)

    Ghosh, Hirendra N; Verma, Sandeep; Nibbering, Erik T J


    Femtosecond infrared spectroscopy is used to study both forward and backward electron transfer (ET) dynamics between coumarin 337 (C337) and the aromatic amine solvents aniline (AN), N-methylaniline (MAN), and N,N-dimethylaniline (DMAN), where all the aniline solvents can donate an electron but only AN and MAN can form hydrogen bonds with C337. The formation of a hydrogen bond with AN and MAN is confirmed with steady state FT-IR spectroscopy, where the C═O stretching vibration is a direct marker mode for hydrogen bond formation. Transient IR absorption measurements in all solvents show an absorption band at 2166 cm(-1), which has been attributed to the C≡N stretching vibration of the C337 radical anion formed after ET. Forward electron transfer dynamics is found to be biexponential with time constants τ(ET)(1) = 500 fs, τ(ET)(2) = 7 ps in all solvents. Despite the presence of hydrogen bonds of C337 with the solvents AN and MAN, no effect has been found on the forward electron transfer step. Because of the absence of an H/D isotope effect on the forward electron transfer reaction of C337 in AN, hydrogen bonds are understood to play a minor role in mediating electron transfer. In contrast, direct π-orbital overlap between C337 and the aromatic amine solvents causes ultrafast forward electron transfer dynamics. Backward electron transfer dynamics, in contrast, is dependent on the solvent used. Standard Marcus theory explains the observed backward electron transfer rates.

  20. 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.

  1. Modifications on the hydrogen bond network by mutations of Escherichia coli copper efflux oxidase affect the process of proton transfer to dioxygen leading to alterations of enzymatic activities

    Energy Technology Data Exchange (ETDEWEB)

    Kajikawa, Takao; Kataoka, Kunishige [Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920-1192 (Japan); Sakurai, Takeshi, E-mail: [Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920-1192 (Japan)


    Highlights: Black-Right-Pointing-Pointer Proton transfer pathway to dioxygen in CueO was identified. Black-Right-Pointing-Pointer Glu506 is the key amino acid to transport proton. Black-Right-Pointing-Pointer The Ala mutation at Glu506 formed a compensatory proton transfer pathway. Black-Right-Pointing-Pointer The Ile mutation at Glu506 shut down the hydrogen bond network. -- Abstract: CueO has a branched hydrogen bond network leading from the exterior of the protein molecule to the trinuclear copper center. This network transports protons in the four-electron reduction of dioxygen. We replaced the acidic Glu506 and Asp507 residues with the charged and uncharged amino acid residues. Peculiar changes in the enzyme activity of the mutants relative to the native enzyme indicate that an acidic amino acid residue at position 506 is essential for effective proton transport. The Ala mutation resulted in the formation of a compensatory hydrogen bond network with one or two extra water molecules. On the other hand, the Ile mutation resulted in the complete shutdown of the hydrogen bond network leading to loss of enzymatic activities of CueO. In contrast, the hydrogen bond network without the proton transport function was constructed by the Gln mutation. These results exerted on the hydrogen bond network in CueO are discussed in comparison with proton transfers in cytochrome oxidase.

  2. Sensitive non-radioactive determination of aminotransferase stereospecificity for C-4' hydrogen transfer on the coenzyme

    Energy Technology Data Exchange (ETDEWEB)

    Jomrit, Juntratip [Department of Biotechnology, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400 (Thailand); Center of Excellence for Agricultural Biotechnology: (AG-BIO/PERDO-CHE), Bangkok (Thailand); Summpunn, Pijug [Department of Biotechnology, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400 (Thailand); Meevootisom, Vithaya [Department of Microbiology, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400 (Thailand); Center of Excellence for Agricultural Biotechnology: (AG-BIO/PERDO-CHE), Bangkok (Thailand); Wiyakrutta, Suthep, E-mail: [Department of Microbiology, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400 (Thailand); Center of Excellence for Agricultural Biotechnology: (AG-BIO/PERDO-CHE), Bangkok (Thailand)


    Research highlights: {yields} Stereochemical mechanism of PLP enzymes is important but difficult to determine. {yields} This new method is significantly less complicated than the previous ones. {yields} This assay is as sensitive as the radioactive based method. {yields} LC-MS/MS positively identify the analyte coenzyme. {yields} The method can be used with enzyme whose apo form is unstable. -- Abstract: A sensitive non-radioactive method for determination of the stereospecificity of the C-4' hydrogen transfer on the coenzymes (pyridoxal phosphate, PLP; and pyridoxamine phosphate, PMP) of aminotransferases has been developed. Aminotransferase of unknown stereospecificity in its PLP form was incubated in {sup 2}H{sub 2}O with a substrate amino acid resulted in PMP labeled with deuterium at C-4' in the pro-S or pro-R configuration according to the stereospecificity of the aminotransferase tested. The [4'-{sup 2}H]PMP was isolated from the enzyme protein and divided into two portions. The first portion was incubated in aqueous buffer with apo-aspartate aminotransferase (a reference si-face specific enzyme), and the other was incubated with apo-branched-chain amino acid aminotransferase (a reference re-face specific enzyme) in the presence of a substrate 2-oxo acid. The {sup 2}H at C-4' is retained with the PLP if the aminotransferase in question transfers C-4' hydrogen on the opposite face of the coenzyme compared with the reference aminotransferase, but the {sup 2}H is removed if the test and reference aminotransferases catalyze hydrogen transfer on the same face. PLP formed in the final reactions was analyzed by LC-MS/MS for the presence or absence of {sup 2}H. The method was highly sensitive that for the aminotransferase with ca. 50 kDa subunit molecular weight, only 2 mg of the enzyme was sufficient for the whole test. With this method, the use of radioactive substances could be avoided without compromising the sensitivity of the assay.

  3. Loss of ammonia during electron-transfer dissociation of deuterated peptides as an inherent gauge of gas-phase hydrogen scrambling

    DEFF Research Database (Denmark)

    Rand, Kasper D; Zehl, Martin; Jensen, Ole Nørregaard;


    detected by a depletion of deuterium when deuterated ammonia is lost from peptides during ETD. This straightforward method requires no modifications to the experimental workflow and has the great advantage that the occurrence of hydrogen scrambling can be directly detected in the actual peptides analyzed......The application of electron-transfer dissociation (ETD) to obtain single-residue resolution in hydrogen exchange-mass spectrometry (HX-MS) experiments has recently been demonstrated. For such measurements, it is critical to ensure that the level of gas-phase hydrogen scrambling is negligible. Here...... we utilize the abundant loss of ammonia upon ETD of peptide ions as a universal reporter of positional randomization of the exchangeable hydrogens (hydrogen scrambling) during HX-ETD experiments. We show that the loss of ammonia from peptide ions proceeds without depletion of deuterium when employing...

  4. Direct electron transfer biosensor for hydrogen peroxide carrying nanocomplex composed of horseradish peroxidase and Au-nanoparticle – Characterization and application to bienzyme systems

    Directory of Open Access Journals (Sweden)

    Yusuke Okawa


    Full Text Available A reagentless electrochemical biosensor for hydrogen peroxide was fabricated. The sensor carries a monolayer of nanocomplex composed of horseradish peroxidase and Au-nanoparticle, and responds to hydrogen peroxide through the highly efficient direct electron transfer at a mild electrode potential without any soluble mediator. Formation of the nanocomplex was studied with visible spectroscopy and size exclusion chromatography. The sensor performance was analyzed based on a hydrodynamic electrochemical technique and enzyme kinetics. The sensor was applied to fabrication of sensors for glucose and uric acid through further modification of the nanocomplex-carrying electrode with the corresponding hydrogen peroxide-generating oxidases, glucose oxidase and urate oxidase, respectively.

  5. Proton transfer through hydrogen bonds in two-dimensional water layers: A theoretical study based on ab initio and quantum-classical simulations (United States)

    Bankura, Arindam; Chandra, Amalendu


    The dynamics of proton transfer (PT) through hydrogen bonds in a two-dimensional water layer confined between two graphene sheets at room temperature are investigated through ab initio and quantum-classical simulations. The excess proton is found to be mostly solvated as an Eigen cation where the hydronium ion donates three hydrogen bonds to the neighboring water molecules. In the solvation shell of the hydronium ion, the three coordinated water molecules with two donor hydrogen bonds are found to be properly presolvated to accept a proton. Although no hydrogen bond needs to be broken for transfer of a proton to such presolvated water molecules from the hydronium ion, the PT rate is still found to be not as fast as it is for one-dimensional chains. Here, the PT is slowed down as the probability of finding a water with two donor hydrogen bonds in the solvation shell of the hydronium ion is found to be only 25%-30%. The hydroxide ion is found to be solvated mainly as a complex anion where it accepts four H-bonds through its oxygen atom and the hydrogen atom of the hydroxide ion remains free all the time. Here, the presolvation of the hydroxide ion to accept a proton requires that one of its hydrogen bonds is broken and the proton comes from a neighboring water molecule with two acceptor and one donor hydrogen bonds. The coordination number reduction by breaking of a hydrogen bond is a slow process, and also the population of water molecules with two acceptor and one donor hydrogen bonds is only 20%-25% of the total number of water molecules. All these factors together tend to slow down the hydroxide ion migration rate in two-dimensional water layers compared to that in three-dimensional bulk water.

  6. Proton transfer through hydrogen bonds in two-dimensional water layers: A theoretical study based on ab initio and quantum-classical simulations

    Energy Technology Data Exchange (ETDEWEB)

    Bankura, Arindam; Chandra, Amalendu, E-mail: [Department of Chemistry, Indian Institute of Technology, Kanpur 208016 (India)


    The dynamics of proton transfer (PT) through hydrogen bonds in a two-dimensional water layer confined between two graphene sheets at room temperature are investigated through ab initio and quantum-classical simulations. The excess proton is found to be mostly solvated as an Eigen cation where the hydronium ion donates three hydrogen bonds to the neighboring water molecules. In the solvation shell of the hydronium ion, the three coordinated water molecules with two donor hydrogen bonds are found to be properly presolvated to accept a proton. Although no hydrogen bond needs to be broken for transfer of a proton to such presolvated water molecules from the hydronium ion, the PT rate is still found to be not as fast as it is for one-dimensional chains. Here, the PT is slowed down as the probability of finding a water with two donor hydrogen bonds in the solvation shell of the hydronium ion is found to be only 25%-30%. The hydroxide ion is found to be solvated mainly as a complex anion where it accepts four H-bonds through its oxygen atom and the hydrogen atom of the hydroxide ion remains free all the time. Here, the presolvation of the hydroxide ion to accept a proton requires that one of its hydrogen bonds is broken and the proton comes from a neighboring water molecule with two acceptor and one donor hydrogen bonds. The coordination number reduction by breaking of a hydrogen bond is a slow process, and also the population of water molecules with two acceptor and one donor hydrogen bonds is only 20%-25% of the total number of water molecules. All these factors together tend to slow down the hydroxide ion migration rate in two-dimensional water layers compared to that in three-dimensional bulk water.

  7. Directionality of Ultrafast Electron Transfer in a Hydrogen Evolving Ru-Pd-Based Photocatalyst

    NARCIS (Netherlands)

    Pan, Qing; Mecozzi, Francesco; Korterik, Jeroen P.; Sharma, Divya; Herek, Jennifer L.; Vos, Johannes G.; Browne, Wesley R.; Huijser, Annemarie


    Directionality of electron transfer and long-lived charge separation are of key importance for efficient photocatalytic water splitting. Knowledge of the processes that follow photoexcitation is essential for the optimization of supramolecular assembly designs in order to improve the efficiency of p

  8. Transfer hydrogenation reactions catalyzed by chiral half-sandwich Ruthenium complexes derived from Proline

    Indian Academy of Sciences (India)



    Chiral ruthenium half-sandwich complexes were prepared using a chelating diamine made from proline with a phenyl, ethyl, or benzyl group, instead of hydrogen on one of the coordinating arms. Three of these complexes were obtained as single diastereoisomers and their configuration identified by X-ray crystallography. The complexes are recyclable catalysts for the reduction of ketones to chiral alcohols in water. A ruthenium hydride species is identified as the active species by NMR spectroscopy and isotopic labelling experiments.Maximum enantio-selectivity was attained when a phenyl group was directly attached to the primary amine on the diamine ligand derived from proline.

  9. Bio-inspired transition metal-organic hydride conjugates for catalysis of transfer hydrogenation: experiment and theory. (United States)

    McSkimming, Alex; Chan, Bun; Bhadbhade, Mohan M; Ball, Graham E; Colbran, Stephen B


    Taking inspiration from yeast alcohol dehydrogenase (yADH), a benzimidazolium (BI(+) ) organic hydride-acceptor domain has been coupled with a 1,10-phenanthroline (phen) metal-binding domain to afford a novel multifunctional ligand (L(BI+) ) with hydride-carrier capacity (L(BI+) +H(-) ⇌L(BI) H). Complexes of the type [Cp*M(L(BI) )Cl][PF6 ]2 (M=Rh, Ir) have been made and fully characterised by cyclic voltammetry, UV/Vis spectroelectrochemistry, and, for the Ir(III) congener, X-ray crystallography. [Cp*Rh(L(BI) )Cl][PF6 ]2 catalyses the transfer hydrogenation of imines by formate ion in very goods yield under conditions where the corresponding [Cp*Ir(L(BI) )Cl][PF6 ] and [Cp*M(phen)Cl][PF6 ] (M=Rh, Ir) complexes are almost inert as catalysts. Possible alternatives for the catalysis pathway are canvassed, and the free energies of intermediates and transition states determined by DFT calculations. The DFT study supports a mechanism involving formate-driven RhH formation (90 kJ mol(-1) free-energy barrier), transfer of hydride between the Rh and BI(+) centres to generate a tethered benzimidazoline (BIH) hydride donor, binding of imine substrate at Rh, back-transfer of hydride from the BIH organic hydride donor to the Rh-activated imine substrate (89 kJ mol(-1) barrier), and exergonic protonation of the metal-bound amide by formic acid with release of amine product to close the catalytic cycle. Parallels with the mechanism of biological hydride transfer in yADH are discussed.

  10. Calculations of Mode-Specific Tunneling of Double-Hydrogen Transfer in Porphycene Agree with and Illuminate Experiment. (United States)

    Homayoon, Zahra; Bowman, Joel M; Evangelista, Francesco A


    We report a theoretical study of mode-specific tunneling splittings in double-hydrogen transfer in trans-porphycene. We use a novel, mode-specific "Qim path method", in which the reaction coordinate is the imaginary-frequency normal mode of the saddle point separating the equivalent minima. The model considers all 108 normal modes and uses no adjustable parameters. The method gives the ground vibrational-state tunneling splitting, as well the increase in the splitting upon excitation of certain modes, in good agreement with experiment. Interpretation of these results is also transparent with this method. In addition, predictions are made for mode excitations not investigated experimentally. Results for d1 and d2 isotopolgues are also in agreement with experiment.

  11. Excitation of heavy hydrogen-like ions by light atoms in relativistic collisions with large momentum transfers

    CERN Document Server

    Najjari, B


    We present a theory for excitation of heavy hydrogen-like projectile-ions by light target-atoms in collisions where the momentum transfers to the atom are very large on the atomic scale. It is shown that in this process the electrons and the nucleus of the atom behave as (quasi-) free particles with respect to each other and that their motion is governed by the field of the nucleus of the ion. The effect of this field on the atomic particles can be crucial for the contribution to the excitation of the ion caused by the electrons of the atom. Due to comparatively very large nuclear mass, however, this field can be neglected in the calculation of the contribution to the excitation due to the nucleus of the atom.

  12. Lewis‐Acid‐assisted Hydrogen Atom Transfer to Manganese(V)‐Oxo Corrole through Valence Tautomerization


    Bougher, Curt J.; Abu‐Omar, Mahdi M.


    Abstract The kinetics of formation of the valence tautomers (tpfc⋅)MnIV(O−LA)] n+ [where LA=ZnII, CaII, ScIII, YbIII, B(C6F5)3, and trifluoroacetic acid (TFA); tpfc=5,10,15‐tris(pentafluorophenyl) corrole] from (tpfc)MnV(O) were followed by UV/Vis spectroscopy, giving second‐order rate constants ranging over five orders of magnitude from 10−2 for Ca to 103  m −1 s−1 for Sc. Hydrogen atom transfer (HAT) rates from 2,4‐di‐tert‐butyl phenol (2,4‐DTBP) to the various Lewis acid valence tautomers ...

  13. 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.

  14. Transferable potentials for phase equilibria. 10. Explicit-hydrogen description of substituted benzenes and polycyclic aromatic compounds. (United States)

    Rai, Neeraj; Siepmann, J Ilja


    The explicit-hydrogen version of the transferable potentials for phase equilibria (TraPPE-EH) force field is extended to various substituted benzenes through the parametrization of the exocyclic groups -F, -Cl, -Br, -C≡N, and -OH and to polycyclic aromatic hydrocarbons through the parametrization of the aromatic linker carbon atom for multiple rings. The linker carbon together with the TraPPE-EH parameters for aromatic heterocycles constitutes a force field for fused-ring heterocycles. Configurational-bias Monte Carlo simulations in the Gibbs ensemble were carried out to compute vapor-liquid coexistence curves for fluorobenzene; chlorobenzene; bromobenzene; di-, tri-, and hexachlorobenzene isomers; 2-chlorofuran; 2-chlorothiophene; benzonitrile; phenol; dihydroxybenzene isomers; 1,4-benzoquinone; naphthalene; naphthalene-2-carbonitrile; naphthalen-2-ol; quinoline; benzo[b]thiophene; benzo[c]thiophene; benzoxazole; benzisoxazole; benzimidazole; benzothiazole; indole; isoindole; indazole; purine; anthracene; and phenanthrene. The agreement with the limited experimental data is very satisfactory, with saturated liquid densities and vapor pressures reproduced to within 1.5% and 15%, respectively. The mean unsigned percentage errors in the normal boiling points, critical temperatures, and critical densities are 0.9%, 1.2%, and 1.4%, respectively. Additional simulations were carried out for binary systems of benzene/benzonitrile, benzene/phenol, and naphthalene/methanol to illustrate the transferability of the developed potentials to binary systems containing compounds of different polarity and hydrogen-bonding ability. A detailed analysis of the liquid-phase structures is provided for selected neat systems and binary mixtures.

  15. Ph(i-PrO)SiH2: An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom Transfers. (United States)

    Obradors, Carla; Martinez, Ruben M; Shenvi, Ryan A


    We report the discovery of an outstanding reductant for metal-catalyzed radical hydrofunctionalization reactions. Observations of unexpected silane solvolysis distributions in the HAT-initiated hydrogenation of alkenes reveal that phenylsilane is not the kinetically preferred reductant in many of these transformations. Instead, isopropoxy(phenyl)silane forms under the reaction conditions, suggesting that alcohols function as important silane ligands to promote the formation of metal hydrides. Study of its reactivity showed that isopropoxy(phenyl)silane is an exceptionally efficient stoichiometric reductant, and it is now possible to significantly decrease catalyst loadings, lower reaction temperatures, broaden functional group tolerance, and use diverse, aprotic solvents in iron- and manganese-catalyzed hydrofunctionalizations. As representative examples, we have improved the yields and rates of alkene reduction, hydration, hydroamination, and conjugate addition. Discovery of this broadly applicable, chemoselective, and solvent-versatile reagent should allow an easier interface with existing radical reactions. Finally, isotope-labeling experiments rule out the alternative hypothesis of hydrogen atom transfer from a redox-active β-diketonate ligand in the HAT step. Instead, initial HAT from a metal hydride to directly generate a carbon-centered radical appears to be the most reasonable hypothesis.

  16. Excitation and charge transfer in low-energy hydrogen atom collisions with neutral atoms: Theory, comparisons, and application to Ca

    CERN Document Server

    Barklem, Paul S


    A theoretical method for the estimation of cross sections and rates for excitation and charge transfer processes in low-energy hydrogen atom collisions with neutral atoms, based on an asymptotic two-electron model of ionic-covalent interactions in the neutral atom-hydrogen atom system, is presented. The calculation of potentials and non-adiabatic radial couplings using the method is demonstrated. The potentials are used together with the multi-channel Landau-Zener model to calculate cross sections and rate coefficients. The main feature of the method is that it employs asymptotically exact atomic wavefunctions, which can be determined from known atomic parameters. The method is applied to Li+H, Na+H, and Mg+H collisions, and the results compare well with existing detailed full-quantum calculations. The method is applied to the astrophysically important problem of Ca+H collisions, and rate coefficients are calculated for temperatures in the range 1000-20000 K.

  17. Single step synthesis of gold-amino acid composite, with the evidence of the catalytic hydrogen atom transfer (HAT) reaction, for the electrochemical recognition of Serotonin (United States)

    Choudhary, Meenakshi; Siwal, Samarjeet; Nandi, Debkumar; Mallick, Kaushik


    A composite architecture of amino acid and gold nanoparticles has been synthesized using a generic route of 'in-situ polymerization and composite formation (IPCF)' [1,2]. The formation mechanism of the composite has been supported by a model hydrogen atom (H•≡H++e-) transfer (HAT) type of reaction which belongs to the proton coupled electron transfer (PCET) mechanism. The 'gold-amino acid composite' was used as a catalyst for the electrochemical recognition of Serotonin.

  18. Atomic capture and transfer of negative pions stopped in binary mixtures of hydrogen with polyatomic gases

    Energy Technology Data Exchange (ETDEWEB)

    Vasilyev, V.A.; Levay, B.; Minkova, A.; Petrukhin, V.I.; Horvath, D.


    The atomic capture and transfer of stopped negative pions have been studied in binary gas mixtures of H/sub 2/+M, where M is CCl/sub 2/F/sub 2/, CClF/sub 3/, CBrF/sub 3/ or SF/sub 6/. The ..pi../sup 0/ yield, versus relative atomic concentration Csub(A) of M, goes through a maximum at Csub(A)proportional0.1 and levels off at zero at high concentrations. This phenomenon together with other observed characteristics of the atomic capture and transfer of pions in these systems is interpreted in the frame of a phenomenological model. The average transfer coefficients anti ..lambda..sub(Z) exhibit a weak concentration dependence. The estimated average atomic capture ratios anti A(Z/H) are lower than those found for noble gases, probably because of the mutual screening of the constituent atoms in the molecules. The probability of pion capture in an atomic orbit is not proportional to the stopping power of the components of the mixture. (orig.).

  19. 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.

  20. Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes (United States)

    Li, Yang; Tu, Xingchen; Wang, Minglang; Wang, Hao; Sanvito, Stefano; Hou, Shimin


    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.

  1. Transient heat transfer from a wire to a forced flow of subcooled liquid hydrogen passing through a vertically- mounted pipe (United States)

    Tatsumoto, H.; Shirai, Y.; Shiotsu, M.; Naruo, Y.; Kobayashi, H.; Nonaka, S.; Inatani, Y.


    Transient heat transfers from Pt-Co wire heaters inserted into vertically-mounted pipes, through which forced flow subcooled liquid hydrogen was passed, were measured by increasing the exponential heat input with various time periods at a pressure of 0.7 MPa and inlet temperature of 21 K. The flow velocities ranged from 0.3 to 7 m/s. The Pt-Co wire heaters had a diameter of 1.2 mm and lengths of 60 mm, 120 mm and 200 mm and were inserted into the pipes with diameters of 5.7mm, 8.0 mm, and 5.0 mm, respectively, which were made of Fiber reinforced plastic due to thermal insulation. With increase in the heat flux to the onset of nucleate boiling, surface temperature increased along the curve predicted by the Dittus-Boelter correlation for longer period, where it can be almost regarded as steady-state. For shorter period, the heat transfer became higher than the Dittus-Boelter correlation. In nucleate boiling regime, the heat flux steeply increased to the transient CHF (critical heat flux) heat flux, which became higher for shorter period. Effect of flow velocity, period, and heated geometry on the transient CHF heat flux was clarified.

  2. 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.

  3. Asymmetric Hydrogenation of Acetophenone and Its Derivatives Catalyzed by L-Proline Stabilized Iridium%L-脯氨酸稳定的铱催化苯乙酮及其衍生物不对称加氢反应

    Institute of Scientific and Technical Information of China (English)

    杨朝芬; 杨俊; 朱艳琴; 孙晓东; 李贤均; 陈华


    A supported iridium catalyst stabilized by L-proline was prepared under mild conditions and was applied to the heterogeneous asymmetric hydrogenation of acetophenone and its derivatives. The effect of the support and L-proline on the supported iridium catalyst was studied. The catalyst was characterized by transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results showed that L-proline had a marked ability to stabilize and disperse the iridium particles. Reaction conditions for the asymmetric hydrogenation of acetophenone were examined in detail. LiOH enhanced the activity and enantioselectivity of the reaction. The alkali metal cation plays an important role in influencing the enantioselectivity. In addition, a synergistic effect between (1S,2S)-1,2-diphenyl-1,2-ethylenediamine ((1S,2S)-DPEN) and L-proline was observed, which significantly accelerated the reaction rate and enhanced the enantioselectivity. In the presence of (1S,2S)-DPEN as chiral modifier the catalyst 5% (w, mass fraction)lr/15(the molar ratio of L-proline to Ir) (L-Proline)-y-AI2C>3 exhibited good catalytic performance in the asymmetric hydrogenation of acetophenone and its derivatives. Under optimum conditions the enantiomeric excess (ee) values of (R)-phenylethanol and (f?)-2'-(trifluoromethyl) phenylethanol were 71.3% and 79.8%, respectively. Without using phosphine as a stabilizer the preparationof the catalyst was simple and the catalyst was reused several times without a significant loss In activity and enantioselectivity.%以L-脯氨酸为稳定剂制备了负载型金属铱催化剂,并用于苯乙酮及其衍生物不对称加氢反应.考察了载体以及L-脯氨酸的量对催化剂性能的影响,以透射电镜(TEM)和X射线光电子能谱(XPS)对催化剂进行了表征.结果表明L-脯氨酸对金属铱粒子具有较好的分散和稳定作用.通过考察反应条件发现:碱金属离子对反应有较大影响; L-脯氨酸与手性修饰

  4. 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...

  5. Interference effects in K vacancy transfer of hydrogen-like S ions colliding with Ar

    Energy Technology Data Exchange (ETDEWEB)

    Schuch, R.; Justiniano, E.; Schulz, M.; Ziegler, F.; Ingwersen, H.; Schmidt-Boecking, H.


    The impact-parameter-dependent K-shell to K-shell vacancy transfer probability has been investigated for 4.7, 7.9, 16, 32 and 90 MeV S/sup 15 +/-Ar collisions by measuring S and Ar K x-ray particle coincidences. With low-energy H-like S beams, oscillating Ar K vacancy probabilities as a function of impact parameter were measured. The interference maxima and minima could be related to values of the phase integral over the 2psigma-1ssigma energy difference from which information about this energy difference could be obtained.

  6. Electron density characteristics and charge transfer effect of hydrogen bond O-H···Pt(II): atoms in molecules study and natural bond orbital analysis (United States)

    Zhang, Guiqiu; Li, Xiwen; Li, Yan; Chen, Dezhan


    In this report, we extended the works of Rizzato et al. [Angew. Chem. Int. Ed. 49, 7440 (2010)] on the nature of O-H...Pt hydrogen bond in trans-[PtCl2(NH3)(N-glycine)].H2O(1.H2O) complex, by computational study of O-H...Pt interaction in [NBu4][Pt(C6F5)3(8-hydroxyquinaldine)], with emphasis on charge transfer effect in this interaction of platinum(II) and hydrogen atom. According to the crystallographic geometry reported by José María Casas et al., [NBu4][Pt(C6F5)3(8-hydroxyquinaldine)] possesses one O-H...Pt hydrogen bridging interaction, similar to the case in trans-[PtCl2(NH3)(N-glycine)].H2O(1.H2O) complex. On the basis of topological criteria of electron density, we characterised this O-H...Pt interaction. Charge transferred between platinum(II) and σ*O-H orbital in this complex was calculated by using NBO method. The stabilised energy associated to charge transfer was estimated using a direct proportionality, that is 2-3 eV per electron transferred. Charge transfer effects in O-H...Pt hydrogen bonds were studied for these two complexes. Our results indicate that the interaction of O-H...Pt is closed-shell in nature with significant charge transfer, and that charge transfer effect is not negligible in the interaction of O-H...Pt. The second conclusion is different from the result of Rizzato et al.

  7. Handshake electron transfer from hydrogen Rydberg atoms incident at a series of metallic thin films

    CERN Document Server

    Gibbard, Jemma A


    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 Rydberg 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...

  8. 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.

  9. Detection of infalling hydrogen in transfer between the interacting galaxies NGC 5426 and NGC 5427

    CERN Document Server

    Font, Joan; Rosado, Margarita; Epinat, Benoît; Fathi, Kambiz; Hernandez, Olivier; Carignan, Claude; Gutiérrez, Leonel; Relaño, Monica; Blasco-Herrera, Javier; Fuentes-Carrera, Isaura


    Using velocity tagging we have detected hydrogen from NGC 5426 falling onto its interacting partner NGC 5427. Our observations, with the GHaFaS Fabry-Perot spectrometer, produced maps of the two galaxies in Halpha surface brightness and radial velocity. We found emission with the range of velocities associated with NGC 5426 along lines of sight apparently emanating from NGC 5427, superposed on the velocity map of the latter. After excluding instrumental effects we assign the anomalous emission to gas pulled from NGC 5426 during its passage close to NGC 5427. Its distribution, more intense between the arms and just outside the disk of NGC 5427, and weak, or absent, in the arms, suggests that the infalling gas is behind the disk., ionized by Lyman continuum photons escaping from NGC 5427. Modeling this, we estimate the distances of these gas clouds- behind the plane: a few hundred pc to a few kpc. We also estimate the mass of the infalling (ionized plus neutral) gas, finding an infall rate of 10 solar masses pe...

  10. 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.)

  11. Slow hydrogen atom transfer reactions of oxo- and hydroxo-vanadium compounds: the importance of intrinsic barriers. (United States)

    Waidmann, Christopher R; Zhou, Xin; Tsai, Erin A; Kaminsky, Werner; Hrovat, David A; Borden, Weston Thatcher; Mayer, James M


    fluoride in place of the py ligands. The calculations reproduce the difference in barrier heights and show that transfer of a hydrogen atom involves more structural reorganization for vanadium than the Ru analogues. The vanadium complexes have larger changes in the metal-oxo and metal-hydroxo bond lengths, which is traced to the difference in d-orbital occupancy in the two systems. This study thus highlights the importance of intrinsic barriers in the transfer of a hydrogen atom, in addition to the thermochemical (bond strength) factors that have been previously emphasized.

  12. Total Synthesis and Stereochemical Assignment of Delavatine A: Rh-Catalyzed Asymmetric Hydrogenation of Indene-Type Tetrasubstituted Olefins and Kinetic Resolution through Pd-Catalyzed Triflamide-Directed C-H Olefination. (United States)

    Zhang, Zhongyin; Wang, Jinxin; Li, Jian; Yang, Fan; Liu, Guodu; Tang, Wenjun; He, Weiwei; Fu, Jian-Jun; Shen, Yun-Heng; Li, Ang; Zhang, Wei-Dong


    Delavatine A (1) is a structurally unusual isoquinoline alkaloid isolated from Incarvillea delavayi. The first and gram-scale total synthesis of 1 was accomplished in 13 steps (the longest linear sequence) from commercially available starting materials. We exploited an isoquinoline construction strategy and developed two reactions, namely Rh-catalyzed asymmetric hydrogenation of indene-type tetrasubstituted olefins and kinetic resolution of β-alkyl phenylethylamine derivatives through Pd-catalyzed triflamide-directed C-H olefination. The substrate scope of the first reaction covered unfunctionalized olefins and those containing polar functionalities such as sulfonamides. The kinetic resolution provided a collection of enantioenriched indane and tetralin-based triflamides, including those bearing quaternary chiral centers. The selectivity factor (s) exceeded 100 for a number of substrates. These reactions enabled two different yet related approaches to a key intermediate 28 in excellent enantiopurity. In the synthesis, the triflamide served as not only an effective directing group for C-H bond activation but also a versatile functional group for further elaborations. The relative and absolute configurations of delavatine A were unambiguously assigned by the syntheses of the natural product and its three stereoisomers. Their cytotoxicity against a series of cancer cell lines were evaluated.

  13. Barrierless proton transfer across weak CH⋯O hydrogen bonds in dimethyl ether dimer

    Energy Technology Data Exchange (ETDEWEB)

    Yoder, Bruce L., E-mail:; West, Adam H. C.; Signorell, Ruth [Laboratory of Physical Chemistry, ETH Zürich, Zürich 8093 (Switzerland); Bravaya, Ksenia B. [Department of Chemistry, Boston University, Boston, Massachusetts 02215-2521 (United States); Bodi, Andras [Molecular Dynamics Group, Paul Scherrer Institut, Villigen 5232 (Switzerland); Sztáray, Bálint [Department of Chemistry, University of the Pacific, Stockton, California 95211 (United States)


    We present a combined computational and threshold photoelectron photoion coincidence study of two isotopologues of dimethyl ether, (DME − h{sub 6}){sub n} and (DME − d{sub 6}){sub n}n = 1 and 2, in the 9–14 eV photon energy range. Multiple isomers of neutral dimethyl ether dimer were considered, all of which may be present, and exhibited varying C–H⋯O interactions. Results from electronic structure calculations predict that all of them undergo barrierless proton transfer upon photoionization to the ground electronic state of the cation. In fact, all neutral isomers were found to relax to the same radical cation structure. The lowest energy dissociative photoionization channel of the dimer leads to CH{sub 3}OHCH{sub 3}{sup +} by the loss of CH{sub 2}OCH{sub 3} with a 0 K appearance energy of 9.71 ± 0.03 eV and 9.73 ± 0.03 eV for (DME − h{sub 6}){sub 2} and deuterated (DME − d{sub 6}){sub 2}, respectively. The ground state threshold photoelectron spectrum band of the dimethyl ether dimer is broad and exhibits no vibrational structure. Dimerization results in a 350 meV decrease of the valence band appearance energy, a 140 meV decrease of the band maximum, thus an almost twofold increase in the ground state band width, compared with DME − d{sub 6} monomer.

  14. Determination of binding constants and stoichiometries of short-range, hydrogen-bonding solvation by use of a proton-transfer indicator reaction (United States)

    Schullery, Stephen E.; Wojdyla, Stephen M.; Ostroski, Robert A.; Scott, Ronald M.


    A recent method for determination of stoichiometries and binding constants for short-range, hydrogen bonding solvation is reviewed and new results are presented. The method exploits the sensitivity of a proton-transfer equilibrium, KPT to changes in solvent composition. Solvation numbers and binding constants for primary and secondary stages of solvation of an aminephenol proton-transfer adduct and the phenol and amine are determined as adjustable parameters when model isotherms are fitted to KPT versus [ S] data, where [ S] is the concentration of a hydrogen-bonding minor component of a mixed solvent, Results for most of the twenty-three aprotic solvents investigated are modeled by bifurcation-type hydrogen bonding of two or more electron pairs to a single polar hydrogen. Results for the seven protic solvents studied, including new data for ethanol, 2-choloroethanol, and 2,2-dichloroethanol, are modeled by two, or possibly three, successive stages of solvation, assumed to involve hydrogen-bonded chains. Preliminary results indicate that solvation by water is amenable to this analysis.

  15. Thermal-Hydraulic Analyses of Heat Transfer Fluid Requirements and Characteristics for Coupling A Hydrogen Production Plant to a High-Temperature Nuclear Reactor

    Energy Technology Data Exchange (ETDEWEB)

    C. B. Davis; C. H. Oh; R. B. Barner; D. F. Wilson


    The Department of Energy is investigating the use of high-temperature nuclear reactors to produce hydrogen using either thermochemical cycles or high-temperature electrolysis. Although the hydrogen production processes are in an early stage of development, coupling either of these processes to the hightemperature reactor requires both efficient heat transfer and adequate separation of the facilities to assure that off-normal events in the production facility do not impact the nuclear power plant. An intermediate heat transport loop will be required to separate the operations and safety functions of the nuclear and hydrogen plants. A next generation high-temperature reactor could be envisioned as a single-purpose facility that produces hydrogen or a dual-purpose facility that produces hydrogen and electricity. Early plants, such as the proposed Next Generation Nuclear Plant, may be dual-purpose facilities that demonstrate both hydrogen and efficient electrical generation. Later plants could be single-purpose facilities. At this stage of development, both single- and dual-purpose facilities need to be understood. Seven possible configurations for a system that transfers heat between the nuclear reactor and the hydrogen and/or electrical generation plants were identified. These configurations included both direct and indirect cycles for the production of electricity. Both helium and liquid salts were considered as the working fluid in the intermediate heat transport loop. Methods were developed to perform thermalhydraulic and cycle-efficiency evaluations of the different configurations and coolants. The thermalhydraulic evaluations estimated the sizes of various components in the intermediate heat transport loop for the different configurations. The relative sizes of components provide a relative indication of the capital cost associated with the various configurations. Estimates of the overall cycle efficiency of the various configurations were also determined. The

  16. Importance of π-stacking interactions in the hydrogen atom transfer reactions from activated phenols to short-lived N-oxyl radicals. (United States)

    Mazzonna, Marco; Bietti, Massimo; DiLabio, Gino A; Lanzalunga, Osvaldo; Salamone, Michela


    A kinetic study of the hydrogen atom transfer from activated phenols (2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols, 2,2,5,7,8-pentamethylchroman-6-ol, caffeic acid, and (+)-cathechin) to a series of N-oxyl radical (4-substituted phthalimide-N-oxyl radicals (4-X-PINO), 6-substituted benzotriazole-N-oxyl radicals (6-Y-BTNO), 3-quinazolin-4-one-N-oxyl radical (QONO), and 3-benzotriazin-4-one-N-oxyl radical (BONO)), was carried out by laser flash photolysis in CH3CN. A significant effect of the N-oxyl radical structure on the hydrogen transfer rate constants (kH) was observed with kH values that monotonically increase with increasing NO-H bond dissociation energy (BDENO-H) of the N-hydroxylamines. The analysis of the kinetic data coupled to the results of theoretical calculations indicates that these reactions proceed by a hydrogen atom transfer (HAT) mechanism where the N-oxyl radical and the phenolic aromatic rings adopt a π-stacked arrangement. Theoretical calculations also showed pronounced structural effects of the N-oxyl radicals on the charge transfer occurring in the π-stacked conformation. Comparison of the kH values measured in this study with those previously reported for hydrogen atom transfer to the cumylperoxyl radical indicates that 6-CH3-BTNO is the best N-oxyl radical to be used as a model for evaluating the radical scavenging ability of phenolic antioxidants.

  17. Fine Control over Site and Substrate Selectivity in Hydrogen Atom Transfer-Based Functionalization of Aliphatic C-H Bonds. (United States)

    Salamone, Michela; Carboni, Giulia; Bietti, Massimo


    The selective functionalization of unactivated aliphatic C-H bonds over intrinsically more reactive ones represents an ongoing challenge of synthetic chemistry. Here we show that in hydrogen atom transfer (HAT) from the aliphatic C-H bonds of alkane, ether, alcohol, amide, and amine substrates to the cumyloxyl radical (CumO(•)) fine control over site and substrate selectivity is achieved by means of acid-base interactions. Protonation of the amines and metal ion binding to amines and amides strongly deactivates the C-H bonds of these substrates toward HAT to CumO(•), providing a powerful method for selective functionalization of unactivated or intrinsically less reactive C-H bonds. With 5-amino-1-pentanol, site-selectivity has been drastically changed through protonation of the strongly activating NH2 group, with HAT that shifts to the C-H bonds that are adjacent to the OH group. In the intermolecular selectivity studies, trifluoroacetic acid, Mg(ClO4)2, and LiClO4 have been employed in a orthogonal fashion for selective functionalization of alkane, ether, alcohol, and amide (or amine) substrates in the presence of an amine (or amide) one. Ca(ClO4)2, that promotes deactivation of amines and amides by Ca(2+) binding, offers, moreover, the opportunity to selectively functionalize the C-H bonds of alkane, ether, and alcohol substrates in the presence of both amines and amides.

  18. Absolute rate constants for hydrogen atom transfer from tertiary amides to the cumyloxyl radical: evaluating the role of stereoelectronic effects. (United States)

    Salamone, Michela; Milan, Michela; DiLabio, Gino A; Bietti, Massimo


    A time-resolved kinetic study of the hydrogen atom transfer (HAT) reactions from a series of alkanamides to the cumyloxyl radical (CumO(•)) was carried out. With N,N-dialkylformamides HAT preferentially occurs from the formyl C-H bond, while in N-formylpyrrolidine HAT mostly occurs from the ring α-C-H bonds. With the acetamides and the alkanamides almost exclusive HAT from the C-H bonds that are α to nitrogen was observed. The results obtained show that alignment between the C-H bond being broken and the amide π-system can lead to significant increases in the HAT rate constant (kH). This finding points toward the important role of stereoelectronic effects on the HAT reactivity and selectivity. The highest kH values were measured for the reactions of CumO(•) with N-acylpyrrolidines. These substrates have ring α-C-H bonds that are held in a conformation that is optimally aligned with the amide π-system, thus allowing for the relatively facile HAT reaction. The lowest kH value was measured for the reaction of N,N-diisobutylacetamide, wherein the steric bulk associated with the N-isobutyl groups increases the energy barrier required to reach the most suitable conformation for HAT. The experimental results are well supported by the computed BDEs for the C-H bonds of the most representative substrates.

  19. Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods (United States)

    Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep


    For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

  20. Hydrogen bonding and proton transfer to ruthenium hydride complex CpRuH(dppe): metal and hydride dichotomy. (United States)

    Silantyev, Gleb A; Filippov, Oleg A; Tolstoy, Peter M; Belkova, Natalia V; Epstein, Lina M; Weisz, Klaus; Shubina, Elena S


    The combination of variable temperature (190-297 K) IR and NMR spectroscopy studies with quantum-chemical calculations at the DFT/B3PW91 and AIM level had the aim to determine the mechanism of proton transfer to CpRuH(dppe) (1, dppe = Ph(2)P(CH(2))(2)PPh(2)) and the structures of intermediates. Dihydrogen bond (DHB) formation was established in the case of interaction with weak proton donors like CF(3)CH(2)OH. Low-temperature protonation (at about 200 K) by stronger proton donors leads via DHB complex to the cationic nonclassical complex [CpRu(η(2)-H(2))(dppe)](+) (2). Thermodynamic parameters of DHB formation (for CF(3)CH(2)OH: ΔH°(HB) = -4.9 ± 0.2 kcal·mol(-1), ΔS°(HB) = -17.8 ± 0.7 cal·mol(-1)·K(-1)) and proton transfer (for (CF(3))(2)CHOH: ΔH°(PT) = -5.2 ± 0.3 kcal·mol(-1), ΔS°(PT) = -23 ± 1 cal·mol(-1)·K(-1)) were determined. Above 240 K 2 transforms into trans-[CpRu(H)(2)(dppe)](+) (3) yielding a mixture of 2 and 3 in 1:2 ratio. Kinetic analysis and activation parameters for the "[Ru(η(2)-H(2))](+) → trans-[Ru(H)(2)](+)" transformation indicate reversibility of this process in contrast to irreversible intramolecular isomerization of the Cp* analogue. Calculations show that the driving force of this process is greater stability (by 1.5 kcal·mol(-1) in ΔE scale) of the dihydride cation in comparison with the dihydrogen complex. The calculations of the potential energy profile indicate the low barrier for deprotonation of 2 suggesting that the formation of trans-[CpRu(H)(2)(dppe)](+) proceeds via deprotonation of [Ru(η(2)-H(2))](+) to DHB complex, formation of hydrogen bond with Ru atom and subsequent proton transfer to the metal site.

  1. New Chiral Metal Cluster Systems for Catalytic Asymmetric Syntheses of Chiral Alcohols

    Institute of Scientific and Technical Information of China (English)

    LI Yan-yun; CHEN Jian-shan; YANG Chuan-bo; DONG Zhen-rong; LI Bao-zhu; ZHANG Hui; GAO Jing-xing; TAKAO Ikariya


    The efficient chiral Ru3(CO)12 systems were prepared in situ from Ru3(CO)12 and various chiral diiminoor diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hydrogenation of propiophenone in 2-propanol, leading to 1-phenyl-1-propanol in a 98% yield and 96% e.e. The IR study suggests that the carbonyl hydride anion [HRu3(CO)11]- most probably exists as a principal species under the reaction conditions. The high chiral efficiency may be due to the synergetic effect produced by the neighboring ruthenium atoms and a special chiral micro-environment involving the polydentate ligand and the Ru3 framework.

  2. Hydrogen transfer reaction of cyclohexanone with 2-propanol catalysed by CeO2-ZnO materials: Promoting effect of ceria

    Indian Academy of Sciences (India)

    Braja Gopal Mishra; G Ranga Rao; B Poongodi


    Ce-Zn-O mixed oxides were prepared by amorphous citrate process and decomposition of the corresponding acetate precursors. The resulting materials were characterised by TGA, XRD, UV-Vis-DRS, EPR, SEM and surface area measurements. XRD and DRS results indicated fine dispersion of the ceria component in the ZnO matrix. EPR results clearly indicate the presence of oxygen vacancy and defect centres in the composite oxide. Addition of CeO2 to ZnO produced mixed oxides of high surface area compared to the pure ZnO. Hydrogen transfer reaction was carried out on these catalytic materials to investigate the effect of rare earth oxide on the activity of ZnO. 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.

  3. Hydrogen-bonding effect on spin-center transfer of tetrathiafulvalene-linked 6-oxophenalenoxyl evaluated using temperature-dependent cyclic voltammetry and theoretical calculations. (United States)

    Nishida, Shinsuke; Fukui, Kozo; Morita, Yasushi


    The stable tetrathiafulvalene (TTF)-linked 6-oxophenalenoxyl neutral radical exhibits a spin-center transfer with a continuous color change in solution caused by an intramolecular electron transfer, which is dependent on solvent and temperature. Cyclic voltammetry measurements showed that addition of 2,2,2-trifluoroethanol (TFE) to a benzonitrile solution of the neutral radical induces a redox potential shift that is favorable for the spin-center transfer. Temperature-dependent cyclic voltammetry of the neutral radical using a novel low-temperature electrochemical cell demonstrated that the redox potentials change with decreasing temperature in a 199:1 CH2Cl2/TFE mixed solvent. Furthermore, theoretical calculation revealed that the energy levels of the frontier molecular orbitals involved in the spin-center transfer are lowered by the hydrogen-bonding interaction of TFE with the neutral radical. These results indicate that the hydrogen-bonding effect is a key factor for the occurrence of the spin-center transfer of TTF-linked 6-oxophenalenoxyl.

  4. 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

  5. Catalytic enantioselective amination of alcohols by the use of borrowing hydrogen methodology: cooperative catalysis by iridium and a chiral phosphoric acid. (United States)

    Zhang, Yao; Lim, Ching-Si; Sim, Derek Sui Boon; Pan, Hui-Jie; Zhao, Yu


    The catalytic asymmetric reduction of ketimines has been explored extensively for the synthesis of chiral amines, with reductants ranging from Hantzsch esters, silanes, and formic acid to H2 gas. Alternatively, the amination of alcohols by the use of borrowing hydrogen methodology has proven a highly atom economical and green method for the production of amines without an external reductant, as the alcohol substrate serves as the H2 donor. A catalytic enantioselective variant of this process for the synthesis of chiral amines, however, was not known. We have examined various transition-metal complexes supported by chiral ligands known for asymmetric hydrogenation reactions, in combination with chiral Brønsted acids, which proved essential for the formation of the imine intermediate and the transfer-hydrogenation step. Our studies led to an asymmetric amination of alcohols to provide access to a wide range of chiral amines with good to excellent enantioselectivity.

  6. Theoretical insight into the excited-state intramolecular proton transfer mechanisms of three amino-type hydrogen-bonding molecules (United States)

    An, Beibei; Yuan, Huijuan; Zhu, Qiuling; Li, Yuanyuan; Guo, Xugeng; Zhang, Jinglai


    Excited-state intramolecular proton transfer (ESIPT) dynamics of the amino-type hydrogen-bonding compound 2-(2‧-aminophenyl)benzothiazole (PBT-NH2) as well as its two derivatives 2-(5‧-cyano-2‧-aminophenyl)benzothiazole (CN-PBT-NH2) and 2-(5‧-cyano-2‧-tosylaminophenyl)benzothiazole (CN-PBT-NHTs) were studied by the time-dependent density functional theory (TD-DFT) approach with the B3LYP density functional, and their absorption and emission spectra were also explored at the same level of theory. A good agreement is observed between the theoretical simulations and experimental spectra, indicating that the present calculations are reasonably reliable. In addition, it is also found that the energy barriers of the first excited singlet state of the three targeted molecules along the ESIPT reaction are computed to be 0.38, 0.34 and 0.12 eV, respectively, showing the trend of gradual decrease, which implies that the introduction of the electron-withdrawing cyano or tosyl group can facilitate the occurrence of the ESIPT reaction of these amino-type H-bonding systems. Following the ESIPT, both CN-PBT-NH2 and CN-PBT-NHTs dye molecules can undergo the cis-trans isomerization reactions in the ground-state and excited-state potential energy curves along the C2-C3 bond between benzothiazole and phenyl moieties, where the energy barriers of the trans-tautomer → cis-tautomer isomerizations in the ground states are calculated to be 0.83 and 0.34 eV, respectively. According to our calculations, it is plausible that there may exist the long-lived trans-tautomer species in the ground states of CN-PBT-NH2 and CN-PBT-NHTs.

  7. 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.

  8. Electron-transfer dependent photocatalytic hydrogen generation over cross-linked CdSe/TiO2 type-II heterostructure. (United States)

    Chen, Yubin; Chuang, Chi-Hung; Qin, Zhixiao; Shen, Shaohua; Doane, Tennyson; Burda, Clemens


    Developing type-II heterostructures with a spatial separation of photoexcited electrons and holes is a useful route to promote photocatalytic hydrogen generation. However, few investigations on the charge transfer process across the heterojunction have been carried out, which can allow us to uncover the reaction mechanism. Herein, CdSe quantum dots (QDs) and TiO2 nanocrystals were synthesized and combined in water yielding CdSe/TiO2 type II heterostructures. It was found that mercaptopropionic acid as bifunctional molecules could bind with CdSe and TiO2 to form a cross-linked morphology. The charge carrier dynamics of bare CdSe and CdSe/TiO2 were detected using femtosecond transient absorption spectroscopy. In the presence of TiO2, the average exciton lifetime of CdSe QDs was apparently decreased, owing to the electron transfer from photoexcited CdSe to TiO2. Particularly, the electron-transfer rate from small CdSe QDs (3.0 nm) was much faster than that from big CdSe QDs (4.2 nm). The improved photocatalytic hydrogen generation was observed for CdSe/TiO2 compared to bare CdSe QDs. The enhancement factor for small CdSe QDs was higher than that for big CdSe QDs, which was in good agreement with the electron-transfer rates. This result indicated that the electron transfer between CdSe and TiO2 played an important role in photocatalytic hydrogen generation on CdSe/TiO2 type-II heterostructure. Our study provides a fundamental guidance to construct efficient heterostructured photocatalysts by delicate control of the band alignment.

  9. 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-Cα 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

  10. 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.

  11. 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.

  12. Transfer Hydrogenation of Acetophenone Catalyzed by in situ Generated 2,6-Bis(5-thioxo-4,5-dihydro-1,2,4-triazole- 3-yl)pyridine-ruthenium(Ⅱ) Complexes

    Institute of Scientific and Technical Information of China (English)

    CETIN,Ahmet; DAYAN,Osman


    2,6-Bis(5-thioxo-4,5-dihydro-1,2,4-triazole-3-yl)pyridines (3, 4) were used for the first time as ligand in ruthe-nium catalyzed transfer hydrogenation of acetophenone. The in situ prepared three-component system Ru(ll)/tridentate triamine ligands (3a-3d, 4a-4d) and KOH catalysed the transfer hydrogenation reaction of ace-tophenone in good yields under mild conditions.

  13. Cryogenic design and test results of 30-m flexible hybrid energy transfer line with liquid hydrogen and superconducting MgB2 cable (United States)

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


    In this paper we present the development of a new hybrid energy transfer line with 30 m length. The line is essentially a flexible 30 m hydrogen cryostat that has three sections with different types of thermal insulation in each section: simple vacuum superinsulation, vacuum superinsulation with liquid nitrogen precooling and active evaporating cryostatting (AEC) system. We performed thermo-hydraulic tests of the cryostat to compare three thermo-insulating methods. The tests were made at temperatures from 20 to 26 K, hydrogen flow from 70 to 450 g/s and pressure from 0.25 to 0.5 MPa. It was found that AEC thermal insulation was the most effective in reducing heat transfer from room temperature to liquid hydrogen in ∼10 m section of the cryostat, indicating that it can be used for long superconducting power cables. High voltage current leads were developed as well. The current leads and superconducting MgB2 cable passed high voltage DC test up to 50 kV DC. Critical current of the cable at ∼21 K was 3500 A. It means that the 30 m hybrid energy system developed is able to deliver ∼50-60 MW of chemical power and ∼50-75 MW of electrical power, i.e. up to ∼135 MW in total.

  14. Homogeneous asymmetric catalysis in fragrance chemistry. (United States)

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


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

  15. Reactions of the phthalimide N-oxyl radical (PINO) with activated phenols: the contribution of π-stacking interactions to hydrogen atom transfer rates. (United States)

    D'Alfonso, Claudio; Bietti, Massimo; DiLabio, Gino A; Lanzalunga, Osvaldo; Salamone, Michela


    The kinetics of reactions of the phthalimide N-oxyl radical (PINO) with a series of activated phenols (2,2,5,7,8-pentamethylchroman-6-ol (PMC), 2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols) were investigated by laser flash photolysis in CH(3)CN and PhCl in order to establish if the reactions with PINO can provide a useful tool for evaluating the radical scavenging ability of phenolic antioxidants. On the basis of the small values of deuterium kinetic isotope effects, the relatively high and negative ρ values in the Hammett correlations and the results of theoretical calculations, we suggest that these reactions proceed by a hydrogen atom transfer (HAT) mechanism having a significant degree of charge transfer resulting from a π-stacked conformation between PINO and the aromatic ring of the phenols. Kinetic solvent effects were analyzed in detail for the hydrogen transfer from 2,4,6-trimethylphenol to PINO and the data obtained are in accordance with the Snelgrove-Ingold equation for HAT. Experimental rate constants for the reactions of PINO with activated phenols are in accordance with those predicted by applying the Marcus cross relation.

  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. Reactions of the cumyloxyl radical with secondary amides. The influence of steric and stereoelectronic effects on the hydrogen atom transfer reactivity and selectivity. (United States)

    Salamone, Michela; Basili, Federica; Mele, Riccardo; Cianfanelli, Marco; Bietti, Massimo


    A time-resolved kinetic study of the hydrogen atom transfer (HAT) reactions from secondary alkanamides to the cumyloxyl radical was carried out in acetonitrile. HAT predominantly occurs from the N-alkyl α-C-H bonds, and a >60-fold decrease in kH was observed by increasing the steric hindrance of the acyl and N-alkyl groups. The role of steric and stereoelectronic effects on the reactivity and selectivity is discussed in the framework of HAT reactions from peptides.

  19. Kinetic Study of the Reaction of the Phthalimide-N-oxyl Radical with Amides: Structural and Medium Effects on the Hydrogen Atom Transfer Reactivity and Selectivity. (United States)

    Bietti, Massimo; Forcina, Veronica; Lanzalunga, Osvaldo; Lapi, Andrea; Martin, Teo; Mazzonna, Marco; Salamone, Michela


    A kinetic study of the hydrogen atom transfer (HAT) reactions from a series of secondary N-(4-X-benzyl)acetamides and tertiary amides to the phthalimide-N-oxyl radical (PINO) has been carried out. The results indicate that HAT is strongly influenced by structural and medium effects; in particular, the addition of Brønsted and Lewis acids determines a significant deactivation of C-H bonds α to the amide nitrogen of these substrates. Thus, by changing the reaction medium, it is possible to carefully control the regioselectivity of the aerobic oxidation of amides catalyzed by N-hydroxyphthalimide, widening the synthetic versatility of this process.

  20. Mechanistic aspects of gas-phase hydrogen-atom transfer from methane to [CO](·+) and [SiO](·+) : why do they differ? (United States)

    Dietl, Nicolas; Troiani, Anna; Schlangen, Maria; Ursini, Ornella; Angelini, Giancarlo; Apeloig, Yitzhak; de Petris, Giulia; Schwarz, Helmut


    The reactivity of the two diatomic congeneric systems [CO](·+) and [SiO](·+) towards methane has been investigated by means of mass spectrometry and quantum-chemical calculations. While [CO](·+) gives rise to three different reaction channels, [SiO](·+) reacts only by hydrogen-atom transfer (HAT) from methane under thermal conditions. A theoretical analysis of the respective HAT processes reveals two distinctly different mechanistic pathways for [CO](·+) and [SiO](·+), and a comparison to the higher metal oxides of Group 14 emphasizes the particular role of carbon as a second-row p element.

  1. Hydrogen-Transfer-Mediated Direct β-Alkylation of Aryl-1,8-naphthyridines with Alcohols under Transition Metal Catalyst Free Conditions. (United States)

    Xiong, Biao; Zhang, Shudi; Jiang, Huanfeng; Zhang, Min


    By employing abundant and sustainable alcohols as the alkylating reagents, a new and direct alkylation method has been demonstrated. This method enables the selective alkylation of the less substituted pyridyl ring at the β-site of aryl-1,8-naphthyridines, affording the desired products in moderate to excellent yields upon isolation. The method proceeds under transition-metal-free conditions in an atom- and step-economic fashion and liberates water as the sole byproduct. Mechanistic investigations suggest the reaction undergoes a hydrogen-transfer-mediated alkylation mode.

  2. Evidence for a Precursor Complex in C-H Hydrogen Atom Transfer Reactions Mediated by a Manganese(IV) Oxo Complex


    Garcia Bosch, Isaac; Company Casadevall, Anna; Cady, Clyde W.; Styring, Stenbjörn; Browne, Wesley R; Ribas Salamaña, Xavi; Costas Salgueiro, Miquel


    HAT trick: [MnIV(OH)2(H,MePytacn)]2+ (A) and [MnIV(O)(OH)(H,MePytacn)]+ (B) differ in their reactions with CH bonds: compound A engages in typical single-step hydrogen atom transfer (HAT) reactions, whereas B first forms a substrate–B encounter complex (C; see scheme). This equilibrium alters the relative CH reactivity from that expected from CH bond dissociation energies Aquest mateix article està publicat a l'edició alemanya d''Angewandte Chemie' (ISSN 0044-8249, EISSN 1521-3757), 2011, ...

  3. 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.

  4. Steric Effect for Proton, Hydrogen-Atom, andHydride Transfer Reactions with Geometric Isomers of NADH-Model Ruthenium Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Fujita E.; Cohen, B.W.; Polyansky, D.E.; Achord, P.; Cabelli, D.; Muckerman, J.T.; Tanaka, K.; Thummel, R.P.; Zong, R.


    Two isomers, [Ru(1)]{sup 2+} (Ru = Ru(bpy){sub 2}, bpy = 2,2{prime}-bipyridine, 1 = 2-(pyrid-2{prime}-yl)-1-azaacridine) and [Ru(2)]{sup 2+} (2 = 3-(pyrid-2{prime}-yl)-4-azaacridine), are bio-inspired model compounds containing the nicotinamide functionality and can serve as precursors for the photogeneration of C-H hydrides for studying reactions pertinent to the photochemical reduction of metal-C{sub 1} complexes and/or carbon dioxide. While it has been shown that the structural differences between the azaacridine ligands of [Ru(1)]{sup 2+} and [Ru(2)]{sup 2+} have a significant effect on the mechanism of formation of the hydride donors, [Ru(1HH)]{sup 2+} and [Ru(2HH)]{sup 2+}, in aqueous solution, we describe the steric implications for proton, net-hydrogen-atom and net-hydride transfer reactions in this work. Protonation of [Ru(2{sup {sm_bullet}-})]{sup +} in aprotic and even protic media is slow compared to that of [Ru(1{sup {sm_bullet}-})]{sup +}. The net hydrogen-atom transfer between *[Ru(1)]{sup 2+} and hydroquinone (H{sub 2}Q) proceeds by one-step EPT, rather than stepwise electron-proton transfer. Such a reaction was not observed for *[Ru(2)]{sup 2+} because the non-coordinated N atom is not easily available for an interaction with H{sub 2}Q. Finally, the rate of the net hydride ion transfer from [Ru(1HH)]{sup 2+} to [Ph{sub 3}C]{sup +} is significantly slower than that of [Ru(2HH)]{sup 2+} owing to steric congestion at the donor site.

  5. Hydrogen atom transfer from 1,n-alkanediamines to the cumyloxyl radical. Modulating C-H deactivation through acid-base interactions and solvent effects. (United States)

    Milan, Michela; Salamone, Michela; Bietti, Massimo


    A time-resolved kinetic study on the effect of trifluoroacetic acid (TFA) on the hydrogen atom transfer (HAT) reactions from 1,n-alkanediamines (R2N(CH2)nNR2, R = H, CH3; n = 1-4), piperazine, and 1,4-dimethylpiperazine to the cumyloxyl radical (CumO(•)), has been carried out in MeCN and DMSO. Very strong deactivation of the α-C-H bonds has been observed following nitrogen protonation and the results obtained have been explained in terms of substrate basicity, of the distance between the two basic centers and of the solvent hydrogen bond acceptor ability. At [substrate] ≤ 1/2 [TFA] the substrates exist in the doubly protonated form HR2N(+)(CH2)nN(+)R2H, and no reaction with CumO(•) is observed. At 1/2 [TFA] [TFA], HAT occurs from the α-C-H bonds of R2N(CH2)nNR2, and the mesured kH values are very close to those obtained in the absence of TFA. Comparison between MeCN and DMSO clearly shows that in the monoprotonated diamines R2N(CH2)nN(+)R2H remote C-H deactivation can be modulated through solvent hydrogen bonding.

  6. Excited state intramolecular proton transfer (ESIPT) in six-coordinated zinc(ii)-quinoxaline complexes with ligand hydrogen bonds: their fluorescent properties sensitive to axial positions. (United States)

    Sakai, Ken-Ichi; Takahashi, Sami; Kobayashi, Ataru; Akutagawa, Tomoyuki; Nakamura, Takayoshi; Dosen, Masaaki; Kato, Masako; Nagashima, Umpei


    Zinc(ii)-quinoxaline complexes, [Zn(hqxc)(2)(py)(2)] and [Zn(hqxc)(2)(DMSO)(2)] (hqxc = 3-hydroxy-2-quinoxalinecarboxylate, py = pyridine, DMSO = dimethyl sulfoxide), were prepared and characterized by X-ray crystallography and fluorescence spectroscopy. In both complexes, the zinc ion is six-coordinated by two equatorial bidentate hqxc ligands with an intramolecular hydrogen bond and two axial monodentate ligands such as pyridine or DMSO. In spite of similar coordination geometries, there is a remarkable difference between their solid-state fluorescent properties. The pyridine complex is strongly fluorescent (fluorescence quantum yield Phi = 0.22), giving rise to a significantly Stokes-shifted spectrum. From its thin film photopumped by a nitrogen gas laser, amplified spontaneous emission was observed. These results suggest that the fluorescence occurs by way of excited-state intramolecular proton-transfer (ESIPT) in the hydrogen bond of hqxc. On the other hand, the DMSO complex shows fluorescent intensity (Phi = 0.08) lower than that of the pyridine complex, and shows normal emission in addition to ESIPT emission. From IR measurements for these complexes, it is concluded that axial ligands influence the hydrogen bond strength of the equatorial hqxc ligand via zinc and thus the ESIPT efficiency.

  7. Proton/hydrogen-transfer coordinate of 2,5-dihydroxybenzoic acid investigated in a supersonic beam: combined IR/UV spectroscopy in the S0, S1, and D0 states. (United States)

    Fricke, Holger; Bartl, Kristina; Funk, Andreas; Gerlach, Andreas; Gerhards, Markus


    As a model system for intramolecular proton/hydrogen-transfer coordinates, the structure of 2,5-dihydroxybenzoic acid is investigated for the ground, first electronically excited and also the ionic state. Combined IR/UV spectroscopy in molecular-beam experiments is applied and the experimental results are interpreted by the application of DFT and CASPT2 methods. No proton or hydrogen transfer is observed, but evidence is given for a hydrogen dislocation of the intramolecular hydrogen bond in the S(1) state and to lesser extent in the D(0) state. To obtain direct information on the proton/hydrogen-transfer coordinate, IR spectra are recorded both in the region of the OH and especially the CO stretching vibrations by also applying two new variants of combined IR/UV spectroscopy for the S(1) and D(0) states. The CO groups are directly involved in the hydrogen bond and, in contrast to the hydrogen-bonded OH groups, the CO stretching frequencies can be observed in all electronic states.

  8. Transferable potentials for phase equilibria. 9. Explicit hydrogen description of benzene and five-membered and six-membered heterocyclic aromatic compounds. (United States)

    Rai, Neeraj; Siepmann, J Ilja


    The explicit hydrogen version of the transferable potentials for phase equilibria (TraPPE-EH) force field is extended to benzene, pyridine, pyrimidine, pyrazine, pyridazine, thiophene, furan, pyrrole, thiazole, oxazole, isoxazole, imidazole, and pyrazole. While the Lennard-Jones parameters for carbon, hydrogen (two types), nitrogen (two types), oxygen, and sulfur are transferable for all 13 compounds, the partial charges are specific for each compound. The benzene dimer energies for sandwich, T-shape, and parallel-displaced configurations obtained for the TraPPE-EH force field compare favorably with high-level electronic structure calculations. Gibbs ensemble Monte Carlo simulations were carried out to compute the single-component vapor-liquid equilibria for benzene, pyridine, three diazenes, and eight five-membered heterocycles. The agreement with experimental data is excellent with the liquid densities and vapor pressures reproduced within 1 and 5%, respectively. The critical temperatures and normal boiling points are predicted with mean deviations of 0.8 and 1.6%, respectively.

  9. Evidence for excited-state intramolecular proton transfer in 4-chlorosalicylic acid from combined experimental and computational studies: Quantum chemical treatment of the intramolecular hydrogen bonding interaction

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Bijan Kumar [Department of Chemistry, University of Calcutta, 92 Acharya Prafulla Chandra Road, Calcutta 700009 (India); Guchhait, Nikhil, E-mail: [Department of Chemistry, University of Calcutta, 92 Acharya Prafulla Chandra Road, Calcutta 700009 (India)


    Highlights: Black-Right-Pointing-Pointer Experimental and computational studies on the photophysics of 4-chlorosalicylic acid. Black-Right-Pointing-Pointer Spectroscopically established ESIPT reaction substantiated by theoretical calculation. Black-Right-Pointing-Pointer Quantum chemical treatment of IMHB unveils strength, nature and directional nature. Black-Right-Pointing-Pointer Superiority of quantum chemical treatment of H-bond over geometric criteria. Black-Right-Pointing-Pointer Role of H-bond as a modulator of aromaticity. -- Abstract: The photophysical study of a pharmaceutically important chlorine substituted derivative of salicylic acid viz., 4-chlorosalicylic acid (4ClSA) has been carried out by steady-state absorption, emission and time-resolved emission spectroscopy. A large Stokes shifted emission band with negligible solvent polarity dependence marks the spectroscopic signature of excited-state intramolecular proton transfer (ESIPT) reaction in 4ClSA. Theoretical calculation by ab initio and Density Functional Theory methods yields results consistent with experimental findings. Theoretical potential energy surfaces predict the occurrence of proton transfer in S{sub 1}-state. Geometrical and energetic criteria, Atoms-In-Molecule topological parameters, Natural Bond Orbital population analysis have been exploited to evaluate the intramolecular hydrogen bond (IMHB) interaction and to explore its directional nature. The inter-correlation between aromaticity and resonance assisted H-bond is also discussed in this context. Our results unveil that the quantum chemical treatment is a more accurate tool to assess hydrogen bonding interaction in comparison to geometrical criteria.

  10. Redox control and hydrogen bonding networks: proton-coupled electron transfer reactions and tyrosine Z in the photosynthetic oxygen-evolving complex. (United States)

    Keough, James M; Zuniga, Ashley N; Jenson, David L; Barry, Bridgette A


    In photosynthetic oxygen evolution, redox active tyrosine Z (YZ) plays an essential role in proton-coupled electron transfer (PCET) reactions. Four sequential photooxidation reactions are necessary to produce oxygen at a Mn(4)CaO(5) cluster. The sequentially oxidized states of this oxygen-evolving cluster (OEC) are called the S(n) states, where n refers to the number of oxidizing equivalents stored. The neutral radical, YZ•, is generated and then acts as an electron transfer intermediate during each S state transition. In the X-ray structure, YZ, Tyr161 of the D1 subunit, is involved in an extensive hydrogen bonding network, which includes calcium-bound water. In electron paramagnetic resonance experiments, we measured the YZ• recombination rate, in the presence of an intact Mn(4)CaO(5) cluster. We compared the S(0) and S(2) states, which differ in Mn oxidation state, and found a significant difference in the YZ• decay rate (t(1/2) = 3.3 ± 0.3 s in S(0); t(1/2) = 2.1 ± 0.3 s in S(2)) and in the solvent isotope effect (SIE) on the reaction (1.3 ± 0.3 in S(0); 2.1 ± 0.3 in S(2)). Although the YZ site is known to be solvent accessible, the recombination rate and SIE were pH independent in both S states. To define the origin of these effects, we measured the YZ• recombination rate in the presence of ammonia, which inhibits oxygen evolution and disrupts the hydrogen bond network. We report that ammonia dramatically slowed the YZ• recombination rate in the S(2) state but had a smaller effect in the S(0) state. In contrast, ammonia had no significant effect on YD•, the stable tyrosyl radical. Therefore, the alterations in YZ• decay, observed with S state advancement, are attributed to alterations in OEC hydrogen bonding and consequent differences in the YZ midpoint potential/pK(a). These changes may be caused by activation of metal-bound water molecules, which hydrogen bond to YZ. These observations document the importance of redox control in proton

  11. Role of hydrogen-bonding and photoinduced electron transfer (PET) on the interaction of resorcinol based acridinedione dyes with Bovine Serum Albumin (BSA) in water

    Energy Technology Data Exchange (ETDEWEB)

    Kumaran, Rajendran, E-mail: [Department of Chemistry, Dwaraka Doss Goverdhan Doss, Vaishnav College (Autonomous), 833, Gokul Bagh, E.V.R. Periyar Road, Arumbakkam, Chennai 600106, Tamil Nadu (India); Vanjinathan, Mahalingam [Department of Chemistry, Dwaraka Doss Goverdhan Doss, Vaishnav College (Autonomous), 833, Gokul Bagh, E.V.R. Periyar Road, Arumbakkam, Chennai 600106, Tamil Nadu (India); Ramamurthy, Perumal [National Centre for Ultrafast Processes, University of Madras, Taramani Campus Chennai 600113, Tamil Nadu (India)


    Resorcinol based acridinedione (ADDR) dyes are a class of laser dyes and have structural similarity with purine derivatives, nicotinamide adenine dinucleotide (NADH) analogs. These dyes are classified into photoinduced electron transfer (PET) and non-photoinduced electron transfer dyes, and the photophysical properties of family of these dyes exhibiting PET behavior are entirely different from that of non-PET dyes. The PET process in ADDR dyes is governed by the solvent polarity such that an ADDR dye exhibits PET process through space in an aprotic solvent like acetonitrile and does not exhibit the same in protic solvents like water and methanol. A comparison on the fluorescence emission, lifetime and nature of interaction of various ADDR dyes with a large globular protein like Bovine Serum Albumin (BSA) was carried out in aqueous solution. The interaction of PET based ADDR dyes with BSA in water is found to be largely hydrophobic, but hydrogen-bonding interaction of BSA with dye molecule influences the fluorescence emission of the dye and shifts the emission towards red region. Fluorescence spectral studies reveal that the excited state properties of PET based ADDR dyes are largely influenced by the addition of BSA. The microenvironment around the dye results in significant change in the fluorescence lifetime and emission. Fluorescence enhancement with a red shift in the emission results after the addition of BSA to ADDR dyes containing free amino hydrogen in the 10th position of basic acridinedione dye. The amino hydrogen (N–H) in the 10th position of ADDR dye is replaced by methyl group (N–CH{sub 3}), a significant decrease in the fluorescence intensity with no apparent shift in the emission maximum was observed after the addition of BSA. The nature of interaction between ADDR dyes with BSA is hydrogen-bonding and the dye remains unbound even at the highest concentration of BSA. Circular Dichroism (CD) studies show that the addition of dye to BSA results in

  12. 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.

  13. 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.

  14. Effects of the large distribution of CdS quantum dot sizes on the charge transfer interactions into TiO2 nanotubes for photocatalytic hydrogen generation (United States)

    González-Moya, Johan R.; Garcia-Basabe, Yunier; Rocco, Maria Luiza M.; Pereira, Marcelo B.; Princival, Jefferson L.; Almeida, Luciano C.; Araújo, Carlos M.; David, Denis G. F.; Ferreira da Silva, Antonio; Machado, Giovanna


    trap for the electrons photogenerated by the population with a larger band gap. Electron transfer from CdS quantum dots to TiO2 semiconductor nanotubes was proven by the results of UPS measurements combined with optical band gap measurements. This property facilitates an improvement of the visible-light hydrogen evolution rate from zero, for TiO2 nanotubes, to approximately 0.3 μmol cm-2 h-1 for TiO2 nanotubes sensitized with CdS quantum dots.

  15. Highly regioselective hydride transfer, oxidative dehydrogenation, and hydrogen-atom abstraction in the thermal gas-phase chemistry of [Zn(OH)](+)/C3H8. (United States)

    Wu, Xiao-Nan; Zhao, Hai-Tao; Li, Jilai; Schlangen, Maria; Schwarz, Helmut


    The thermal reactions of [Zn(OH)](+) with C3H8 have been studied by means of gas-phase experiments and computational investigation. Two types of C-H bond activation are observed in the experiment, and pertinent mechanistic features include inter alia: (i) the metal center of [Zn(OH)](+) serves as active site in the hydride transfer to generate [i-C3H7](+) as major product, (ii) generally, a high regioselectivity is accompanied by remarkable chemoselectivity: for example, the activation of a methyl C-H bond results mainly in the formation of water and [Zn(C3,H7)](+). According to computational work, this ionic product corresponds to [HZn(CH3CH=CH2)](+). Attack of the zinc center at a secondary C-H bond leads preferentially to hydride transfer, thus giving rise to the generation of [i-C3H7](+); (iii) upon oxidative dehydrogenation (ODH), liberation of CH3CH2=CH2 occurs to produce [HZn(H2O)](+). Both, ODH as well as H2O loss proceed through the same intermediate which is characterized by the fact that a methylene hydrogen atom from the substrate is transferred to the zinc and one hydrogen atom from the methyl group to the OH group of [Zn(OH)](+). The combined experimental/computational gas-phase study of C-H bond activation by zinc hydroxide provides mechanistic insight into related zinc-catalyzed large-scale processes and identifies the crucial role that the Lewis-acid character of zinc plays.

  16. General model of depolarization and transfer of polarization of singly ionized atoms by collisions with hydrogen atoms

    CERN Document Server

    Derouich, Moncef


    Simulations of the generation of the atomic polarization is necessary for interpreting the second solar spectrum. For this purpose, it is important to rigorously determine the effects of the isotropic collisions with neutral hydrogen on the atomic polarization of the neutral atoms, ionized atoms and molecules. Our aim is to treat in generality the problem of depolarizing isotropic collisions between singly ionized atoms and neutral hydrogen in its ground state. Using our numerical code, we computed the collisional depolarization rates of the $p$-levels of ions for large number of values of the effective principal quantum number $n^{*}$ and the Uns\\"old energy $E_p$. Then, genetic programming has been utilized to fit the available depolarization rates. As a result, strongly non-linear relationships between the collisional depolarization rates, $n^{*}$ and $E_p$ are obtained, and are shown to reproduce the original data with accuracy clearly better than 10\\%. These relationships allow quick calculations of the ...

  17. Electronic Origins of the Variable Efficiency of Room-Temperature Methane Activation by Homo- and Heteronuclear Cluster Oxide Cations [XYO2](+) (X, Y = Al, Si, Mg): Competition between Proton-Coupled Electron Transfer and Hydrogen-Atom Transfer. (United States)

    Li, Jilai; Zhou, Shaodong; Zhang, Jun; Schlangen, Maria; Weiske, Thomas; Usharani, Dandamudi; Shaik, Sason; Schwarz, Helmut


    The reactivity of the homo- and heteronuclear oxide clusters [XYO2](+) (X, Y = Al, Si, Mg) toward methane was studied using Fourier transform ion cyclotron resonance mass spectrometry, in conjunction with high-level quantum mechanical calculations. The most reactive cluster by both experiment and theory is [Al2O2](•+). In its favorable pathway, this cluster abstracts a hydrogen atom by means of proton-coupled electron transfer (PCET) instead of following the conventional hydrogen-atom transfer (HAT) route. This mechanistic choice originates in the strong Lewis acidity of the aluminum site of [Al2O2](•+), which cleaves the C-H bond heterolytically to form an Al-CH3 entity, while the proton is transferred to the bridging oxygen atom of the cluster ion. In addition, a comparison of the reactivity of heteronuclear and homonuclear oxide clusters [XYO2](+) (X, Y = Al, Si, Mg) reveals a striking doping effect by aluminum. Thus, the vacant s-p hybrid orbital on Al acts as an acceptor of the electron pair from methyl anion (CH3(-)) and is therefore eminently important for bringing about thermal methane activation by PCET. For the Al-doped cluster ions, the spin density at an oxygen atom, which is crucial for the HAT mechanism, acts here as a spectator during the course of the PCET mediated C-H bond cleavage. A diagnostic plot of the deformation energy vis-à-vis the barrier shows the different HAT/PCET reactivity map for the entire series. This is a strong connection to the recently discussed mechanism of oxidative coupling of methane on magnesium oxide surfaces proceeding through Grignard-type intermediates.

  18. Highly enantioselective transfer hydrogenation of ketones with chiral (NH)2 P2 macrocyclic iron(II) complexes. (United States)

    Bigler, Raphael; Huber, Raffael; Mezzetti, Antonio


    Bis(isonitrile) iron(II) complexes bearing a C2 -symmetric diamino (NH)2 P2 macrocyclic ligand efficiently catalyze the hydrogenation of polar bonds of a broad scope of substrates (ketones, enones, and imines) in high yield (up to 99.5 %), excellent enantioselectivity (up to 99 % ee), and with low catalyst loading (generally 0.1 mol %). The catalyst can be easily tuned by modifying the substituents of the isonitrile ligand.

  19. Chirality Transfer and Modulation in LB Films Derived From the Diacetylene/Melamine Hydrogen-Bonded Complex. (United States)

    Zhu, Yu; Xu, Yangyang; Zou, Gang; Zhang, Qijin


    Introduction of hydrogen-bonding interaction into π-conjugated systems is a promising strategy, since the highly selective and directional hydrogen-bonding can increase the binding strength, provide enhanced stability to the assemblies, and position the π-conjugated molecules in a desired arrangement. The helical packing of the rigid melamine cores seems to play a dominating role in the subsequent formation of the peripheral helical PDA backbone. The polymerized Langmuir-Blodgett (LB) films exhibited reversible colorimetric and chiroptical changes during repeated heating-cooling cycles, which should be ascribed to the strong hydrogen-bonding interaction between the carboxylic acid and the melamine core. Further, the closely helical packing of the melamine cores could be destroyed upon exposure to HCl or NH(3) gas, whereas the peripheral helical polyaniline and polydiacetylene (PDA) backbone exhibited excellent stability. Although similar absorption changes could be observed for the films upon exposure to HCl or NH(3) gas, their distinct circular dichroism (CD) responses enabled us to distinguish the above two stimuli.

  20. Optimum bifunctionality in a 2-(2-pyridyl-2-ol)-1,10-phenanthroline based ruthenium complex for transfer hydrogenation of ketones and nitriles: impact of the number of 2-hydroxypyridine fragments. (United States)

    Paul, Bhaskar; Chakrabarti, Kaushik; Kundu, Sabuj


    Considerable differences in reactivity and selectivity for 2-hydroxypyridine (2-HP) derived ruthenium complexes in transfer hydrogenation are described. Bifunctional Ru(ii)-(phenpy-OH) [phenpy-OH: 2-(2-pyridyl-2-ol)-1,10-phenanthroline] complex () exhibited excellent catalytic activity in transfer hydrogenation (TH) of ketones and nitriles. Notably, in comparison with all the reported 2-hydroxypyridine (2-HP) derived ruthenium complexes in transfer hydrogenation, complex displayed significantly higher activity. Additionally, exploiting the metal-ligand cooperativity in complex , chemoselective TH of ketones was achieved and sterically demanding ketones were readily reduced. An outer-sphere mechanism is proposed for this system as exogenous PPh3 has no significant effect on the rate of this reaction. This is a rare example of a highly active bifunctional Ru(ii) catalyst bearing only one 2-HP unit.

  1. Hydrogen transfer experiments and modelization in clay rocks for radioactive waste deep geological repository; Experimentation et modelisation du transfert d'hydrogene a travers des argiles de centre de stockage de dechets radioactifs

    Energy Technology Data Exchange (ETDEWEB)

    Boulin, P


    Gases will be generated by corrosion of high radioactive waste containers in deep geological repositories. A gas phase will be generated. Gas pressure will build up and penetrated the geological formation. If gases do not penetrate the geological barrier efficiently, the pressure build up may create a risk of fracturing and of creation of preferential pathways for radionuclide migration. The present work focuses on Callovo-Oxfordian argillites characterisation. An experiment, designed to measure very low permeabilities, was used with hydrogen/helium and analysed using the Dusty Gas Model. Argillites close to saturation have an accessible porosity to gas transfer that is lower than 0,1% to 1% of the porosity. Analysis of the Knudsen effect suggests that this accessible network should be made of 50 nm to 200 nm diameter pores. The permeabilities values were integrated to an ANDRA operating model. The model showed that the maximum pressure expected near the repository would be 83 bar. (author)

  2. Hydrogen-bonded sheets in benzylmethylammonium hydrogen maleate. (United States)

    Santacruz, Lynay; Abonia, Rodrigo; Cobo, Justo; Low, John N; Glidewell, Christopher


    In the title compound, C(8)H(12)N(+).C(4)H(3)O(4)(-), there is a short and almost linear but asymmetric O-H...O hydrogen bond in the anion. The ions are linked into C(2)(2)(6) chains by two short and nearly linear N-H...O hydrogen bonds and the chains are further weakly linked into sheets by a single C-H...O hydrogen bond.

  3. Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H and its role in proton transfer. (United States)

    Dub, Pavel A; Filippov, Oleg A; Belkova, Natalia V; Daran, Jean-Claude; Epstein, Lina M; Poli, Rinaldo; Shubina, Elena S


    The interaction of the carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H with Brønsted (fluorinated alcohols, (CF(3))(n)CH(3-n)OH (n = 1-3), and CF(3)COOH) and Lewis (Hg(C(6)F(5))(2), BF(3).OEt(2)) acids was studied by variable temperature IR and NMR ((1)H, (31)P, (13)C) spectroscopies in combination with DFT/B3LYP calculations. Among the two functionalities potentially capable of the interaction - carbonyl and hydride ligands - the first was found to be the preferential binding site for weak acids, yielding CO...HOR or CO...Hg complexes as well as CO...(HOR)(2) adducts. For stronger proton donors ((CF(3))(3)COH, CF(3)COOH) hydrogen-bonding to the hydride ligand can be revealed as an intermediate of the proton transfer reaction. Whereas proton transfer to the CO ligand is not feasible, protonation of the hydride ligand yields an (eta(2)-H(2)) complex. Above 230 K dihydrogen evolution is observed leading to decomposition. Among the decomposition products compound [Cp*Mo(PMe(3))(3)(CO)](+)[(CF(3))(3)CO.2HOC(CF(3))(3)](-) resulting from a phosphine transfer reaction was characterized by X-ray diffraction. Reaction with BF(3).OEt(2) was found to produce [Cp*Mo(PMe(3))(2)(CO)BF(4)] via initial attack of the hydride ligand.

  4. 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.

  5. 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, G.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 (R

  6. General model of depolarization and transfer of polarization of singly ionized atoms by collisions with hydrogen atoms (United States)

    Derouich, M.


    Simulations of the generation of the atomic polarization is necessary for interpreting the second solar spectrum. For this purpose, it is important to rigorously determine the effects of the isotropic collisions with neutral hydrogen on the atomic polarization of the neutral atoms, ionized atoms and molecules. Our aim is to treat in generality the problem of depolarizing isotropic collisions between singly ionized atoms and neutral hydrogen in its ground state. Using our numerical code, we computed the collisional depolarization rates of the p-levels of ions for large number of values of the effective principal quantum number n* and the Unsöld energy Ep. Then, genetic programming has been utilized to fit the available depolarization rates. As a result, strongly non-linear relationships between the collisional depolarization rates, n* and Ep are obtained, and are shown to reproduce the original data with accuracy clearly better than 10%. These relationships allow quick calculations of the depolarizing collisional rates of any simple ion which is very useful for the solar physics community. In addition, the depolarization rates associated to the complex ions and to the hyperfine levels can be easily derived from our results. In this work we have shown that by using powerful numerical approach and our collisional method, general model giving the depolarization of the ions can be obtained to be exploited for solar applications.

  7. Breaking scaling relations to achieve low-temperature ammonia synthesis through LiH-mediated nitrogen transfer and hydrogenation (United States)

    Wang, Peikun; Chang, Fei; Gao, Wenbo; Guo, Jianping; Wu, Guotao; He, Teng; Chen, Ping


    Ammonia synthesis under mild conditions is a goal that has been long sought after. Previous investigations have shown that adsorption and transition-state energies of intermediates in this process on transition metals (TMs) scale with each other. This prevents the independent optimization of these energies that would result in the ideal catalyst: one that activates reactants well, but binds intermediates relatively weakly. Here we demonstrate that these scaling relations can be broken by intervening in the TM-mediated catalysis with a second catalytic site, LiH. The negatively charged hydrogen atoms of LiH act as strong reducing agents, which remove activated nitrogen atoms from the TM or its nitride (TMN), and as an immediate source of hydrogen, which binds nitrogen atoms to form LiNH2. LiNH2 further splits H2 heterolytically to give off NH3 and regenerate LiH. This synergy between TM (or TMN) and LiH creates a favourable pathway that allows both early and late 3d TM-LiH composites to exhibit unprecedented lower-temperature catalytic activities.

  8. The tert-butoxyl radical mediated hydrogen atom transfer reactions of the Parkinsonian proneurotoxin 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine and selected tertiary amines. (United States)

    Suleman, N Kamrudin; Flores, Joey; Tanko, James M; Isin, Emre Mehmet; Castagnoli, Neal


    Previous studies have shown that the hydrogen atom transfer (HAT) reactions of tert-butoxyl radical from the Parkinsonian proneurotoxin 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) occur with low selectivity at the allylic and non-allylic alpha-C-H positions. In this paper, we report a more comprehensive regiochemical study on the reactivity of the tert-butoxyl radical as well as on the associated primary kinetic deuterium isotope effects for the various hydrogen atom abstractions of MPTP. In addition, the results of a computational study to estimate the various C-H bond dissociation energies of MPTP are presented. The results of the present study show the allylic/non-allylic selectivity is approximately 73:21. The behavior of the tert-butoxyl radical mediated oxidation of MPTP contrasts with this reaction as catalyzed by monoamine oxidase B (MAO-B) that occurs selectively at the allylic alpha-carbon. These observations lead to the conclusion that the tert-butoxyl radical is not a good chemical model for the MAO-B-catalyzed bioactivation of MPTP.

  9. Solid H2 versus solid noble-gas environment: Influence on photoinduced hydrogen-atom transfer in matrix-isolated 4(3H)-pyrimidinone (United States)

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


    UV-induced transformations have been studied for 4(3H)-pyrimidinone monomers isolated in low-temperature Ar, Ne, n-D2, and n-H2 matrices. The observed photochemical behavior of the compound drastically depended on the solid matrix environment. For 4(3H)-pyrimidinone isolated in solid Ar, the UV-induced phototautomeric transformation was clearly the dominating process, leading to a nearly quantitative conversion of the oxo reactant into the hydroxy product. For solid Ne environment, the oxo → hydroxy transformation was still the major photoprocess, but yielding less of the hydroxy product (ca. 64% of the yield in solid Ar). For 4(3H)-pyrimidinone isolated in solid n-H2, the oxo → hydroxy phototautomeric conversion did not occur (or occurred at a very tiny scale). Also for deuterated 4(3D)-pyrimidinone isolated in solid hydrogen, the analogous oxo → deuteroxy phototransformation was not observed. Finally, for the compound trapped in solid n-D2, the oxo → hydroxy phototautomerism clearly occurred, but the yield of the hydroxy tautomer was small (ca. 18% of the yield in solid Ar). Apart from hydrogen-atom-transfer processes, two other phototransformations: generation of open-ring conjugated ketene and valence Dewar isomer were observed for the compound isolated in Ar, Ne, n-D2, and n-H2 matrices.

  10. 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


    Biological biogas upgrading coupling CO2 with external H2 to form biomethane opens new avenues for sustainable biofuel production. For developing this technology, efficient H2 to liquid transfer is fundamental. This study proposes an innovative setup for in-situ biogas upgrading converting the CO2...... 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...

  11. 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 CO2 with external H2 to form biomethane opens new avenues for sustainable biofuel production. For developing this technology, efficient H2 to liquid transfer is fundamental. This study proposes an innovative setup for in-situ biogas upgrading converting the CO2 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% and the final biogas was upgraded from 58 to 82% CH4 content.

  12. Multi-scale modeling of the heat and mass transfer in a monolithic methane steam-reformer for hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Acevedo, Luis Evelio Garcia; Oliveira, Amir Antonio Martins [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Dept. de Engenharia Mecanica], e-mail:, e-mail:


    Here we present a heat and mass transfer analysis for the catalytic methane steam-reforming in a porous monolithic reactor. Thermodynamic analysis provides the bounds for temperature, pressure and steam-methane molar ration for optimum operation. However, the reactor operation is also constrained by chemical kinetics and heat and mass transfer limitations. Porous wash coated monoliths have been used for a long time in the automotive industry as catalytic converters for destruction of gas and particulate pollutants. Here we analyze the modeling issues related to a multi-scale porous structure and develop a model able to assess the advantages and drawbacks of using a monolith as support for a catalyst layer for steam-reforming. (author)

  13. 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 Ce(3+) matching to the adsorption energy of Tb(3+)((4)fn) results in the efficient energy transfer from Ce(3+) to Tb(3+), thus the synthesized ATP-Ce/Tb-Tris CPNs exhibit the characteristic green emission of Tb(3+). 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 Ce(3+) in ATP-Ce/Tb-Tris CNPs to Ce(4+) would interrupt the energy transfer from Ce(3+) to Tb(3+), leading to fluorescence quenching of Tb(3+). 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.

  14. Intermolecular hydrogen transfer between guest species in small and large cages of methane + propane mixed gas hydrates. (United States)

    Sugahara, Takeshi; Kobayashi, Yusuke; Tani, Atsushi; Inoue, Tatsuya; Ohgaki, Kazunari


    To investigate the molecular interaction between guest species inside of the small and large cages of methane + propane mixed gas hydrates, thermal stabilities of the methyl radical (possibly induced in small cages) and the normal propyl and isopropyl radicals (induced in large cages) were investigated by means of electron spin resonance measurements. The increase of the total amount of the normal propyl and isopropyl radicals reveals that the methyl radical in the small cage withdraws one hydrogen atom from the propane molecule enclathrated in the adjacent large cage of the structure-II hydrate. A guest species in a hydrate cage has the ability to interact closely with the other one in the adjacent cages. The clathrate hydrate may be utilized as a possible nanoscale reaction field.

  15. Interspecies electron transfer via hydrogen and formate rather than direct electrical connections in cocultures of Pelobacter carbinolicus and Geobacter sulfurreducens. (United States)

    Rotaru, Amelia-Elena; Shrestha, Pravin M; Liu, Fanghua; Ueki, Toshiyuki; Nevin, Kelly; Summers, Zarath M; Lovley, Derek R


    Direct interspecies electron transfer (DIET) is an alternative to interspecies H(2)/formate transfer as a mechanism for microbial species to cooperatively exchange electrons during syntrophic metabolism. To understand what specific properties contribute to DIET, studies were conducted with Pelobacter carbinolicus, a close relative of Geobacter metallireducens, which is capable of DIET. P. carbinolicus grew in coculture with Geobacter sulfurreducens with ethanol as the electron donor and fumarate as the electron acceptor, conditions under which G. sulfurreducens formed direct electrical connections with G. metallireducens. In contrast to the cell aggregation associated with DIET, P. carbinolicus and G. sulfurreducens did not aggregate. Attempts to initiate cocultures with a genetically modified strain of G. sulfurreducens incapable of both H(2) and formate utilization were unsuccessful, whereas cocultures readily grew with mutant strains capable of formate but not H(2) uptake or vice versa. The hydrogenase mutant of G. sulfurreducens compensated, in cocultures, with significantly increased formate dehydrogenase gene expression. In contrast, the transcript abundance of a hydrogenase gene was comparable in cocultures with that for the formate dehydrogenase mutant of G. sulfurreducens or the wild type, suggesting that H(2) was the primary electron carrier in the wild-type cocultures. Cocultures were also initiated with strains of G. sulfurreducens that could not produce pili or OmcS, two essential components for DIET. The finding that P. carbinolicus exchanged electrons with G. sulfurreducens via interspecies transfer of H(2)/formate rather than DIET demonstrates that not all microorganisms that can grow syntrophically are capable of DIET and that closely related microorganisms may use significantly different strategies for interspecies electron exchange.

  16. Heteropolymolybdate as a New Reaction-controlled Phase-transfer Catalyst for Efficient Alcohol Oxidation with Hydrogen Peroxide

    Institute of Scientific and Technical Information of China (English)

    Zhi Huan WENG; Jin Yan WANG; Xi Gao JIAN


    A new catalytic process for the synthesis of aldehyde from alcohol by oxidation with H2O2 with high selectivity was studied. In this system, heteropolymolybdate [C7H7N(CH3)3]3{PO4[MoO(O2)2]4} was utilized as the reaction-controlled phase-transfer catalyst to catalyze oxidation of benzyl and aliphatic alcohols. The molar ratio of H2O2 and alcohol was 0.75, no other by-products were detected by gas chromatography, the results of oxidation reaction indicated that the catalyst has high activity and stability.

  17. 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.

  18. Intramolecular proton or hydrogen-atom transfer in the ground- and excited-states of 2-hydroxybenzophenone: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Yi, Ping G. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China); Liang, Yong H. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China)], E-mail:; Cao, Chen Z. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China)


    The internal rotational motion and the ground- and excited-state intramolecular proton transfer (GISPT, EISPT) reaction of 2-hydroxybenzophenone (HBP) are studied at the B3LYP/6-31G**, CIS/6-31G** and TD B3LYP/6-31++G** level. The calculated results show that there is only one minimum at the S{sub 0} and S{sub 1} state, the enol form (E) is the single minimum at the S{sub 0} state, and its rotamers and tautomers are with more than 8.24 and 10.43 kcal/mol less stable, respectively, however, the keto tautomer (K*) is the single minimum at the S{sub 1} state. Therefore, the ground- and excited-state intramolecular proton transfer reacts without a barrier between E and K or E* and K*. The energy gap between the first excited electronic state S{sub 1} 1({pi}, {pi}*){sup 1} and the second excited electronic state S{sub 2} 2(n, {pi}*){sup 1} of E is only 0.019 eV at CIS/6-31G** level. So the S{sub 0} {yields} S{sub 1} and S{sub 0} {yields} S{sub 2} excitation may occur at the same time, and the S{sub 1} state may occur the EISPT process and result a large Stokes shifted fluorescence. And the S{sub 2} state may through internal conversion to the S{sub 1} state or intersystem crossing to the T{sub 2} state. These theoretical results contrast with the conclusion of Nakayama and his coworkers [M. Hagiri, N. Ichinose, J. Kinugasa, T. Iwasa, T. Nakayama, Chem. Lett. 33 (2004) 326] stating the present of two ground-state conformers of HBP.

  19. 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.

  20. 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.

  1. 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.

  2. 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 asymmet

  3. Asymmetric reactions in continuous flow

    Directory of Open Access Journals (Sweden)

    Xiao Yin Mak


    Full Text Available An overview of asymmetric synthesis in continuous flow and microreactors is presented in this review. Applications of homogeneous and heterogeneous asymmetric catalysis as well as biocatalysis in flow are discussed.

  4. Asymmetric catalysis with helical polymers

    NARCIS (Netherlands)

    Megens, Rik P.; Roelfes, Gerard


    Inspired by nature, the use of helical biopolymer catalysts has emerged over the last years as a new approach to asymmetric catalysis. In this Concept article the various approaches and designs and their application in asymmetric catalysis will be discussed.

  5. Orbital-optimized coupled-electron pair theory and its analytic gradients: accurate equilibrium geometries, harmonic vibrational frequencies, and hydrogen transfer reactions. (United States)

    Bozkaya, Uğur; Sherrill, C David


    Orbital-optimized coupled-electron pair theory [or simply "optimized CEPA(0)," OCEPA(0), for short] and its analytic energy gradients are presented. For variational optimization of the molecular orbitals for the OCEPA(0) method, a Lagrangian-based approach is used along with an orbital direct inversion of the iterative subspace algorithm. The cost of the method is comparable to that of CCSD [O(N(6)) scaling] for energy computations. However, for analytic gradient computations the OCEPA(0) method is only half as expensive as CCSD since there is no need to solve the λ2-amplitude equation for OCEPA(0). The performance of the OCEPA(0) method is compared with that of the canonical MP2, CEPA(0), CCSD, and CCSD(T) methods, for equilibrium geometries, harmonic vibrational frequencies, and hydrogen transfer reactions between radicals. For bond lengths of both closed and open-shell molecules, the OCEPA(0) method improves upon CEPA(0) and CCSD by 25%-43% and 38%-53%, respectively, with Dunning's cc-pCVQZ basis set. Especially for the open-shell test set, the performance of OCEPA(0) is comparable with that of CCSD(T) (ΔR is 0.0003 Å on average). For harmonic vibrational frequencies of closed-shell molecules, the OCEPA(0) method again outperforms CEPA(0) and CCSD by 33%-79% and 53%-79%, respectively. For harmonic vibrational frequencies of open-shell molecules, the mean absolute error (MAE) of the OCEPA(0) method (39 cm(-1)) is fortuitously even better than that of CCSD(T) (50 cm(-1)), while the MAEs of CEPA(0) (184 cm(-1)) and CCSD (84 cm(-1)) are considerably higher. For complete basis set estimates of hydrogen transfer reaction energies, the OCEPA(0) method again exhibits a substantially better performance than CEPA(0), providing a mean absolute error of 0.7 kcal mol(-1), which is more than 6 times lower than that of CEPA(0) (4.6 kcal mol(-1)), and comparing to MP2 (7.7 kcal mol(-1)) there is a more than 10-fold reduction in errors. Whereas the MAE for the CCSD method is

  6. Water-Soluble Iron(IV)-Oxo Complexes Supported by Pentapyridine Ligands: Axial Ligand Effects on Hydrogen Atom and Oxygen Atom Transfer Reactivity. (United States)

    Chantarojsiri, Teera; Sun, Yujie; Long, Jeffrey R; Chang, Christopher J


    We report the photochemical generation and study of a family of water-soluble iron(IV)-oxo complexes supported by pentapyridine PY5Me2-X ligands (PY5Me2 = 2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine; X = CF3, H, Me, or NMe2), in which the oxidative reactivity of these ferryl species correlates with the electronic properties of the axial pyridine ligand. Synthesis of a systematic series of [Fe(II)(L)(PY5Me2-X)](2+) complexes, where L = CH3CN or H2O, and characterizations by several methods, including X-ray crystallography, cyclic voltammetry, and Mössbauer spectroscopy, show that increasing the electron-donating ability of the axial pyridine ligand tracks with less positive Fe(III)/Fe(II) reduction potentials and quadrupole splitting parameters. The Fe(II) precursors are readily oxidized to their Fe(IV)-oxo counterparts using either chemical outer-sphere oxidants such as CAN (ceric ammonium nitrate) or flash-quench photochemical oxidation with [Ru(bpy)3](2+) as a photosensitizer and K2S2O8 as a quencher. The Fe(IV)-oxo complexes are capable of oxidizing the C-H bonds of alkane (4-ethylbenzenesulfonate) and alcohol (benzyl alcohol) substrates via hydrogen atom transfer (HAT) and an olefin (4-styrenesulfonate) substrate by oxygen atom transfer (OAT). The [Fe(IV)(O)(PY5Me2-X)](2+) derivatives with electron-poor axial ligands show faster rates of HAT and OAT compared to their counterparts supported by electron-rich axial donors, but the magnitudes of these differences are relatively modest.

  7. 苯乙胺衍生的手性膦-亚磷酰胺酯配体在Rh-催化α-烯醇酯膦酸酯的不对称氢化反应中的应用%Rh-Catalyzed Asymmetric Hydrogenation of α-Enol Ester Phosphonates with 1-Phenylethylamine-Derived Phosphine-Phosphoramidite Ligands

    Institute of Scientific and Technical Information of China (English)

    胡娟; 王道永; 郑卓; 胡向平


    A series of phosphine-phosphoramidite ligands derived from commercially available,inexpensive chiral 1-phenylethylamine were employed in the Rh-catalyzed asymmetric hydrogenation of various α-enol ester phosphonates.The results indicated that the ligand(Sc,Sa)-2b bearing a Me-group on amino moiety exhibited similar enantioselectivity but superior catalytic activity to(Rc,Ra)-THNAPhos.Excellent enantioselectivities(up to 99% ee) and high catalytic activity(S/C up to 5 000) have been achieved in the hydrogenation of various β-alkyl and β-aryl substituted substrates,demonstrating the high potential of this phosphine-phosphoramidite ligand in the preparation of optically active α-hydroxyphosphonates%将苯乙胺衍生的手性膦-亚磷酰胺酯配体应用在Rh-催化α-烯醇酯膦酸酯的不对称氢化反应中,考察了配体结构及反应条件对反应结果的影响,并在优化的条件下研究了各种底物的适用范围,产物的对映选择性最高〉99%ee.

  8. Enhanced Reactivity in Hydrogen Atom Transfer from Tertiary Sites of Cyclohexanes and Decalins via Strain Release: Equatorial C-H Activation vs Axial C-H Deactivation. (United States)

    Salamone, Michela; Ortega, Vanesa B; Bietti, Massimo


    Absolute rate constants for hydrogen atom transfer (HAT) from cycloalkanes and decalins to the cumyloxyl radical (CumO(•)) were measured by laser flash photolysis. Very similar reactivities were observed for the C-H bonds of cyclopentane and cyclohexane, while the tertiary C-H bond of methylcyclopentane was found to be 6 times more reactive than the tertiary axial C-H bond of methylcyclohexane, pointing toward a certain extent of tertiary axial C-H bond deactivation. Comparison between the cis and trans isomers of 1,2-dimethylcyclohexane, 1,4-dimethylcyclohexane and decalin provides a quantitative evaluation of the role played by strain release in these reactions. kH values for HAT from tertiary equatorial C-H bonds were found to be at least 1 order of magnitude higher than those for HAT from the corresponding tertiary axial C-H bonds (kH(eq)/kH(ax) = 10-14). The higher reactivity of tertiary equatorial C-H bonds was explained in terms of 1,3-diaxial strain release in the HAT transition state. Increase in torsional strain in the HAT transition state accounts instead for tertiary axial C-H bond deactivation. The results are compared with those obtained for the corresponding C-H functionalization reactions by dioxiranes and nonheme metal-oxo species indicating that CumO(•) can represent a convenient model for the reactivity patterns of these oxidants.

  9. Three-dimensional radiative transfer simulations of the scattering polarization of the hydrogen Ly$\\alpha$ line in a MHD model of the chromosphere-corona transition region

    CERN Document Server

    Stepan, Jiri; Leenaarts, Jorrit; Carlsson, Mats


    Probing the magnetism of the upper solar chromosphere requires measuring and modeling the scattering polarization produced by anisotropic radiation pumping in UV spectral lines. Here we apply PORTA (a novel radiative transfer code) to investigate the hydrogen Ly$\\alpha$ line in a 3D model of the solar atmosphere resulting from a state of the art MHD simulation. At full spatial resolution the linear polarization signals are very significant all over the solar disk, with a large fraction of the field of view showing line-center amplitudes well above the 1% level. Via the Hanle effect the line-center polarization signals are sensitive to the magnetic field of the model's transition region, even when its mean field strength is only 15 G. The breaking of the axial symmetry of the radiation field produces significant forward-scattering polarization in Ly$\\alpha$, without the need of an inclined magnetic field. Interestingly, the Hanle effect tends to decrease such forward-scattering polarization signals in most of ...

  10. Asymmetric information and economics (United States)

    Frieden, B. Roy; Hawkins, Raymond J.


    We present an expression of the economic concept of asymmetric information with which it is possible to derive the dynamical laws of an economy. To illustrate the utility of this approach we show how the assumption of optimal information flow leads to a general class of investment strategies including the well-known Q theory of Tobin. Novel consequences of this formalism include a natural definition of market efficiency and an uncertainty principle relating capital stock and investment flow.

  11. Asymmetric extractions in orthodontics


    Camilo Aquino Melgaço; Mônica Tirre de Souza Araújo


    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 Portugue...

  12. 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.

  13. 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.

  14. Asymmetric dark matter models in SO(10) (United States)

    Nagata, Natsumi; Olive, Keith A.; Zheng, Jiaming


    We systematically study the possibilities for asymmetric dark matter in the context of non-supersymmetric SO(10) models of grand unification. Dark matter stability in SO(10) is guaranteed by a remnant Z2 symmetry which is preserved when the intermediate scale gauge subgroup of SO(10) is broken by a {126} dimensional representation. The asymmetry in the dark matter states is directly generated through the out-of-equilibrium decay of particles around the intermediate scale, or transferred from the baryon/lepton asymmetry generated in the Standard Model sector by leptogenesis. We systematically classify possible asymmetric dark matter candidates in terms of their quantum numbers, and derive the conditions for each case that the observed dark matter density is (mostly) explained by the asymmetry of dark matter particles.

  15. Asymmetric Dark Matter Models in SO(10)

    CERN Document Server

    Nagata, Natsumi; Zheng, Jiaming


    We systematically study the possibilities for asymmetric dark matter in the context of non-supersymmetric SO(10) models of grand unification. Dark matter stability in SO(10) is guaranteed by a remnant $\\mathbb{Z}_2$ symmetry which is preserved when the intermediate scale gauge subgroup of SO(10) is broken by a ${\\bf 126}$ dimensional representation. The asymmetry in the dark matter states is directly generated through the out-of-equilibrium decay of particles around the intermediate scale, or transferred from the baryon/lepton asymmetry generated in the Standard Model sector by leptogenesis. We systematically classify possible asymmetric dark matter candidates in terms of their quantum numbers, and derive the conditions for each case that the observed dark matter density is (mostly) explained by the asymmetry of dark matter particles.

  16. Axially chiral imidodiphosphoric Acid catalyst for asymmetric sulfoxidation reaction: insights on asymmetric induction. (United States)

    Jindal, Garima; Sunoj, Raghavan B


    Insights into chiral induction for an asymmetric sulfoxidation reaction involving a single oxygen atom transfer are gained through analyzing the stereocontrolling transition states. The fitting of the substrate into the chiral cavity of a new class of imidodiphosphoric Brønsted acids, as well as weak CH⋅⋅⋅π and CH⋅⋅⋅O noncovalent interactions, are identified as responsible for the observed chiral induction.

  17. Asymmetric Hydrogenation of Aromatic Ketones Catalyzed by Cinchona-Modified Ir/SiO2%金鸡纳碱衍生物修饰的负载铱催化剂催化芳香酮不对称加氢

    Institute of Scientific and Technical Information of China (English)

    蒋和雁; 吴志峰; 陈华


    The asymmetric hydrogenation of aromatic ketones catalyzed by cinchona-and triphenylphosphine (tpp)-modified Ir/SiO2 was studied.The heterogeneous enantioselective hydrogenation of heterocyclic ketones using a supported iridium catalyst was also investigated.Different analytical techniques,including inductively coupled plasma-atomic emission spectroscopy (ICP-AES),high resolution transmission electron microscopy (HRTEM),X-ray photoelectron spectroscopy (XPS),the Brunauer-Emmett-Teller (BET) method,infrared (IR) spectroscopy,31p solid state nuclear magnetic resonance (NMR)spectroscopy,homogeneous-heterogeneous comparison experiment,conventional filtering test,and mercury poisoning experiment,were used to characterize the catalytic system.HRTEM,XPS,and the BET method clearly characterized the catalytic system.IR and 31p solid state NMR spectra provided useful information about the interactions between modifier,metal,and stabilizer.The homogeneous-heterogeneous comparison experiment,conventional filtering test,and mercury poisoning experiment clearly showed the differences between supported,and homogeneous catalysts.In addition,the effects of different stabilizers,modifiers,iridium content,solvents,and base additives on the asymmetric hydrogenation of aromatic ketones were investigated in detail.The results showed that cinchona alkaloids positively modified the Ir/SiO2 catalyst.Under the optimum conditions,the hydrogenation enantioselectivities of acetophenone and its derivatives were 52%-96%.The enantioselectivities of the hydrogenation products of 4-acetopyridine,2-acetothiophene,and 2-acetofuran reached 74%,75%,and 63%,respectively.%以金鸡纳碱衍生物作为手性修饰剂,研究了三苯基膦稳定的Ir/SiO2催化剂催化芳香酮多相不对称加氢.通过电感耦合等离子体原子发射发谱(ICP-AES)、高分辨透射电镜(HRTEM)、X射线光电子能谱(XPS)、Brunauer-Emmett-Teller (BET)比表面积测试等固体表面分析手段对

  18. 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 [Co-III{CH-(OAc)CH

  19. Acid/base and hydrogen bonding effects on the proton-coupled electron transfer of quinones and hydroquinones in acetonitrile: Mechanistic investigation by voltammetry, {sup 1}H NMR and computation

    Energy Technology Data Exchange (ETDEWEB)

    Alligrant, Timothy M. [Department of Chemistry, Virginia Commonwealth University, 1001 West Main St., P.O. Box 842006, Richmond, VA 23284 (United States); Hackett, John C. [Institute for Structural Biology and Drug Discovery, Virginia Commonwealth University, P.O. Box 980133, Richmond, VA 23219 (United States); Alvarez, Julio C., E-mail: jcalvarez2@vcu.ed [Department of Chemistry, Virginia Commonwealth University, 1001 West Main St., P.O. Box 842006, Richmond, VA 23284 (United States)


    This report seeks to address the role of hydrogen bonding with Bronsted acids and bases in proton-coupled electron transfer (PCET) as it pertains to concerted or stepwise pathways of quinone (Q) and hydroquinone (QH{sub 2}) electrochemistry. This study was performed using a series of techniques that included cyclic voltammetry (CV), digital simulations, computational chemistry and {sup 1}H NMR. Hydrogen bonding was inferred by a decrease in diffusion coefficient (D) values measured using a pulsed gradient echo- (PGE-) {sup 1}H NMR technique. Changes of 40.8% and 37.9% in D values were only noted after the addition of two equivalents of acetate to 1,4-hydroquinone (1,4-QH{sub 2}) and catechol (1,2-QH{sub 2}), respectively. In contrast, the D values for the addition of selected amines (pyridine, N,N-diisopropylethylamine and triethylamine) changed only 3.2% on average. Quantum mechanical calculations were conducted to determine the pK{sub a} of all quinoid species to serve as a starting point for the determination of equilibrium constants in voltammetric simulations. Simulations indicate that 1,4-benzoquinone undergoes stepwise electron-proton transfer upon addition of acetic acid, N-ethyldiisopropylammonium perchlorate and pyridinium nitrate and were simulated without the presence of hydrogen bonds. The QH{sub 2} compounds show stepwise proton-electron transfers after addition of the both the conjugate amines and acetate.

  20. Tuning reactivity and selectivity in hydrogen atom transfer from aliphatic C-H bonds to alkoxyl radicals: role of structural and medium effects. (United States)

    Salamone, Michela; Bietti, Massimo


    Hydrogen atom transfer (HAT) is a fundamental reaction that takes part in a wide variety of chemical and biological processes, with relevant examples that include the action of antioxidants, damage to biomolecules and polymers, and enzymatic and biomimetic reactions. Moreover, great attention is currently devoted to the selective functionalization of unactivated aliphatic C-H bonds, where HAT based procedures have been shown to play an important role. In this Account, we describe the results of our recent studies on the role of structural and medium effects on HAT from aliphatic C-H bonds to the cumyloxyl radical (CumO(•)). Quantitative information on the reactivity and selectivity patterns observed in these reactions has been obtained by time-resolved kinetic studies, providing a deeper understanding of the factors that govern HAT from carbon and leading to the definition of useful guidelines for the activation or deactivation of aliphatic C-H bonds toward HAT. In keeping with the electrophilic character of alkoxyl radicals, polar effects can play an important role in the reactions of CumO(•). Electron-rich C-H bonds are activated whereas those that are α to electron withdrawing groups are deactivated toward HAT, with these effects being able to override the thermodynamic preference for HAT from the weakest C-H bond. Stereoelectronic effects can also influence the reactivity of the C-H bonds of ethers, amines, and amides. HAT is most rapid when these bonds can be eclipsed with a lone pair on an adjacent heteroatom or with the π-system of an amide functionality, thus allowing for optimal orbital overlap. In HAT from cyclohexane derivatives, tertiary axial C-H bond deactivation and tertiary equatorial C-H bond activation have been observed. These effects have been explained on the basis of an increase in torsional strain or a release in 1,3-diaxial strain in the HAT transition states, with kH(eq)/kH(ax) ratios that have been shown to exceed one order of

  1. Interplay of Charge Transfer, Dimensionality, and Amide Hydrogen Bond Network Adaptability in TCNQF 4 Complexes of EDO-TTF-CONH 2 and EDT-TTF-CONH 2 (United States)

    Baudron, Stéphane A.; Mézière, Cécile; Heuzé, Karine; Fourmigué, Marc; Batail, Patrick; Molinié, Philippe; Auban-Senzier, Pascale


    [EDO-TTF-CONH 2][TCNQF 4], triclinic system, space group P-1, a=8.2479(12) Å, b=12.282(2) Å, c=12.6842(18) Å, α=113.850(17)°, β=106.420(17)°, γ=90.284(19)°, V=1116.8(4) Å 3; and [EDT-TTF-CONH 2] 2[TCNQF 4], triclinic system, space group P-1, a=6.5858(9) Å, b=11.699(2) Å, c=12.2281(18) Å, α=104.000(19)°, β=93.611(17)°, γ=98.279(19)°, V=899.9(3) Å 3, whose π-donor molecules, (ethylenedioxo)-carbamoyltetrathiafulvalene and (ethylenedithio)-carbamoyltetrathiafulvalene, respectively, differ solely by the nature of the chalcogen atoms in their outer ethylene dichalcogeno bridge, yet form very different charge-transfer complexes with the same π-acceptor. [EDO-TTF-CONH 2•+] 2 [TCNQF 4•-] 2 is a diamagnetic insulating ionic salt with a three-dimensional rock-salt-type structure based on discrete dimers while in the semi-conducting mixed-valence complex, [EDT-TTF-CONH 2] 2•+[TCNQF 4•-], the mixed-valence dimers aggregate into infinite chains interspersed within parallel rows of non-interacting radical anions. It is shown how the robust and adaptable supramolecular amide hydrogen bond tweezers-like motifs common to the two solids simply comply to the 3-to-1 dimensionality reduction upon substitution of O for S.

  2. 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

  3. Asymmetric flow networks


    Olaizola Ortega, María Norma; Valenciano Llovera, Federico


    This paper provides a new model of network formation that bridges the gap between the two benchmark models by Bala and Goyal, the one-way flow model, and the two-way flow model, and includes both as particular extreme cases. As in both benchmark models, in what we call an "asymmetric flow" network a link can be initiated unilaterally by any player with any other, and the flow through a link towards the player who supports it is perfect. Unlike those models, in the opposite direction there is ...

  4. Comments on liquid hydrogen absorbers for MICE

    Energy Technology Data Exchange (ETDEWEB)

    Green, Michael A.


    This report describes the heat transfer problems associatedwith a liquid hydrogen absorber for the MICE experiment. This reportdescribes a technique for modeling heat transfer from the outside world,to the abosrber case and in its vacuum vessel, to the hydrogen and theninto helium gas at 14 K. Also presented are the equation for freeconvection cooling of the liquid hydrogen in the absorber.


    NARCIS (Netherlands)



    A density matrix evolution (DME) method (Berendsen, H. J. C.; Mavri, J. J. Phys. Chem. the preceding paper in this issue) in combination with classical molecular dynamics simulation was applied to calculate the rate of proton tunneling in the intramolecular double-well hydrogen bond of hydrogen malo

  6. Recent advances in cooperative bimetallic asymmetric catalysis: dinuclear Schiff base complexes. (United States)

    Matsunaga, Shigeki; Shibasaki, Masakatsu


    Cooperative catalysis has proven to be a powerful strategy for realizing high reactivity and selectivity in asymmetric transformations. A variety of cooperative asymmetric catalysts have been developed over the last two decades. In this feature article, recent advances from our research on cooperative asymmetric catalysis, focusing on dinuclear Schiff base catalysis, are described. Design of dinuclear Schiff base catalysts and their applications in several asymmetric C-C and C-N bond-forming reactions under simple proton transfer conditions with perfect atom-economy are discussed in detail.

  7. Diastereoselective Hydrogenation and Kinetic Resolution of Imines Using Rhodium/Diphosphine Catalyzed Hydrogenation.

    NARCIS (Netherlands)

    Lensink, Cornelis; Vries, Johannes G. de


    Kinetic resolution of racemic α-methylbenzyl amine can be achieved with 98% ee. of the remaining amine at 70% conversion using the Rhodium/2S,4S-BDPP catalyzed asymmetric hydrogenation of imines. The same catalyst will hydrogenate optically pure α-methylbenzyl amines with a diastereoselectivity of u

  8. 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.

  9. Additive Effects on Asymmetric Catalysis. (United States)

    Hong, Liang; Sun, Wangsheng; Yang, Dongxu; Li, Guofeng; Wang, Rui


    This review highlights a number of additives that can be used to make asymmetric reactions perfect. Without changing other reaction conditions, simply adding additives can lead to improved asymmetric catalysis, such as reduced reaction time, improved yield, or/and increased selectivity.

  10. The asymmetric sandwich theorem

    CERN Document Server

    Simons, Stephen


    We discuss the asymmetric sandwich theorem, a generalization of the Hahn-Banach theorem. As applications, we derive various results on the existence of linear functionals that include bivariate, trivariate and quadrivariate generalizations of the Fenchel duality theorem. Most of the results are about affine functions defined on convex subsets of vector spaces, rather than linear functions defined on vector spaces. We consider both results that use a simple boundedness hypothesis (as in Rockafellar's version of the Fenchel duality theorem) and also results that use Baire's theorem (as in the Robinson-Attouch-Brezis version of the Fenchel duality theorem). This paper also contains some new results about metrizable topological vector spaces that are not necessarily locally convex.

  11. 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.

  12. Effect of Hydrogen Peroxide in Combination with Minimal Thermal Treatment for Reducing Bacterial Populations on Cantaloupe Rind Surfaces and Transfer to Fresh-Cut Pieces. (United States)

    Ukuku, Dike O; Mukhopadhyay, Sudarsan; Geveke, David; Olanya, Modesto; Niemira, Brendan


    Surface structure and biochemical characteristics of bacteria and produce play a major role in how and where bacteria attach, complicating decontamination treatments. Whole cantaloupe rind surfaces were inoculated with Salmonella, Escherichia coli O157:H7, and Listeria monocytogenes at 10(7) CFU/ml. Average population size of Salmonella, Escherichia coli O157:H7, and L. monocytogenes recovered after surface inoculation was 4.8 ± 0.12, 5.1 ± 0.14, and 3.6 ± 0.13 log CFU/cm(2), respectively. Inoculated melons were stored at 5 and 22°C for 7 days before washing treatment interventions. Intervention treatments used were (i) water (H2O) at 22°C, (ii) H2O at 80°C, (iii) 3% hydrogen peroxide (H2O2) at 22°C, and (iv) a combination of 3% H2O2 and H2O at 80°C for 300 s. The strength of pathogen attachment (SR value) at days 0, 3, and 7 of storage was determined, and then the efficacy of the intervention treatments to detach, kill, and reduce transfer of bacteria to fresh-cut pieces during fresh-cut preparation was investigated. Populations of E. coli O157:H7 attached to the rind surface at significantly higher levels (P < 0.05) than Salmonella and L. monocytogenes, but Salmonella exhibited the strongest attachment (SR value) at all days tested. Washing with 3% H2O2 alone led to significant reduction (P < 0.05) of bacteria and caused some changes in bacterial cell morphology. A combination treatment with H2O and 3% H2O2 at 8°C led to an average 4-log reduction of bacterial pathogens, and no bacterial pathogens were detected in fresh-cut pieces prepared from this combination treatment, including enriched fresh-cut samples. The results of this study indicate that the microbial safety of fresh-cut pieces from treated cantaloupes was improved at day 6 of storage at 5°C and day 3 of storage at 10°C.

  13. 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

  14. Photoinduced hydrogen-bonding dynamics. (United States)

    Chu, Tian-Shu; Xu, Jinmei


    Hydrogen bonding dynamics has received extensive research attention in recent years due to the significant advances in femtolaser spectroscopy experiments and quantum chemistry calculations. Usually, photoexcitation would cause changes in the hydrogen bonding formed through the interaction between hydrogen donor and acceptor molecules on their ground electronic states, and such transient strengthening or weakening of hydrogen bonding could be crucial for the photophysical transformations and the subsequent photochemical reactions that occurred on a time scale from tens of femtosecond to a few nanoseconds. In this article, we review the combined experimental and theoretical studies focusing on the ultrafast electronic and vibrational hydrogen bonding dynamics. Through these studies, new mechanisms and proposals and common rules have been put forward to advance our understanding of the hydrogen bondings dynamics in a variety of important photoinduced phenomena like photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer processes, chemosensor fluorescence sensing, rearrangements of the hydrogen-bond network including forming and breaking hydrogen bond in water. Graphical Abstract We review the recent advances on exploring the photoinduced hydrogen bonding dynamics in solutions through a joint approach of laser spectroscopy and theoretical calculation. The reviewed studies have put forward a new mechanism, new proposal, and new rule for a variety of photoinduced phenomena such as photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer, chemosensor fluorescence sensing, and rearrangements of the hydrogen-bond network in water.

  15. Application of Schrödinger equation to study the tunnelling dynamics of proton transfer in the hydrogen bond of 2,5-dinitrobenzoic acid: proton T1 T1rho, and deuteron T1 relaxation methods. (United States)

    Latanowicz, L; Medycki, W


    Temperature measurements of proton T1 (24.7 MHz), deuteron (deuterated hydroxyl group) T1 (55.2 MHz), and proton T1(rho) (B1 = 9 G) spin-lattice relaxation times of 2,5-dinitrobenzoic acid have been performed. An analysis of present experimental data together with previously published proton T1 (55.2 MHz) data has revealed the following molecular motions: proton/deuteron transfer in the hydrogen bond and two-site hopping of the whole dimer. It is shown that the proton-transfer dynamics are characterized by two correlation times tau(ov) and tau(tu), describing two fundamentally different motional processes, namely, thermally activated jumps over the barrier and tunneling through the barrier. The temperature dependence of 1/tau(tu) is the solution of Schrödinger's equation, which also yields the temperature T(tun), where begins the tunnel pathway for proton transfer. A new equation for the spectral density function of complex motion consisting of the three motions is derived. The third motion (two-site hopping of the whole dimer characterized by tau(lib) correlation time) is responsible for a proton T1(rho) minimum in high temperatures, just below the melting point. Such a minimum is not reached by T1 temperature dependencies. The minimum of T1(rho) assigned to the classical hopping of a hydrogen-bonded proton occurs in the same low-temperature regime in which the flattening of the temperature dependencies of T1 points to the dominance of incoherent tunneling. This experimental fact denies the known theories predicting the intermediate temperature regime where a smooth transition between classical and quantum tunneling dynamics is expected. The fit of the derived theoretical equations to the experimental data T1(rho) and T1 is satisfactory. The correlation times obtained for deuterons indicate deuteron-transfer dynamics much slower than proton-transfer dynamics. It is concluded that the classical proton transfer takes place over the whole temperature regime, while

  16. Asymmetric Gepner Models (Revisited)

    CERN Document Server

    Gato-Rivera, B


    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 th...

  17. Heats of transfer in the diffusion layer before the surface and the surface temperature for a catalytic hydrogen oxidation (H2 + (1/2)O2 --> H2O) reaction. (United States)

    Zhu, Lianjie; Koper, Ger J M; Bedeaux, Dick


    The surface temperature and surface mole fractions are calculated for a catalytic hydrogen oxidation reaction over a Pt/Al2O3 catalyst pellet. The thermodynamics of irreversible processes was used in order to ensure the correct introduction of coupled heat and mass transfer. Two pathways, one using the 4 x 4 resistivity matrix and the other using a simplified effective conductivity matrix, were proven to yield equivalent results. By using expressions for the thermal diffusion coefficients, heats of transfer, and the Maxwell-Stefan diffusion coefficients given in the literature, available experimental data could be reproduced. The Dufour effect was found to be negligible for the prediction of the surface temperature. Neglecting the Soret effect would increase the predicted value of the surface temperature significantly-more than 30 K out of an average of about 400 K. It is found that the reaction rate can be used to predict the surface temperature.

  18. 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....

  19. 非对称风险态度下的企业间知识转移效果研究%The Effect of Knowledge Transfer Between Enterprises under Asymmetric Risk Attitude

    Institute of Scientific and Technical Information of China (English)

    陈果; 齐二石


    In order to optimize the effect of knowledge transfer between enterprises with risks of knowledge loss, the influences of both the information disclosure strategy of the knowledge sender and the information processing strategy of the knowledge accepter on knowledge transfer when the degrees of trust between both sides are different are analyzed, and the way of the government to optimize the effect of knowledge transfer between enterprises is found.The conclusions are illustrated by numerical simulations.The results show that the risk aversion party and the knowledge accepter will positively optimize the effect of knowledge transfer;that the higher the expected revenue of the risk aversion party than that of the risk preference par-ty , the more easily the effect of knowledge transfer can be optimized;and that the government can improve the probability of optimizing the effect of knowledge transfer by formulating appropriate policies to adjust the compensation demanded by the knowledge sender and its monitoring cost.%为了最优化存在知识流失风险的企业间知识转移效果,分析了受双方信任程度影响的知识发送方风险态度披露决策和知识接收方信息处理决策,及其对知识转移的影响,探讨了政府应如何促进知识转移效果最优,并用算例验证了结论.研究表明风险厌恶方和知识接收方会积极最优化知识转移效果;风险厌恶方期望收益比风险偏好方高时,知识转移效果较易最优化;政府应制定政策调整知识发送方索要的赔偿金及监督成本,促进知识转移效果最优.

  20. Theoretical studies on concerted versus two steps hydrogen atom transfer reaction by non-heme Mn(IV/III)=O complexes: how important is the oxo ligand basicity in the C-H activation step? (United States)

    Jaccob, Madhavan; Ansari, Azaj; Pandey, Bhawana; Rajaraman, Gopalan


    High-valent metal-oxo complexes have been extensively studied over the years due to their intriguing properties and their abundant catalytic potential. The majority of the catalytic reactions performed by these metal-oxo complexes involves a C-H activation step and extensive efforts over the years have been undertaken to understand the mechanistic aspects of this step. The C-H activation by metal-oxo complexes proceeds via a hydrogen atom transfer reaction and this could happen by multiple pathways, (i) via a proton-transfer followed by an electron transfer (PT-ET), (ii) via an electron-transfer followed by a proton transfer (ET-PT), (iii) via a concerted proton-coupled electron transfer (PCET) mechanism. Identifying the right mechanism is a surging topic in this area and here using [Mn(III)H3buea(O)](2-) (1) and [Mn(IV)H3buea(O)](-) (2) species (where H3buea = tris[(N'-tert-butylureaylato)-N-ethylene]aminato) and its C-H activation reaction with dihydroanthracene (DHA), we have explored the mechanism of hydrogen atom transfer reactions. The experimental kinetic data reported earlier (T. H. Parsell, M.-Y. Yang and A. S. Borovik, J. Am. Chem. Soc., 2009, 131, 2762) suggests that the mechanism between 1 and 2 is drastically different. By computing the transition states, reaction energies and by analyzing the wavefunction of the reactant and transitions states, we authenticate the proposal that the Mn(III)=O undergoes a step wise PT-ET mechanism where as the Mn(IV)=O species undergo a concerted PCET mechanism. Both the species pass through a [Mn(III)-OH] intermediate and the stability of this species hold the key to the difference in the reactivity. The electronic origin for the difference in reactivity is routed back to the strength and basicity of the Mn-oxo bond and the computed results are in excellent agreement with the experimental results.

  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. On Asymmetric Quantum MDS Codes

    CERN Document Server

    Ezerman, Martianus Frederic; Ling, San


    Assuming the validity of the MDS Conjecture, the weight distribution of all MDS codes is known. Using a recently-established characterization of asymmetric quantum error-correcting codes, linear MDS codes can be used to construct asymmetric quantum MDS codes with $d_{z} \\geq d_{x}\\geq 2$ for all possible values of length $n$ for which linear MDS codes over $\\F_{q}$ are known to exist.

  3. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong


    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...... 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...

  4. 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.

  5. Asymmetric photoredox transition-metal catalysis activated by visible light (United States)

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


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

  6. 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 spectrom...

  7. 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.

  8. 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.

  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. 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.

  11. Probing chiral solute-water hydrogen bonding networks by chirality transfer effects: A vibrational circular dichroism study of glycidol in water (United States)

    Yang, Guochun; Xu, Yunjie


    Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra of (S)-(-)-glycidol were measured in water with a concentration of 6.0M in the 1000-1750 cm-1 region. Prominent and complex VCD spectral features were detected at the water bending vibrational region. Our experimental results show that water molecules can become optically active through hydrogen bonding interactions with glycidol molecules. To model the glycidol-water hydrogen bonding network in the solution, molecular dynamics simulations using the AMBER9 suite of programs were carried out. Altogether, 34 conformers of the small glycidol-(water)N clusters with N =1, 2, 3, and 4 were considered. Geometry optimizations, harmonic frequency calculations, and the VA and VCD intensity predictions of these small glycidol-water clusters were performed at the B3LYP/6-311++G(d,p) level of theory using the GAUSSIAN 03 program package. Strong cooperative hydrogen bonding effects were detected in the larger glycidol-(water)N clusters. The population weighted VA and VCD spectra of each N group of glycidol (water)N=1,2,3,4 were used to produce the simulated VA and VCD spectra, which are in good agreement with the experimental VA and VCD spectra. The study shows that all these clusters make important contributions to the observed spectra and are the most important species in the aqueous solution with complicated equilibriums among them.

  12. Nonlinear effects in asymmetric catalysis. (United States)

    Satyanarayana, Tummanapalli; Abraham, Susan; Kagan, Henri B


    There is a need for the preparation of enantiomerically pure compounds for various applications. An efficient approach to achieve this goal is asymmetric catalysis. The chiral catalyst is usually prepared from a chiral auxiliary, which itself is derived from a natural product or by resolution of a racemic precursor. The use of non-enantiopure chiral auxiliaries in asymmetric catalysis seems unattractive to preparative chemists, since the anticipated enantiomeric excess (ee) of the reaction product should be proportional to the ee value of the chiral auxiliary (linearity). In fact, some deviation from linearity may arise. Such nonlinear effects can be rich in mechanistic information and can be synthetically useful (asymmetric amplification). This Review documents the advances made during the last decade in the use of nonlinear effects in the area of organometallic and organic catalysis.

  13. 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.

  14. Fiber optic hydrogen sensor

    Energy Technology Data Exchange (ETDEWEB)

    Butler, M.A.; Sanchez, R.; Dulleck, G.R.


    This report covers the development of fiber optic hydrogen and temperature sensors for monitoring dissolved hydrogen gas in transformer oil. The concentration of hydrogen gas is a measure of the corona and spark discharge within the transformer and reflects the state of health of the transformer. Key features of the instrument include use of palladium alloys to enhance hydrogen sensitivity, a microprocessor controlled instrument with RS-232, liquid crystal readout, and 4-20 ma. current loop interfaces. Calibration data for both sensors can be down loaded to the instrument through the RS-232 interface. This project was supported by the Technology Transfer Initiative in collaboration with J. W. Harley, Inc. through the mechanism of a cooperative research and development agreement (CRADA).

  15. 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). (United States)

    Goswami, Monalisa; Rebreyend, Christophe; de Bruin, Bas


    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.

  16. 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......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...

  17. 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...

  18. Development of Asymmetric Hydrogenation Catalysts via High Throughput Experimentation

    NARCIS (Netherlands)

    Vries, J.G. de; Lefort, L.


    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-efficienc

  19. A nordehydroabietyl amide-containing chiral diene for rhodium-catalysed asymmetric arylation to nitroolefins. (United States)

    Li, Ruikun; Wen, Zhongqing; Wu, Na


    A highly enantioselective rhodium catalysed asymmetric arylation (RCAA) of nitroolefins with arylboronic acids is presented using a newly developed, C1-symmetric, non-covalent interacted, phellandrene derived, nordehydroabietyl amide-containing chiral diene under mild conditions. Stereoelectronic effects were studied, suggesting an activation of the bound substrate through the secondary amide as a hydrogen-bond donor.

  20. Asymmetric Synthesis of Mixed Metal Clusters Induced by Phase-transfer Catalysts%光学活性四面体过渡金属簇合物的诱导合成

    Institute of Scientific and Technical Information of China (English)

    张玉华; 吴树林; 李庆山; 殷元骐


    报导了用手性季铵盐诱导合成SFeCoMo等手性四面体过渡金属簇合物的新方法. 发现, 苄基辛可宁对四面体簇的合成有手性诱导作用; 在不同溶剂中, 手性簇产物的绝对构型不同, 而且含钌簇的旋光度比含铁簇的旋光度小.%Three series of chiral metal clusters induced by two kinds of phase-transfer catalysts have been synthesized. Benzyl cinchonium chloride is active to all kinds of metal clusters under all sorts of conditions. Ether is found to be the most suitable solvent, and the enantiomer obtained is different if the synthesis was proceeded in different solvents. Unfortunately, the e.e. value was not obtained, so only some tentative conclusions were postulated.

  1. 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.

  2. Synthesis of Asymmetric Propanetriol Analogues

    Institute of Scientific and Technical Information of China (English)


    From natural tartaric acid, (R)-2-benzyloxy-3-(2-tetrahydropyranyloxy) propanol 3 was designed and synthesized, and (R)-2-benzyloxy-3-(4-methoxybenzyloxy) propanol 7 was prepared in a new method. They can be used as chiral synthons of lysophosphatidic acid and other compounds with asymmetric propanetriol backbone.

  3. Catalytic Asymmetric Bromocyclization of Polyenes. (United States)

    Samanta, Ramesh C; Yamamoto, Hisashi


    The first catalytic asymmetric bromonium ion-induced polyene cyclization has been achieved by using a chiral BINOL-derived thiophosphoramide catalyst and 1,3-dibromo-5,5-dimethylhydantoin as an electrophilic bromine source. Bromocyclization products are obtained in high yields, with good enantiomeric ratios and high diastereoselectivity, and are abundantly found as scaffolds in natural products.

  4. Water-soluble IrIII N-heterocyclic carbene based catalysts for the reduction of CO2 to formate by transfer hydrogenation and the deuteration of aryl amines in water. (United States)

    Azua, Arturo; Sanz, Sergio; Peris, Eduardo


    Two new water-soluble [IrI(2)(AcO)(bis-NHC)] complexes (NHC=N-heterocyclic carbene) incorporating a sulfonate functionality have been synthesized. The two complexes have been tested in the reduction of CO(2) with H(2) and iPrOH, and their activity has been compared with similar species without the sulfonate moiety. In both reactions, the complex with the two abnormally bound NHCs shows the best catalytic efficiencies, due to the higher σ-electron-donor character of the ligand. Remarkably, the activities obtained for the reduction of CO(2) under the transfer hydrogenation conditions are the best reported to date in terms of TON value (max. TON=2700). The two new complexes have also shown very good activity in the selective deuteration of arylamines, a process that is known to proceed through a chelate assisted N-directed process.

  5. Asymmetric Hydrogenation of Ethyl 2-Oxo-4-Phenylbutyrate on Pt-Ir/Al2O3 Catalysts%Pt-Ir/Al2O3催化剂催化2-氧-4-苯基丁酸乙酯不对称加氢

    Institute of Scientific and Technical Information of China (English)

    张学勤; 何年志; 肖美添; 刘勇军; 叶静


    A series of Pt/γ-Al2O3 、Ir/γ-Al2O3 and Pt-Ir/γ-Al2O3 catalysts with different ratios of Pt and Ir were prepared by impregnation methods.The catalytic performance for asymmetric hydrogenation of ethyl 2-oxo-4-phenylbutyrate to ethyl (R)-2-hydroxy-4-phenylbutyrate was tested.The mechanism of chiral induction on cinchona-modified platinum and iridium catalysts and their physical and chemical properties were investigated by X-ray diffraction (XRD),transmission electron microscopy(TEM),H2-temperature programmed reduction (H2-TPR),X-ray photoelectron spectroscopy(XPS) and ultraviolet-visible spectroscopy(UV-Vis).The average metal particles size for Pt/γ-Al2O3 and Pt-Ir/γ-Al2O3 catalγsts were 3-4 nm; Pt and Ir existed as Pt(0) and Ir(0) for Pt-Ir/γ-Al2O3 ; Ir acted as an inactive species,covering and diluting the Pt active site in the surface.The results showed that a small amount of Ir obviously suppressed the hydrogenation activity and selectivity of Pt/γ-Al2O3.The notable differences in reaction rate and enantioselectivity of platinum and iridium attributed to different behaviour adsorption (adsorption strength,mode and conformation) of chiral modifier on the metal surface.%用浸渍法制备了一系列γ-Al2O3负载的Pt、Ir单金属及不同Pt/Ir比例的双金属催化剂,在辛可尼定修饰下用于对2-氧-4-苯基丁酸乙酯不对称加氢合成(R)-2-羟基-4-苯基丁酸乙酯反应.运用XRD、TEM、TPR、XPS、UV-Vis等表征手段,对催化剂的物化性质进行了研究,并对Pt、Ir金属表面辛可尼定手性诱导机理进行了初步探讨.结果表明,金属组分在催化剂上分散均匀,无团聚现象,平均粒径为3 ~4 nm; Pt-Ir/γ-Al2O3上Pt、Ir组分以单质形式存在;Ir作为低活性物种,在Pt/γ-Al2O3催化剂掺杂Ir组分遮盖和稀释了催化剂表面总体Pt活性位点数目,降低了Pt-Ir/γ-Al2O3催化剂加氢性能.辛可尼定在Pt、Ir表面的不同吸附行为(吸附方式、吸附强度、吸附

  6. Reactivity and selectivity patterns in hydrogen atom transfer from amino acid C-H bonds to the cumyloxyl radical: polar effects as a rationale for the preferential reaction at proline residues. (United States)

    Salamone, Michela; Basili, Federica; Bietti, Massimo


    Absolute rate constants for hydrogen atom transfer (HAT) from the C-H bonds of N-Boc-protected amino acids to the cumyloxyl radical (CumO(•)) were measured by laser flash photolysis. With glycine, alanine, valine, norvaline, and tert-leucine, HAT occurs from the α-C-H bonds, and the stability of the α-carbon radical product plays a negligible role. With leucine, HAT from the α- and γ-C-H bonds was observed. The higher kH value measured for proline was explained in terms of polar effects, with HAT that predominantly occurs from the δ-C-H bonds, providing a rationale for the previous observation that proline residues represent favored HAT sites in the reactions of peptides and proteins with (•)OH. Preferential HAT from proline was also observed in the reactions of CumO(•) with the dipeptides N-BocProGlyOH and N-BocGlyGlyOH. The rate constants measured for CumO(•) were compared with the relative rates obtained previously for the corresponding reactions of different hydrogen-abstracting species. The behavior of CumO(•) falls between those observed for the highly reactive radicals Cl(•) and (•)OH and the significantly more stable Br(•). Taken together, these results provide a general framework for the description of the factors that govern reactivity and selectivity patterns in HAT reactions from amino acid C-H bonds.

  7. 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.

  8. Hydrogen Production

    Energy Technology Data Exchange (ETDEWEB)



    This 2-page fact sheet provides a brief introduction to hydrogen production technologies. Intended for a non-technical audience, it explains how different resources and processes can be used to produce hydrogen. It includes an overview of research goals as well as “quick facts” about hydrogen energy resources and production technologies.

  9. Hydrogen storage

    NARCIS (Netherlands)

    Peters, C.J.; Sloan, E.D.


    The invention relates to the storage of hydrogen. The invention relates especially to storing hydrogen in a clathrate hydrate. The clathrate hydrate according to the present invention originates from a composition, which comprises water and hydrogen, as well as a promotor compound. The promotor comp

  10. Electron transfer and hydrogen generation from a molecular dyad: platinum(II) alkynyl complex anchored to [FeFe] hydrogenase subsite mimic. (United States)

    Wang, Wen-Guang; Wang, Feng; Wang, Hong-Yan; Tung, Chen-Ho; Wu, Li-Zhu


    A PS-Fe(2)S(2) molecular dyad 1a directly anchoring a platinum(II) alkynyl complex to a Fe(2)S(2) active site of a [FeFe] H(2)ase mimic, and an intermolecular system of its reference complexes 1b and 2, have been successfully constructed. Time-dependence of H(2) evolution shows that PS-Fe(2)S(2)1a as well as complex 2 with 1b can produce H(2) in the presence of a proton source and sacrificial donor under visible light irradiation. Spectroscopic and electrochemical studies on the electron transfer event reveal that the reduced Fe(I)Fe(0) species generated by the first electron transfer from the excited platinum(II) complex to the Fe(2)S(2) active site in PS-Fe(2)S(2)1a and complex 2 with 1b is essential for photochemical H(2) evolution, while the second electron transfer from the excited platinum(II) complex to the protonated Fe(I)Fe(0) species is thermodynamically unfeasible, which might be an obstacle for the relatively small amount of H(2) obtained by PS-Fe(2)S(2) molecular dyads reported so far.

  11. 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

  12. 单取代氧/硫杂紫菜嗪内氢迁移反应的理论研究%Theoretical study on transfer reaction of inner hydrogen atoms in oxa-and thiaporphyrazine

    Institute of Scientific and Technical Information of China (English)

    廖玉婷; 饶火瑜; 王海江; 邹丽霞; 胡宝群


    采用B3LYP/6-31G**方法在Gaussian 03程序下,对氧杂紫菜嗪,硫杂紫菜嗪的稳定结构和能量进行优化,并寻找与内氢迁移反应相关的过渡态构型.计算结果表明,芳香性与各体系构象稳定性密切相关,但并不是决定构象稳定性的唯一因素;在中心空穴较小的紫菜嗪体系中,空间位阻,静电作用才是影响构象稳定性的关键因素.由于分子内氢键的存在,氧杂化会明显降低内氢迁移正负反应速率;而S杂化体系的IHAT速率降低则与静电斥力和空间位阻密切相关.%The theoretical study of the mechanism and kinetics of the inner hydrogen atom-transfer process in oxa- porphyrazine, thia-porphyrazine was presented. The structures and energies of reactants, products and transition-states in the transfer reaction of inner hydrogen atoms in OPzH and SPzH were calculated with B3LYP/6-31G** method under certain symmetry restriction. The results show that the relative stability of conformations are directly correlated to aromaticity, but aromaticity is not the only determining factor which affects the relative stability of conformations; while in the porphyrazine systems with smaller central holes, the steric hindrance and the electrostatic interaction are more important factors which should not be neglected. The results also represent that oxa- can reduce speeds of positive and negative reactions, which is due to the existence of intra-molecular hydrogen bonds; but the decrease of NAT reaction speeds of thia-systems is resulted from steric hindrance and electrostatic interaction.

  13. Asymmetric Multilevel Diversity Coding and Asymmetric Gaussian Multiple Descriptions

    CERN Document Server

    Mohajer, Soheil; Diggavi, Suhas N


    We consider the asymmetric multilevel diversity (A-MLD) coding problem, where a set of $2^K-1$ information sources, ordered in a decreasing level of importance, is encoded into $K$ messages (or descriptions). There are $2^K-1$ decoders, each of which has access to a non-empty subset of the encoded messages. Each decoder is required to reproduce the information sources up to a certain importance level depending on the combination of descriptions available to it. We obtain a single letter characterization of the achievable rate region for the 3-description problem. In contrast to symmetric multilevel diversity coding, source-separation coding is not sufficient in the asymmetric case, and ideas akin to network coding need to be used strategically. Based on the intuitions gained in treating the A-MLD problem, we derive inner and outer bounds for the rate region of the asymmetric Gaussian multiple description (MD) problem with three descriptions. Both the inner and outer bounds have a similar geometric structure t...

  14. 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 ......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...

  15. 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.

  16. Transition State Models for Understanding the Origin of Chiral Induction in Asymmetric Catalysis. (United States)

    Sunoj, Raghavan B


    In asymmetric catalysis, a chiral catalyst bearing chiral center(s) is employed to impart chirality to developing stereogenic center(s). A rich and diverse set of chiral catalysts is now available in the repertoire of synthetic organic chemistry. The most recent trends point to the emergence of axially chiral catalysts based on binaphthyl motifs, in particular, BINOL-derived phosphoric acids and phosphoramidites. More fascinating ideas took shape in the form of cooperative multicatalysis wherein organo- and transition-metal catalysts are made to work in concert. At the heart of all such manifestations of asymmetric catalysis, classical or contemporary, is the stereodetermining transition state, which holds a perennial control over the stereochemical outcome of the catalytic process. Delving one step deeper, one would find that the origin of the stereoselectivity is delicately dependent on the relative stabilization of one transition state, responsible for the formation of the predominant stereoisomer, over the other transition state for the minor stereoisomer. The most frequently used working hypothesis to rationalize the experimentally observed stereoselectivity places an undue emphasis on steric factors and tends to regard the same as the origin of facial discrimination between the prochiral faces of the reacting partners. In light of the increasing number of asymmetric catalysts that rely on hydrogen bonding as well as other weak non-covalent interactions, it is important to take cognizance of the involvement of such interactions in the sterocontrolling transition states. Modern density functional theories offer a pragmatic and effective way to capture non-covalent interactions in transition states. Aided by the availability of such improved computational tools, it is quite timely that the molecular origin of stereoselectivity is subjected to more intelligible analysis. In this Account, we describe interesting molecular insights into the stereocontrolling

  17. The Unique Gas-Phase Chemistry of the [AuO](+) /CH4 Couple: Selective Oxygen-Atom Transfer to, Rather than Hydrogen-Atom Abstraction from, Methane. (United States)

    Zhou, Shaodong; Li, Jilai; Schlangen, Maria; Schwarz, Helmut


    The thermal reaction of [AuO](+) with methane has been explored using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. In contrast to the previously studied congener [CuO](+) , and to [AgO](+) , [AuO](+) reacts with CH4 exclusively via oxygen-atom transfer to form CH3 OH, and a novel mechanistic scenario for this selective oxidation process has been revealed. Also, the origin of the inertness of the [AgO](+) /CH4 couple has been addressed computationally.

  18. Direct observation of the excited-state proton transfer and decay kinetics of internally hydrogen-bonded photostabilizers in copolymer films (United States)

    Oconnor, D. B.; Scott, G. W.; Coulter, D. R.; Gupta, A.; Webb, S. P.


    The excited-state dynamics of a 2-hydroxyphenylbenzotriazole (HPB) photostabilizer copolymerized with polystyrene are reported. HPB fluorescence from these copolymer films is observed at approximately 630 nm, characteristic of the proton-transferred excited state of HPB, and it has a risetime of less than 10 ps and a decay time of 28 + or - 4 ps at room temperature. Measurement of the relative fluorescence quantum yield as a function of temperature gives the activation energy for nonradiative decay of this state to be E/hc = 259 + or 25/cm.

  19. Terahertz metamaterial with asymmetric transmission

    CERN Document Server

    Singh, R; Menzel, C; Rockstuhl, C; Azad, A K; Cheville, R A; Lederer, F; Zhang, W; Zheludev, N I


    We show for the first time that a planar metamaterial, an array of coupled metal split-ring resonators with a unit cell lacking mirror symmetry, exhibits asymmetric transmission of terahertz radiation propagating through it in opposite directions. This intriguing effect, that is compatible with Lorentz reciprocity and time-reversal, depends on a directional difference in conversion efficiency of the incident circularly polarized wave into one of opposite handedness, that is only possible in lossy low-symmetry planar chiral metamaterials. We show that asymmetric transmission is linked to excitation of enantiomerically sensitive plasmons, these are induced charge-field excitations that depend on the mutual handedness of incident wave and metamaterial pattern. Various bands of positive, negative and zero phase and group velocities have been identified indicating the opportunity to develop polarization sensitive negative index and slow light media based on such metamaterials.

  20. Theoretical study on hydrogenation catalysts containing a metal hydride as additional hydrogen supply

    NARCIS (Netherlands)

    Snijder, E.D.; Versteeg, G.F.; Swaaij, W.P.M. van


    A hypothetical hydrogenation catalyst consisting of porous, catalytically active particles embedded with metal hydride powder was evaluated. The metal hydride provides temporarily additional hydrogen if the mass transfer rate of the hydrogen to the internal of the particle is not sufficient. A numer

  1. 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.

  2. Asymmetrical Γ-Source Inverters

    DEFF Research Database (Denmark)

    Wei, Mo; Poh Chiang, Loh; Blaabjerg, Frede


    , inverters with coupled transformers have been introduced, but they usually lead to high turns ratio, and hence many winding turns, at high gain. An alternative would then be the asymmetrical Γ-source inverters proposed in this paper, whose gain is raised by lowering their turns ratio toward unity. The input...... current drawn by the proposed inverters is smoother and, hence, more adaptable by the source. Theories and experimental results have been presented in this paper for validating the concepts proposed....

  3. 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...

  4. 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.

  5. 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

  6. 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...

  7. Comparative study of symmetric and asymmetric somatic hybridization between common wheat and Haynaldia villosa

    Institute of Scientific and Technical Information of China (English)


    Symmetric and asymmetric protoplast fusion between long term cell suspension-derived protoplasts of Triticum aestivum (cv. Jinan 177) and protoplasts of Haynaldia villosa prepared from one-year-old embryogeneric calli was performed by PEG method. In asymmetric fusion, donor calli were treated with gamma ray at a dose of 40, 60, 80 Gy (1.3 Gy/min) respectively and then used to isolate protoplasts. Results of morphological, cytological, biochemical (isozyme) and 5S rDNA spacer sequence analysis revealed that we obtained somatic hybrid lines at high frequency from both symmetric and asymmetric fusion. Hybrid plants were recovered from symmetric and low dose g-fusion combinations. GISH (genomic in situ hybridization) analysis proved exactly the existence of both parental chromosomes and the common occurrence of several kinds of translocation between them in the hybrid clones regenerated from symmetric and asymmetric fusion. And the elimination of donor DNA in hybrid clones regenerated from asymmetric fusion combinations was found to increase with the increasing gamma doses. It is concluded that transference and recombination of nuclear DNA can be achieved effectively by symmetric and asymmetric fusion, hybrids with small fragment translocation which are valuable in plant breeding can be obtained directly by asymmetric fusion.

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

    CERN Document Server

    Smykalla, Lars; Mende, Carola; Lang, Heinrich; Knupfer, Martin; Hietschold, Michael


    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(111), on the more reactive Ag(110) 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{\\deg}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 de...

  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. Reaction pathways of proton transfer in hydrogen-bonded phenol-carboxylate complexes explored by combined UV-vis and NMR spectroscopy. (United States)

    Koeppe, Benjamin; Tolstoy, Peter M; Limbach, Hans-Heinrich


    Combined low-temperature NMR/UV-vis spectroscopy (UVNMR), where optical and NMR spectra are measured in the NMR spectrometer under the same conditions, has been set up and applied to the study of H-bonded anions A··H··X(-) (AH = 1-(13)C-2-chloro-4-nitrophenol, X(-) = 15 carboxylic acid anions, 5 phenolates, Cl(-), Br(-), I(-), and BF(4)(-)). In this series, H is shifted from A to X, modeling the proton-transfer pathway. The (1)H and (13)C chemical shifts and the H/D isotope effects on the latter provide information about averaged H-bond geometries. At the same time, red shifts of the π-π* UV-vis absorption bands are observed which correlate with the averaged H-bond geometries. However, on the UV-vis time scale, different tautomeric states and solvent configurations are in slow exchange. The combined data sets indicate that the proton transfer starts with a H-bond compression and a displacement of the proton toward the H-bond center, involving single-well configurations A-H···X(-). In the strong H-bond regime, coexisting tautomers A··H···X(-) and A(-)···H··X are observed by UV. Their geometries and statistical weights change continuously when the basicity of X(-) is increased. Finally, again a series of single-well structures of the type A(-)···H-X is observed. Interestingly, the UV-vis absorption bands are broadened inhomogeneously because of a distribution of H-bond geometries arising from different solvent configurations.

  11. Hydrogen Spectrum (United States)

    Murdin, P.


    The series of absorption or emission lines that are characteristic of the hydrogen atom. According to the Bohr theory of the hydrogen atom, devised by Danish physicist Neils Bohr (1885-1962) in 1913, the hydrogen atom can be envisaged as consisting of a central nucleus (a proton) around which a single electron revolves. The electron is located in one of a number of possible permitted orbits, each...

  12. A search for pure compounds suitable for use as matrix in spectroscopic studies of radiation-produced radical cations. III. A selection of compounds based on the thermochemistry of hydrogen and proton transfer reactions between neutral molecules and their cations (United States)

    Van den Bosch, Ann; Ceulemans, Jan

    A systematic investigation is made of the thermochemistry of hydrogen and proton transfer between neutral molecules and their cations covering the entire organic chemistry, with the aim of selecting those compounds that are suitable for use as matrices in spectroscopic studies of radiation-produced radical cations. Compounds that are characterized by positive reaction enthalpies may be considered promising for use as matrices in such studies. Calculations are based on experimentally determined ionization energies and proton affinities and on carbon-hydrogen bond strengths that are arbitrarily taken as 418 kJ.mol -1 (100 kcal.mol -1). Effects of actual deviations from this value are considered. In the aliphatic series of compounds, reaction enthalpies depend strongly on functional groups present. Marked positive reaction enthalpies are obtained for alkenes, alkadienes, thioethers, mercaptans, iodoalkanes and tertiary amines. Non-aromatic cyclic compounds generally behave as their aliphatic counterparts. Thus, positive reaction enthalpies are generally obtained for unsaturated alicyclic hydrocarbons and cyclic thioethers. Positive reaction enthalpies are also obtained for piperidine, quinuclidine, manxine and derivatives. In the homocyclic aromatic series of compounds, reaction enthalpies are generally positive. Thus, positive reaction enthalpies are obtained for aromatic hydrocarbons, fluoro- and chlorobenzenes, aromatic amines (amino group attached directly to the ring) and halo- and methoxyanilines. In the heterocyclic aromatic series of compounds reaction enthalpies are generally negative. This is for instance the case for a large number of pyridine derivatives, di- and triazines and a number of bi- and tricyclic compounds. Positive reaction enthalpies are however obtained for furan and pyrrole.

  13. Stability of the Hydrogen and Hydrogen-like Molecules


    Richard, Jean-Marc


    We present a simple proof of the stability of the hydrogen molecule $(M^+M^+m^-m^-)$. It does not rely on the proton-to-electron mass ratio $M/m$ being very large, and actually holds for arbitrary values of $M/m$. Some asymmetric molecules of the type $(m_1^+m_2^+m_3^-m_4^-)$ are also stable. Possible applications to molecules containing antiparticles and to exotic hadrons in the quark model are briefly outlined. Revtex Version 3.0, 4 Figures available on request by Fax or Mail.

  14. Asymmetric Schiff bases derived from diaminomaleonitrile and their metal complexes (United States)

    Yang, Jianjie; Shi, Rufei; Zhou, Pei; Qiu, Qiming; Li, Hui


    Asymmetric Schiff bases, due to its asymmetric structure, can be used as asymmetric catalyst, antibacterial, and mimic molecules during simulate biological processes, etc. In recent years, research on synthesis and properties of asymmetric Schiff bases have become an increase interest of chemists. This review summarizes asymmetric Schiff bases derived from diaminomaleonitrile (DAMN) and DAMN-based asymmetric Schiff bases metal complexes. Applications of DAMN-based asymmetric Schiff bases are also discussed in this review.

  15. The engineering sizing of the packed desorption column of hydrogen isotopes from Pb–17Li eutectic alloy. A rate based model using experimental mass transfer coefficients from a Melodie loop

    Energy Technology Data Exchange (ETDEWEB)

    Linek, V., E-mail: [Prague Institute of Chemical Technology, Department of Chemical Engineering, CZ-166 28 Prague 6 (Czech Republic); Košek, L. [Research Centre Řež, CZ-250 68 Husinec-Řež (Czech Republic); Moucha, T.; Rejl, F.J.; Kordač, M.; Valenz, L.; Opletal, M. [Prague Institute of Chemical Technology, Department of Chemical Engineering, CZ-166 28 Prague 6 (Czech Republic)


    Highlights: • The model of hydrogen isotopes desorption from lead lithium alloy in packed column is presented. • Mass transfer coefficient k{sub L}a are evaluated from Alpy's Melodie loop experiments. • Packing height and efficiency of packed columns in DEMO plant for DCLL and HCLL are evaluated. • Effects of liquid phase axial dispersion, surface tension and wettability of packing are evaluated. • Effect of flow rate of the purge gas on packing height and desorption efficiency is evaluated. - Abstract: The model of the desorption of hydrogen isotopes from lead lithium alloy in a packed column is derived from the first principles using the plug flow in the liquid phase either the plug flow or ideal mixing in the gas phases. Sievert's law of non-linear equilibrium is followed. The volumetric mass transfer coefficient k{sub L}a and its dependence on the liquid metal flow rate are evaluated on the basis of the Melodie loop experiments. The presented model is used for evaluation of the minimum flow rate of the purge gas for which the concentration of the isotope in the gas leaving the column is at its highest, while the driving force of the interfacial transport of the isotope is still not reduced and the tritium desorption efficiency is therefore retained. The potential effect of the axial dispersion in the gas and liquid phase is evaluated. Highlighted are the issues of the optimum packing geometric surface area, above which the efficiency starts to decrease, and of the role of the surface tension and the contact angle with regard to the wettability of the packing. On the basis of the findings related to these factors, the Mellapak 500 Y and Mellapak packings with flat surfaces are recommended for the tests aiming to intensify the tritium desorption efficiency in the packed columns. The models were used for the engineering sizing of the packed columns in two breeding blanket concepts for the DEMO plant – utilizing DCLL (dual coolant lead lithium

  16. 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.

  17. Spontaneous baryogenesis from asymmetric inflaton

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Fuminobu [Tohoku Univ., Sendai (Japan). Dept. of Physics; Tokyo Univ., Chiba (Japan). Kavli IPMU (WPI), UTIAS; Yamada, Masaki [Tokyo Univ., Chiba (Japan). Kavli IPMU (WPI), UTIAS; Tokyo Univ., Chiba (Japan). Inst. for Cosmic Ray Research; DESY Hamburg (Germany)


    We propose a variant scenario of spontaneous baryogenesis from asymmetric inflaton based on current-current interactions between the inflaton and matter fields with a non-zero B-L charge. When the inflaton starts to oscillate around the minimum after inflation, it may lead to excitation of a CP-odd component, which induces an effective chemical potential for the B-L number through the current-current interactions. We study concrete inflation models and show that the spontaneous baryogenesis scenario can be naturally implemented in the chaotic inflation in supergravity.

  18. The asymmetric Goos-H\\"anchen effect


    Araujo, Manoel P.; Carvalho, Silvânia A.; De Leo, Stefano


    We show in which conditions optical gaussian beams, propagating throughout an homogeneous dielectric right angle prism, present an asymmetric Goos-H\\"anchen (GH) effect. This asymmetric behavior is seen for incidence at critical angles and happens in the propagation direction of the outgoing beam. The asymmetric GH effect can be also seen as an amplification of the standard GH shift. Due to the fact that it only depends on the ratio between the wavelength and the minimal waist size of the inc...

  19. Review of Composite Asymmetric Spur Gear


    Sandeep C. Dhaduti; Dr. S. G. Sarganachari


    Gears made from composite materials are widely used in many power and motion transmission applications. Due to lower weight to stiffness ratio, composite gears may be replaced by conventional material gears in power transmission systems. Design of gears with asymmetric teeth enables to increase load capacity, reduce weight, size and vibration level. This article includes a summary of asymmetric gear design parameters, new developments of asymmetric spur gear and their ...

  20. Hydrogen carriers (United States)

    He, Teng; Pachfule, Pradip; Wu, Hui; Xu, Qiang; Chen, Ping


    Hydrogen has the potential to be a major energy vector in a renewable and sustainable future energy mix. The efficient production, storage and delivery of hydrogen are key technical issues that require improvement before its potential can be realized. In this Review, we focus on recent advances in materials development for on-board hydrogen storage. We highlight the strategic design and optimization of hydrides of light-weight elements (for example, boron, nitrogen and carbon) and physisorbents (for example, metal-organic and covalent organic frameworks). Furthermore, hydrogen carriers (for example, NH3, CH3OH-H2O and cycloalkanes) for large-scale distribution and for on-site hydrogen generation are discussed with an emphasis on dehydrogenation catalysts.

  1. 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.

  2. The asymmetric Goos-H\\"anchen effect

    CERN Document Server

    Araujo, Manoel P; De Leo, Stefano


    We show in which conditions optical gaussian beams, propagating throughout an homogeneous dielectric right angle prism, present an asymmetric Goos-H\\"anchen (GH) effect. This asymmetric behavior is seen for incidence at critical angles and happens in the propagation direction of the outgoing beam. The asymmetric GH effect can be also seen as an amplification of the standard GH shift. Due to the fact that it only depends on the ratio between the wavelength and the minimal waist size of the incoming gaussian beam, it can be also used to determine one of these parameters. Multiple peaks interference is an additional phenomenon seen in the presence of such asymmetric effects.

  3. 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

  4. 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.

  5. Excitons in asymmetric quantum wells (United States)

    Grigoryev, P. S.; Kurdyubov, A. S.; Kuznetsova, M. S.; Ignatiev, I. V.; Efimov, Yu. P.; Eliseev, S. A.; Petrov, V. V.; Lovtcius, V. A.; Shapochkin, P. Yu.


    Resonance dielectric response of excitons is studied for the high-quality InGaAs/GaAs heterostructures with wide asymmetric quantum wells (QWs). To highlight effects of the QW asymmetry, we have grown and studied several heterostructures with nominally square QWs as well as with triangle-like QWs. Several quantum confined exciton states are experimentally observed as narrow exciton resonances. A standard approach for the phenomenological analysis of the profiles is generalized by introducing different phase shifts for the light waves reflected from the QWs at different exciton resonances. Good agreement of the phenomenological fit to the experimentally observed exciton spectra for high-quality structures allowed us to reliably obtain parameters of the exciton resonances: the exciton transition energies, the radiative broadenings, and the phase shifts. A direct numerical solution of the Schrödinger equation for the heavy-hole excitons in asymmetric QWs is used for microscopic modeling of the exciton resonances. Remarkable agreement with the experiment is achieved when the effect of indium segregation is taken into account. The segregation results in a modification of the potential profile, in particular, in an asymmetry of the nominally square QWs.

  6. 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.

  7. A kinetic and structural investigation of DNA-Based asymmetric catalysis using first-generation ligands

    NARCIS (Netherlands)

    Rosati, Fiora; Boersma, Arnold J.; Klijn, Jaap E.; Meetsma, Auke; Feringa, Ben L.; Roelfes, Gerard


    The recently developed concept of DNA-based asymmetric catalysis involves the transfer of chirality from the DNA double helix in reactions using a noncovalently bound catalyst. To date, two generations of DNA-based catalysts have been reported that differ in the design of the ligand for the metal. H

  8. Binding to Redox-Inactive Alkali and Alkaline Earth Metal Ions Strongly Deactivates the C-H Bonds of Tertiary Amides toward Hydrogen Atom Transfer to Reactive Oxygen Centered Radicals. (United States)

    Salamone, Michela; Carboni, Giulia; Mangiacapra, Livia; Bietti, Massimo


    The effect of alkali and alkaline earth metal ions on the reactions of the cumyloxyl radical (CumO(•)) with N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA) was studied by laser flash photolysis. In acetonitrile, a >2 order of magnitude decrease in the rate constant for hydrogen atom transfer (HAT) from the C-H bonds of these substrates (kH) was measured after addition of Li(+). This behavior was explained in terms of a strong interaction between Li(+) and the oxygen atom of both DMF and DMA that increases the extent of positive charge on the amide, leading to C-H bond deactivation toward HAT to the electrophilic radical CumO(•). Similar effects were observed after addition of Ca(2+), which was shown to strongly bind up to four equivalents of the amide substrates. With Mg(2+), weak C-H deactivation was observed for the first two substrate equivalents followed by stronger deactivation for two additional equivalents. No C-H deactivation was observed in DMSO after addition of Li(+) and Mg(2+). These results point toward the important role played by metal ion Lewis acidity and solvent Lewis basicity, indicating that C-H deactivation can be modulated by varying the nature of the metal cation and solvent and allowing for careful control over the HAT reactivity of amide substrates.

  9. Model Insensitive and Calibration Independent Method for Determination of the Downstream Neutral Hydrogen Density Through Ly-alpha Glow Observations (United States)

    Gangopadhyay, P.; Judge, D. L.


    Our knowledge of the various heliospheric phenomena (location of the solar wind termination shock, heliopause configuration and very local interstellar medium parameters) is limited by uncertainties in the available heliospheric plasma models and by calibration uncertainties in the observing instruments. There is, thus, a strong motivation to develop model insensitive and calibration independent methods to reduce the uncertainties in the relevant heliospheric parameters. We have developed such a method to constrain the downstream neutral hydrogen density inside the heliospheric tail. In our approach we have taken advantage of the relative insensitivity of the downstream neutral hydrogen density profile to the specific plasma model adopted. We have also used the fact that the presence of an asymmetric neutral hydrogen cavity surrounding the sun, characteristic of all neutral densities models, results in a higher multiple scattering contribution to the observed glow in the downstream region than in the upstream region. This allows us to approximate the actual density profile with one which is spatially uniform for the purpose of calculating the downstream backscattered glow. Using different spatially constant density profiles, radiative transfer calculations are performed, and the radial dependence of the predicted glow is compared with the observed I/R dependence of Pioneer 10 UV data. Such a comparison bounds the large distance heliospheric neutral hydrogen density in the downstream direction to a value between 0.05 and 0.1/cc.

  10. Crystal structure and Raman spectra of rubidium hydrogen squarate (United States)

    Georgopoulos, Stéfanos L.; Diniz, Renata; Rodrigues, Bernardo L.; de Oliveira, Luiz F. C.


    Rubidium hydrogen squarate (RbHC 4O 4, RbHSQ) crystallized in monoclinic space group P2 1/ c. This compound form a short asymmetric intermolecular hydrogen bond whose O-O distance is 2.482(4) Å. The hydrogen squarate anions are forming head-to-tail infinite chain hydrogen-bonding motifs. A long interplanar separation (4.15 Å) indicates that a weak π interaction occurs between hydrogen squarate anions in RbHSQ. The hydrogen bond and cation-anion interactions are the predominant driving forces in the crystal packing. The Raman spectrum of RbHSQ shows an average behaviour between squaric acid and squarate dianion, however, the vibrational modes at ca. 1800 cm -1 (CO stretching mode) and in the region 1500-1700 cm -1 (CO+CC stretching modes) are the most affected by the presence of strong hydrogen bonding interactions.

  11. Asymmetric catalysis : ligand design and microwave acceleration


    Bremberg, Ulf


    This thesis deals partly with the design and synthesis ofligands for use in asymmetric catalysis, and partly with theapplication of microwave heating on metal-based asymmetriccatalytic reactions. Enantiomerically pure pyridyl alcohols and bipyridylalcohols were synthesized from the chiral pool for future usein asymmetric catalysis. Lithiated pyridines were reacted withseveral chiral electrophiles, yielding diastereomeric mixturesthat could be separated without the use of resolutiontechniques....

  12. 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...

  13. 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...

  14. The Catalytic Asymmetric Intramolecular Stetter Reaction. (United States)

    de Alaniz, Javier Read; Rovis, Tomislav


    This account chronicles our efforts at the development of a catalytic asymmetric Stetter reaction using chiral triazolium salts as small molecule organic catalysts. Advances in the mechanistically related azolium-catalyzed asymmetric benzoin reaction are discussed, particularly as they apply to catalyst design. A chronological treatise of reaction discovery, catalyst optimization and reactivity extension follows.

  15. 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

  16. Condensation on Slippery Asymmetric Bumps

    CERN Document Server

    Park, Kyoo-Chul; He, Neil; Aizenberg, Joanna


    Bumps are omnipresent from human skin to the geological structures on planets, which offer distinct advantages in numerous phenomena including structural color, drag reduction, and extreme wettability. Although the topographical parameters of bumps such as radius of curvature of convex regions significantly influence various phenomena including anti-reflective structures and contact time of impacting droplets, the effect of the detailed bump topography on growth and transport of condensates have not been clearly understood. Inspired by the millimetric bumps of the Namib Desert beetle, here we report the identified role of radius of curvature and width of bumps with homogeneous surface wettability in growth rate, coalescence and transport of water droplets. Further rational design of asymmetric convex topography and synergetic combination with slippery coating simultaneously enable self-transport, leading to unseen five-fold higher growth rate and an order of magnitude faster shedding time of droplets compared...

  17. Baker's yeast catalyzed asymmetric reduction of methyl acetoacetate in glycerol containing systems

    Directory of Open Access Journals (Sweden)

    Adi Wolfson


    Full Text Available The asymmetric hydrogenation of methyl acetoacetate was successfully performed with baker's yeast in pure glycerol and mixtures of glycerol and water. Though yeast viability was very low after exposure to glycerol, the enzymatic activity in pure glycerol was preserved for some days. In addition, a mixture of glycerol and water combined the advantageous of each individual solvent and resulted in high catalytic performance and efficient product extraction yield

  18. 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.

  19. Hydrogen permeation in stationary arc-melted nickel 200 (United States)

    Li, H.; North, T. H.; Sommerville, I. D.; McLean, A.


    A combination of hydrogen permeation experiments and computer simulation was used to evaluate the distributions of temperature and of the hydrogen transfer flux in a stationary arcmelted Nickel 200 disc over the entire hydrogen permeation zone. The results indicate that the markedly nonuniform temperature distribution in the hydrogen permeation zone involves widely varying hydrogen fluxes and even transfer of hydrogen in different directions. At steady state, the hydrogen distribution is determined by a thermally produced dynamic equilibrium. Hydrogen supersaturation occurs in solid nickel at the solid/liquid interface in the arc-melted pool. An increase in hydrogen partial pressure in the shielding gas increases the heat input to the melt and decreases the stability of the arc melting process.

  20. Performance characterization of a hydrogen catalytic heater.

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Terry Alan; Kanouff, Michael P.


    This report describes the performance of a high efficiency, compact heater that uses the catalytic oxidation of hydrogen to provide heat to the GM Hydrogen Storage Demonstration System. The heater was designed to transfer up to 30 kW of heat from the catalytic reaction to a circulating heat transfer fluid. The fluid then transfers the heat to one or more of the four hydrogen storage modules that make up the Demonstration System to drive off the chemically bound hydrogen. The heater consists of three main parts: (1) the reactor, (2) the gas heat recuperator, and (3) oil and gas flow distribution manifolds. The reactor and recuperator are integrated, compact, finned-plate heat exchangers to maximize heat transfer efficiency and minimize mass and volume. Detailed, three-dimensional, multi-physics computational models were used to design and optimize the system. At full power the heater was able to catalytically combust a 10% hydrogen/air mixture flowing at over 80 cubic feet per minute and transfer 30 kW of heat to a 30 gallon per minute flow of oil over a temperature range from 100 C to 220 C. The total efficiency of the catalytic heater, defined as the heat transferred to the oil divided by the inlet hydrogen chemical energy, was characterized and methods for improvement were investigated.

  1. 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.


    Institute of Scientific and Technical Information of China (English)

    Cuihua ZHANG; Haibin YU; Guangshu CHANG


    In this paper, the issue of quality evaluation level decision problem in outsourcing is studied under different information backgrounds. Based on the quality contracting optimization models of Stanley and others, a principal agent model concerned with quality prevention level and evaluation level is set up with regards to buyer as principal and supplier as agent. In the models, quality prevention level is a variable decided by the supplier, quality evaluation level and transfer payment are variables decided by the buyer. We focus on the study of quality evaluation level and transfer payment decision in outsourcing under asymmetric information. Maximal principle is used to get the solution to quality evaluation level when supplier quality prevention level information is hidden. At last simulation calculation is performed concerned with tractor production outsourcing business of an agricultural machine company. Simulation results under different information backgrounds are analyzed and compared.

  3. Enantioselective Hydrogenation of Aromatic Ketones Catalyzed by Ru Complex Using a New Bipyridyl Diphosphine

    Institute of Scientific and Technical Information of China (English)

    CHEN Li; FU Xing-Li; MING Fang-Yong; CHEN Hua; LI Xian-Jun


    A series of RuCl2(bipyridyldiphosphine)(1,2-diamine)complexes were synthesized and applied to the asymmetric hydrogenation of aromatic ketones.Solvent effect and a wide variety of aromatic ketones were explored and up to 96% enantioselectivity was achieved in the hydrogenation of o-bromoacetophenone.

  4. Experimental realization of optimal asymmetric cloning and telecloning via partial teleportation

    CERN Document Server

    Zhao, Z; Zhou, X Q; Chen, Y A; Lu, C Y; Karlsson, A; Pan, J W; Zhao, Zhi; Zhang, An-Ning; Zhou, Xiao-Qi; Chen, Yu-Ao; Lu, Chao-Yang; Karlsson, Anders; Pan, Jian-Wei


    We report an experimental realization of both optimal asymmetric cloning and telecloning of single photons by making use of partial teleportation of an unknown state. In the experiment, we demonstrate that, conditioned on the success of partial teleportation of single photons, not only the optimal asymmetric cloning can be accomplished, but also one of two outputs can be transfered to a distant location, realizing the telecloning. The experimental results represented a novel way to achieve the quantum cloning and may have potential applications in the context of quantum cryptography.

  5. 氮杂环卡宾的合成及在氢转移反应中的应用%Synthesis and Application of N-Heterocyclic Carbene in Transfer Hydrogenation

    Institute of Scientific and Technical Information of China (English)

    高艳炫; 周宏勇; 李云庆; 王家喜


    利用氯甲基吡啶与咪唑反应制备了一系列含吡啶取代咪唑 L1~L5,考察了所得咪唑衍生物与钌化合物在碱性条件下原位形成的氮杂卡宾钌络合物对苯胺与醇氢转移反应的催化活性.研究了碱的种类、钌前体、温度等对反应的影响,结果表明 RuCl3·H2O/1-(2-吡啶甲基)-3-甲基碘化咪唑(L3)/KOH催化体系在185℃时对苯胺与乙二醇反应的催化活性较高,选择性生成N-羟乙基苯胺,TON(单化活性转化的底物分数)可达2130.此外,还考察了RuCl3·H2O/L3/KOH催化体系对苯胺与丁醇、环己醇、异丙醇、苯甲醇反应的催化性能.在催化剂作用下,醇与苯胺可形成亚胺及仲胺,伯醇可以自氢转移反应形成酯,反应产物的结构及选择性取决于醇的结构及反应条件.%A series of pyridine substituted imidazoles L1~L5 have been synthesized via reaction of chloromethylpyridine with imidazole. The effects of base, ruthenium precursor and temperature on the activity of catalyst formed in situ of N-heterocyclic carbene ligands with Ru precursor in catalytic hydrogen transfer reaction of aniline with glycol were evaluated. The results showed that the reaction of aniline with glycol promoted by RuCl3·H2O/3-methyl-1(2-pyridinylmethyl)-imidazole iodide (L3)/KOH at 185 ℃ selectively produced 2-(phenylamino)ethanol with the TON (turnover number) of 2130. In addition, the catalytic properties of RuCl3·H2O/L3/KOH in reaction of aniline with butanol, cyclohexanol, wo-propanol and phenyltnethanol were also investigated. Under promotion of catalyst, the aniline reacted with alcohol to produce imine and secondary amine. In addition, the ester was formed by self transfer hydrogenation of primary alcohol. The selectivity and product structures were depended on the structure of alcohol and the reaction conditions.

  6. 醇醛物质的量比对不饱和醛催化氢转移反应的影响%Influence of isopropanol/citral molar ratio on citral hydrogen transfer reaction

    Institute of Scientific and Technical Information of China (English)

    周勤; 陈希慧


    The influence of isopropanol/citral ratio on the reaction rate of citral and isopropanol hydrogen transfer reaction catalyzed by ZrO2/SiO2 was investigated. The results showed that the boiling point of reaction mixtures lowered with the increase of isopropanol/citral ratio under the experimental condition.The conversion of citral and selectivity to aim product were obviously influenced by isopropanol/citral ratio.The change of boiling point caused by the change of isopropanol/citral ratio could be the main influencing factor of the reaction rate. The optimum isopropanol/citral mole ratio of 5 and the experimental apparent activation energy of 100.5 kJ · mol -1 were attained.%探讨了ZrO2/SiO2催化柠檬醛和异丙醇的氢转移反应醇醛物质的量比对反应速率的影响.结果表明,实验条件下,反应混合物的沸点随醇醛物质的量比的增大而降低;柠檬醛转化率和目标产物选择性明显受醇醛物质的量比的影响,醇醛物质的量比变化导致混合物沸点的改变可能是影响反应速率的主要因素.研究条件下,反应最适宜的醇醛物质的量比为5,表观活化能为100.5 kJ·mol-1.

  7. Negative hydrogen ion production mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Bacal, M. [UPMC, LPP, Ecole Polytechnique, UMR CNRS 7648, Palaiseau (France); Wada, M. [School of Science and Engineering, Doshisha University, Kyoto 610-0321 (Japan)


    Negative hydrogen/deuterium ions can be formed by processes occurring in the plasma volume and on surfaces facing the plasma. The principal mechanisms leading to the formation of these negative ions are dissociative electron attachment to ro-vibrationally excited hydrogen/deuterium molecules when the reaction takes place in the plasma volume, and the direct electron transfer from the low work function metal surface to the hydrogen/deuterium atoms when formation occurs on the surface. The existing theoretical models and reported experimental results on these two mechanisms are summarized. Performance of the negative hydrogen/deuterium ion sources that emerged from studies of these mechanisms is reviewed. Contemporary negative ion sources do not have negative ion production electrodes of original surface type sources but are operated with caesium with their structures nearly identical to volume production type sources. Reasons for enhanced negative ion current due to caesium addition to these sources are discussed.

  8. Negative hydrogen ion production mechanisms (United States)

    Bacal, M.; Wada, M.


    Negative hydrogen/deuterium ions can be formed by processes occurring in the plasma volume and on surfaces facing the plasma. The principal mechanisms leading to the formation of these negative ions are dissociative electron attachment to ro-vibrationally excited hydrogen/deuterium molecules when the reaction takes place in the plasma volume, and the direct electron transfer from the low work function metal surface to the hydrogen/deuterium atoms when formation occurs on the surface. The existing theoretical models and reported experimental results on these two mechanisms are summarized. Performance of the negative hydrogen/deuterium ion sources that emerged from studies of these mechanisms is reviewed. Contemporary negative ion sources do not have negative ion production electrodes of original surface type sources but are operated with caesium with their structures nearly identical to volume production type sources. Reasons for enhanced negative ion current due to caesium addition to these sources are discussed.

  9. Stark-induced resonances in the photoionization of hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Glab, W.L.; Nayfeh, M.H.


    We report the first observation of electric-field-induced resonances in the multistep photoionization of hydrogen. Asymmetric profiles having blue wings are observed near the photoionization limit resulting from tunneling across the Stark-Coulomb combined potential (shape resonance). We measured the dependence of the spacing of the resonances on the electric field strength.

  10. Light-Induced Charge Transport within a Single Asymmetric Nanowire

    Energy Technology Data Exchange (ETDEWEB)



    Artificial photosynthetic systems using semiconductor materials have been explored for more than three decades in order to store solar energy in chemical fuels such as hydrogen. By mimicking biological photosynthesis with two light-absorbing centers that relay excited electrons in a nanoscopic space, a dual-band gap photoelectrochemical (PEC) system is expected to have higher theoretical energy conversion efficiency than a single band gap system. This work demonstrates the vectorial charge transport of photo-generated electrons and holes within a single asymmetric Si/TiO2 nanowire using Kelvin probe force microscopy (KPFM). Under UV illumination, higher surface potential was observed on the n-TiO₂ side, relative to the potential of the p-Si side, as a result of majority carriers’ recombination at the Si/TiO₂ interface. These results demonstrate a new approach to investigate charge separation and transport in a PEC system. This asymmetric nanowire heterostructure, with a dual band gap configuration and simultaneously exposed anode and cathode surfaces represents an ideal platform for the development of technologies for the generation of solar fuels, although better photoanode materials remain to be discovered.

  11. 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.

  12. Asymmetric stem cell division: lessons from Drosophila. (United States)

    Wu, Pao-Shu; Egger, Boris; Brand, Andrea H


    Asymmetric cell division is an important and conserved strategy in the generation of cellular diversity during animal development. Many of our insights into the underlying mechanisms of asymmetric cell division have been gained from Drosophila, including the establishment of polarity, orientation of mitotic spindles and segregation of cell fate determinants. Recent studies are also beginning to reveal the connection between the misregulation of asymmetric cell division and cancer. What we are learning from Drosophila as a model system has implication both for stem cell biology and also cancer research.

  13. On-chip asymmetric microcavity optomechanics. (United States)

    Soltani, Soheil; Hudnut, Alexa W; Armani, Andrea M


    High quality factor (Q) optical resonators have enabled rapid growth in the field of cavity-enhanced, radiation pressure-induced optomechanics. However, because research has focused on axisymmetric devices, the observed regenerative excited mechanical modes are similar. In the present work, a strategy for fabricating high-Q whispering gallery mode microcavities with varying degrees of asymmetry is developed and demonstrated. Due to the combination of high optical Q and asymmetric device design, two previously unobserved modes, the asymmetric cantilever and asymmetric crown mode, are demonstrated with sub-mW thresholds for onset of oscillations. The experimental results are in good agreement with computational modeling predictions.

  14. Regenerating a symmetry in asymmetric dark matter. (United States)

    Buckley, Matthew R; Profumo, Stefano


    Asymmetric dark matter theories generically allow for mass terms that lead to particle-antiparticle mixing. Over the age of the Universe, dark matter can thus oscillate from a purely asymmetric configuration into a symmetric mix of particles and antiparticles, allowing for pair-annihilation processes. Additionally, requiring efficient depletion of the primordial thermal (symmetric) component generically entails large annihilation rates. We show that unless some symmetry completely forbids dark matter particle-antiparticle mixing, asymmetric dark matter is effectively ruled out for a large range of masses, for almost any oscillation time scale shorter than the age of the Universe.

  15. Absolute Asymmetric Synthesis Using A Cocrystal Approach

    Institute of Scientific and Technical Information of China (English)



    1 Results Absolute asymmetric synthesis by means of solid-state reaction of chiral crystals self-assembled from achiral molecules is an attractive and promising methodology for asymmetric synthesis because it is not necessary to employ any external chiral source like a chiral catalyst.In order to design reliably absolute asymmetric syntheses in the solid state,it is inevitable to prepare and predict the formation of chiral crystals from achiral compounds.We have prepared a number of chiral cocrystals co...

  16. Asymmetric dark matter in braneworld cosmology

    Energy Technology Data Exchange (ETDEWEB)

    Meehan, Michael T.; Whittingham, Ian B., E-mail:, E-mail: [School of Engineering and Physical Sciences, James Cook University, Townsville, 4811 Australia (Australia)


    We investigate the effect of a braneworld expansion era on the relic density of asymmetric dark matter. We find that the enhanced expansion rate in the early universe predicted by the Randall-Sundrum II (RSII) model leads to earlier particle freeze-out and an enhanced relic density. This effect has been observed previously by Okada and Seto (2004) for symmetric dark matter models and here we extend their results to the case of asymmetric dark matter. We also discuss the enhanced asymmetric annihilation rate in the braneworld scenario and its implications for indirect detection experiments.

  17. Enantiopure sulfoxides: recent applications in asymmetric synthesis. (United States)

    Carreño, M Carmen; Hernández-Torres, Gloria; Ribagorda, María; Urbano, Antonio


    Sulfoxides are nowadays recognised as powerful chiral auxiliaries that may participate in a wide range of asymmetric reactions. Their high configurational stability, the existence of several efficient methods allowing the access to both configurations as well as their synthetic versatility are characteristic features offering a tremendous potential to develop new applications. Significant recent advances leading to high asymmetric inductions in carbon-carbon and carbon-oxygen bond forming reactions, and applications of homochiral sulfoxides to atroposelective synthesis and asymmetric catalysis are discussed. New uses of sulfoxides in the design of chiroptical switches are also shown.

  18. Buoyancy Effects on Unsteady MHD Flow of a Reactive Third-Grade Fluid with Asymmetric Convective Cooling

    Directory of Open Access Journals (Sweden)

    Tirivanhu Chinyoka


    Full Text Available This article examines the combined effects of buoyancy force and asymmetrical convective cooling on unsteady MHD channel flow and heat transfer characteristics of an incompressible, reactive, variable viscosity and electrically conducting third grade fluid. The chemical kinetics in the flow system is exothermic and the asymmetric convective heat transfers at the channel walls follow the Newton’s law of cooling. The coupled nonlinear partial differential equations governing the problem are derived and solved numerically using a semi-implicit finite difference scheme. Graphical results are presented and physical aspects of the problem are discussed with respect to various parameters embedded in the system.

  19. Asymmetric dark matter bound state (United States)

    Bi, Xiao-Jun; Kang, Zhaofeng; Ko, P.; Li, Jinmian; Li, Tianjun


    We propose an interesting framework for asymmetric scalar dark matter (ADM), which has novel collider phenomenology in terms of an unstable ADM bound state (ADMonium) produced via Higgs portals. ADMonium is a natural consequence of the basic features of ADM: the (complex scalar) ADM is charged under a dark local U (1 )d symmetry which is broken at a low scale and provides a light gauge boson X . The dark gauge coupling is strong and then ADM can annihilate away into X -pair effectively. Therefore, the ADM can form a bound state due to its large self-interaction via X mediation. To explore the collider signature of ADMonium, we propose that ADM has a two-Higgs doublet portal. The ADMonium can have a sizable mixing with the heavier Higgs boson, which admits a large cross section of ADMonium production associated with b b ¯. The resulting signature at the LHC depends on the decays of X . In this paper we consider a case of particular interest: p p →b b ¯ +ADMonium followed by ADMonium→2 X →2 e+e- where the electrons are identified as (un)converted photons. It may provide a competitive explanation to heavy di-photon resonance searches at the LHC.

  20. Twin Higgs Asymmetric Dark Matter. (United States)

    García García, Isabel; Lasenby, Robert; March-Russell, John


    We study asymmetric dark matter (ADM) in the context of the minimal (fraternal) twin Higgs solution to the little hierarchy problem, with a twin sector with gauged SU(3)^{'}×SU(2)^{'}, a twin Higgs doublet, and only third-generation twin fermions. Naturalness requires the QCD^{'} scale Λ_{QCD}^{'}≃0.5-20  GeV, and that t^{'} is heavy. We focus on the light b^{'} quark regime, m_{b^{'}}≲Λ_{QCD}^{'}, where QCD^{'} is characterized by a single scale Λ_{QCD}^{'} with no light pions. A twin baryon number asymmetry leads to a successful dark matter (DM) candidate: the spin-3/2 twin baryon, Δ^{'}∼b^{'}b^{'}b^{'}, with a dynamically determined mass (∼5Λ_{QCD}^{'}) in the preferred range for the DM-to-baryon ratio Ω_{DM}/Ω_{baryon}≃5. Gauging the U(1)^{'} group leads to twin atoms (Δ^{'}-τ^{'}[over ¯] bound states) that are successful ADM candidates in significant regions of parameter space, sometimes with observable changes to DM halo properties. Direct detection signatures satisfy current bounds, at times modified by dark form factors.

  1. Force on an Asymmetric Capacitor

    CERN Document Server

    Bahder, T B; Bahder, Thomas B.; Fazi, Chris


    When a high voltage (~30 kV) is applied to a capacitor whose electrodes have different physical dimensions, the capacitor experiences a net force toward the smaller electrode (Biefeld-Brown effect). We have verified this effect by building four capacitors of different shapes. The effect may have applications to vehicle propulsion and dielectric pumps. We review the history of this effect briefly through the history of patents by Thomas Townsend Brown. At present, the physical basis for the Biefeld-Brown effect is not understood. The order of magnitude of the net force on the asymmetric capacitor is estimated assuming two different mechanisms of charge conduction between its electrodes: ballistic ionic wind and ionic drift. The calculations indicate that ionic wind is at least three orders of magnitude too small to explain the magnitude of the observed force on the capacitor. The ionic drift transport assumption leads to the correct order of magnitude for the force, however, it is difficult to see how ionic dr...

  2. Asymmetric total synthesis of vindoline. (United States)

    Kato, Daisuke; Sasaki, Yoshikazu; Boger, Dale L


    A concise asymmetric total synthesis of (-)-vindoline (1) is detailed based on a tandem intramolecular [4+2]/[3+2] cycloaddition cascade of a 1,3,4-oxadiazole inspired by the natural product structure, in which the tether linking the initiating dienophile and oxadiazole bears a chiral substituent that controls the facial selectivity of the initiating Diels-Alder reaction and sets absolute stereochemistry of the remaining six stereocenters in the cascade cycloadduct. This key reaction introduces three rings and four C-C bonds central to the pentacyclic ring system setting all six stereocenters and introducing essentially all the functionality found in the natural product in a single step. Implementation of the approach also required the development of a unique ring expansion reaction to provide a six-membered ring suitably functionalized for introduction of the Delta (6, 7)-double bond found in the core structure of vindoline and defined our use of a protected hydroxymethyl group as the substituent used to control the stereochemical course of the cycloaddition cascade.

  3. Coupled transfers; Transferts couples

    Energy Technology Data Exchange (ETDEWEB)

    Nicolas, X.; Lauriat, G.; Jimenez-Rondan, J. [Universite de Marne-la-Vallee, Lab. d' Etudes des Transferts d' Energie et de Matiere (LETEM), 77 (France); Bouali, H.; Mezrhab, A. [Faculte des Sciences, Dept. de Physique, Lab. de Mecanique et Energetique, Oujda (Morocco); Abid, C. [Ecole Polytechnique Universitaire de Marseille, IUSTI UMR 6595, 13 Marseille (France); Stoian, M.; Rebay, M.; Lachi, M.; Padet, J. [Faculte des Sciences, Lab. de Thermomecanique, UTAP, 51 - Reims (France); Mladin, E.C. [Universitaire Polytechnique Bucarest, Faculte de Genie Mecanique, Bucarest (Romania); Mezrhab, A. [Faculte des Sciences, Lab. de Mecanique et Energetique, Dept. de Physique, Oujda (Morocco); Abid, C.; Papini, F. [Ecole Polytechnique, IUSTI, 13 - Marseille (France); Lorrette, C.; Goyheneche, J.M.; Boechat, C.; Pailler, R. [Laboratoire des Composites ThermoStructuraux, UMR 5801, 33 - Pessac (France); Ben Salah, M.; Askri, F.; Jemni, A.; Ben Nasrallah, S. [Ecole Nationale d' Ingenieurs de Monastir, Lab. d' Etudes des Systemes Thermiques et Energetiques (Tunisia); Grine, A.; Desmons, J.Y.; Harmand, S. [Laboratoire de Mecanique et d' Energetique, 59 - Valenciennes (France); Radenac, E.; Gressier, J.; Millan, P. [ONERA, 31 - Toulouse (France); Giovannini, A. [Institut de Mecanique des Fluides de Toulouse, 31 (France)


    This session about coupled transfers gathers 30 articles dealing with: numerical study of coupled heat transfers inside an alveolar wall; natural convection/radiant heat transfer coupling inside a plugged and ventilated chimney; finite-volume modeling of the convection-conduction coupling in non-stationary regime; numerical study of the natural convection/radiant heat transfer coupling inside a partitioned cavity; modeling of the thermal conductivity of textile reinforced composites: finite element homogenization on a full periodical pattern; application of the control volume method based on non-structured finite elements to the problems of axisymmetrical radiant heat transfers in any geometries; modeling of convective transfers in transient regime on a flat plate; a conservative method for the non-stationary coupling of aero-thermal engineering codes; measurement of coupled heat transfers (forced convection/radiant transfer) inside an horizontal duct; numerical simulation of the combustion of a water-oil emulsion droplet; numerical simulation study of heat and mass transfers inside a reactor for nano-powders synthesis; reduction of a combustion and heat transfer model of a direct injection diesel engine; modeling of heat transfers inside a knocking operated spark ignition engine; heat loss inside an internal combustion engine, thermodynamical and flamelet model, composition effects of CH{sub 4}H{sub 2} mixtures; experimental study and modeling of the evolution of a flame on a solid fuel; heat transfer for laminar subsonic jet of oxygen plasma impacting an obstacle; hydrogen transport through a A-Si:H layer submitted to an hydrogen plasma: temperature effects; thermal modeling of the CO{sub 2} laser welding of a magnesium alloy; radiant heat transfer inside a 3-D environment: application of the finite volume method in association with the CK model; optimization of the infrared baking of two types of powder paints; optimization of the emission power of an infrared

  4. A novel asymmetric synthesis of cinacalcet hydrochloride


    Arava, Veera R; Laxminarasimhulu Gorentla; Pramod K. Dubey


    A novel route to asymmetric synthesis of cinacalcet hydrochloride by the application of (R)-tert-butanesulfinamide and regioselective N-alkylation of the naphthyl ethyl sulfinamide intermediate is described.

  5. A novel asymmetric synthesis of cinacalcet hydrochloride

    Directory of Open Access Journals (Sweden)

    Veera R. Arava


    Full Text Available A novel route to asymmetric synthesis of cinacalcet hydrochloride by the application of (R-tert-butanesulfinamide and regioselective N-alkylation of the naphthyl ethyl sulfinamide intermediate is described.

  6. A novel asymmetric synthesis of cinacalcet hydrochloride (United States)

    Gorentla, Laxminarasimhulu; Dubey, Pramod K


    Summary A novel route to asymmetric synthesis of cinacalcet hydrochloride by the application of (R)-tert-butanesulfinamide and regioselective N-alkylation of the naphthyl ethyl sulfinamide intermediate is described. PMID:23019473

  7. Catalytic Asymmetric Synthesis of Phosphine Boronates

    NARCIS (Netherlands)

    Hornillos, Valentin; Vila, Carlos; Otten, Edwin; Feringa, Ben L.


    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of ,-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good y

  8. Asymmetric Swiss-cheese brane-worlds

    CERN Document Server

    Gergely, L A; K\\'{e}p\\'{\\i}r\\'{o}, Ibolya


    We consider Swiss-cheese brane universes embedded asymmetrically into the bulk. Neither the junction conditions between the Schwarzschild spheres and the sorrounding Friedmann brane regions with cosmological constant $\\Lambda $, nor the evolution of the scale factor are changed with respect to the symmetric case. The universe expands and decelerates forever. The asymmetry however has a drastic influence on the evolution of the cosmological fluid. Instead of the two branches of the symmetric case, in the asymmetric case four branches emerge. Moreover, the future pressure singularity arising in the symmetric case only for huge values of $\\Lambda $ becomes quite generic in the asymmetric case. Such pressure singularities emerge also when $\\Lambda=0$ is set. Then they are due entirely to the asymmetric embedding. For generic values of $\\Lambda $ we introduce a critical value of a suitably defined asymmetry parameter, which separates Swiss-cheese cosmologies with and without pressure singularities.

  9. 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.

  10. 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.

  11. 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...



    Claudiu Botoc


    The main aim of the paper is to examine if the stock market volatility exhibits asymmetric or an asymmetric response to past shocks, for certain CEE countries (Romania,Hungary, Bulgaria, Poland) over the period May 2004 - September 2014. For the stock marketsfrom East Europe the results are in line with the symmetric volatility, i.e. volatility is similaraffected by both positive and negative returns with the same magnitude. For the stock marketsfrom Central Europe the results are consistent ...

  13. Metallic Hydrogen (United States)

    Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan


    Hydrogen is the simplest and most abundant element in the Universe. At high pressure it is predicted to transform to a metal with remarkable properties: room temperature superconductivity, a metastable metal at ambient conditions, and a revolutionary rocket propellant. Both theory and experiment have been challenged for almost 80 years to determine its condensed matter phase diagram, in particular the insulator-metal transition. Hydrogen is predicted to dissociate to a liquid atomic metal at multi-megabar pressures and T =0 K, or at megabar pressures and very high temperatures. Thus, its predicted phase diagram has a broad field of liquid metallic hydrogen at high pressure, with temperatures ranging from thousands of degrees to zero Kelvin. In a bench top experiment using static compression in a diamond anvil cell and pulsed laser heating, we have conducted measurements on dense hydrogen in the region of 1.1-1.7 Mbar and up to 2200 K. We observe a first-order phase transition in the liquid phase, as well as sharp changes in optical transmission and reflectivity when this phase is entered. The optical signature is that of a metal. The mapping of the phase line of this transition is in excellent agreement with recent theoretical predictions for the long-sought plasma phase transition to metallic hydrogen. Research supported by the NSF, Grant DMR-1308641, the DOE Stockpile Stewardship Academic Alliance Program, Grant DE-FG52-10NA29656, and NASA Earth and Space Science Fellowship Program, Award NNX14AP17H.

  14. Asymmetric autocatalysis of pyrimidyl alkanol and its application to the study on the origin of homochirality. (United States)

    Soai, Kenso; Kawasaki, Tsuneomi; Matsumoto, Arimasa


    triggered by the morphology of inorganic chiral crystals such as quartz, sodium chlorate, and cinnabar. Chiral organic crystals of achiral compounds also act as chiral initiators, and during the study of a crystal of cytosine, enantioselective chiral crystal phase transformation of the cytosine crystal was achieved by removal of the water of crystallization in an achiral monohydrate crystal. Enantioselective C-C bond formation was realized on the surfaces of achiral single crystals based on the oriented prochirality of achiral aldehydes. Furthermore, asymmetric autocatalysis of pyrimidyl alkanols is a highly sensitive reaction that can recognize and amplify the significantly small effect of a chiral compound arising solely from isotope substitution of hydrogen, carbon, and oxygen (D/H, (13)C/(12)C, and (18)O/(16)O). These examples show that asymmetric autocatalysis with an amplification of chirality is a powerful tool for correlating the origin of chirality with highly enantioenriched organic compounds. Asymmetric autocatalysis using two β-amino alcohols reveals a reversal of enantioselectivity in the addition of i-Pr2Zn to aldehyde and is one approach toward understanding the mechanism of asymmetric dialkylzinc addition, where heteroaggregates act as the catalytic species.

  15. Electron transfer in peptides. (United States)

    Shah, Afzal; Adhikari, Bimalendu; Martic, Sanela; Munir, Azeema; Shahzad, Suniya; Ahmad, Khurshid; Kraatz, Heinz-Bernhard


    In this review, we discuss the factors that influence electron transfer in peptides. We summarize experimental results from solution and surface studies and highlight the ongoing debate on the mechanistic aspects of this fundamental reaction. Here, we provide a balanced approach that remains unbiased and does not favor one mechanistic view over another. Support for a putative hopping mechanism in which an electron transfers in a stepwise manner is contrasted with experimental results that support electron tunneling or even some form of ballistic transfer or a pathway transfer for an electron between donor and acceptor sites. In some cases, experimental evidence suggests that a change in the electron transfer mechanism occurs as a result of donor-acceptor separation. However, this common understanding of the switch between tunneling and hopping as a function of chain length is not sufficient for explaining electron transfer in peptides. Apart from chain length, several other factors such as the extent of the secondary structure, backbone conformation, dipole orientation, the presence of special amino acids, hydrogen bonding, and the dynamic properties of a peptide also influence the rate and mode of electron transfer in peptides. Electron transfer plays a key role in physical, chemical and biological systems, so its control is a fundamental task in bioelectrochemical systems, the design of peptide based sensors and molecular junctions. Therefore, this topic is at the heart of a number of biological and technological processes and thus remains of vital interest.

  16. 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.

  17. 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.

  18. Development of the asymmetric human (United States)

    Wolpert, Lewis


    Symmetry across the midline is present in many animals, together with the left/right asymmetry of several organs, such as the heart in vertebrates. The development of such asymmetries during embryonic development requires first the specification of the midline and then specification of left/right. One model proposes the transfer of molecular asymmetry to the multicellular level. Nodal expression on the left side in mammals and chicks is a key event, and is due to the release of calcium on the left possibly involving an ion pump and the Notch pathway

  19. Asymmetric tandem organic solar cells (United States)

    Howells, Thomas J.

    where it is used to predict the short-circuit current (Jsc) generation of the sub-cells, which is not accessible experimentally. Current-matching is then used to predict the Jsc of the complete tandem device. . As a support to the optical modelling, ellipsometry measurements of thin films of ClAlPc are presented. These films of known thickness are analysed to extract the complex refractive index for use in optical modelling calculations. A dependence of the complex refractive index on film thickness and substrate is also noted. Finally, the external quantum efficiency (EQE) technique is considered as applied to solar cells, and an additional method is proposed to characterise current balancing in asymmetric tandem cells under illumination. This technique is verified experimentally by two separate sets of data..

  20. Alternative energy sources II; Proceedings of the Second Miami International Conference, Miami Beach, Fla., December 10-13, 1979. Volume 8 - Hydrogen energy (United States)

    Veziroglu, T. N.

    The book discusses the topics of electrolytic hydrogen production, thermochemical hydrogen production, solar hydrogen production, metal hydrides, and hydrogen utilization. Several papers are presented on the development status of the steam-iron process for hydrogen production, the production of hydrogen from carbonaceous materials, biophotolysis systems for hydrogen production, and heat transfer enhancement in metal hydride systems. Fixed site hydrogen storage is examined with a view to the applications impact, and a comparison of technologies and economics.

  1. Collocation method for the solution of the neutron transport equation with both symmetric and asymmetric scattering

    Energy Technology Data Exchange (ETDEWEB)

    Morel, J.E.


    A collocation method is developed for the solution of the one-dimensional neutron transport equation in slab geometry with both symmetric and polarly asymmetric scattering. For the symmetric scattering case, it is found that the collocation method offers a combination of some of the best characteristics of the finite-element and discrete-ordinates methods. For the asymmetric scattering case, it is found that the computational cost of cross-section data processing under the collocation approach can be significantly less than that associated with the discrete-ordinates approach. A general diffusion equation treating both symmetric and asymmetric scattering is developed and used in a synthetic acceleration algorithm to accelerate the iterative convergence of collocation solutions. It is shown that a certain type of asymmetric scattering can radically alter the asymptotic behavior of the transport solution and is mathematically equivalent within the diffusion approximation to particle transport under the influence of an electric field. The method is easily extended to other geometries and higher dimensions. Applications exist in the areas of neutron transport with highly anisotropic scattering (such as that associated with hydrogenous media), charged-particle transport, and particle transport in controlled-fusion plasmas. 23 figures, 6 tables.

  2. 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.

  3. Asymmetric similarity-weighted ensembles for image segmentation

    DEFF Research Database (Denmark)

    Cheplygina, V.; Van Opbroek, A.; Ikram, M. A.


    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...... and the direction of measurement needs to be chosen carefully. We also show that a point set similarity measure is robust across different studies, and outperforms state-of-the-art results on a multi-center brain tissue segmentation task....

  4. 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

  5. [Development of new methods in asymmetric reactions and their applications]. (United States)

    Node, Manabu


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

  6. Optical asymmetric watermarking using modified wavelet fusion and diffractive imaging (United States)

    Mehra, Isha; Nishchal, Naveen K.


    In most of the existing image encryption algorithms the generated keys are in the form of a noise like distribution with a uniform distributed histogram. However, the noise like distribution is an apparent sign indicating the presence of the keys. If the keys are to be transferred through some communication channels, then this may lead to a security problem. This is because; the noise like features may easily catch people's attention and bring more attacks. To address this problem it is required to transfer the keys to some other meaningful images to disguise the attackers. The watermarking schemes are complementary to image encryption schemes. In most of the iterative encryption schemes, support constraints play an important role of the keys in order to decrypt the meaningful data. In this article, we have transferred the support constraints which are generated by axial translation of CCD camera using amplitude-, and phase- truncation approach, into different meaningful images. This has been done by developing modified fusion technique in wavelet transform domain. The second issue is, in case, the meaningful images are caught by the attacker then how to solve the copyright protection. To resolve this issue, watermark detection plays a crucial role. For this purpose, it is necessary to recover the original image using the retrieved watermarks/support constraints. To address this issue, four asymmetric keys have been generated corresponding to each watermarked image to retrieve the watermarks. For decryption, an iterative phase retrieval algorithm is applied to extract the plain-texts from corresponding retrieved watermarks.

  7. Hydrogen as a fuel

    Energy Technology Data Exchange (ETDEWEB)


    A panel of the Committee on Advanced Energy Storage Systems of the Assembly of Engineering has examined the status and problems of hydrogen manufacturing methods, hydrogen transmission and distribution networks, and hydrogen storage systems. This examination, culminating at a time when rapidly changing conditions are having noticeable impact on fuel and energy availability and prices, was undertaken with a view to determining suitable criteria for establishing the pace, timing, and technical content of appropriate federally sponsored hydrogen R and D programs. The increasing urgency to develop new sources and forms of fuel and energy may well impact on the scale and timing of potential future hydrogen uses. The findings of the panel are presented. Chapters are devoted to hydrogen sources, hydrogen as a feedstock, hydrogen transport and storage, hydrogen as a heating fuel, automotive uses of hydrogen, aircraft use of hydrogen, the fuel cell in hydrogen energy systems, hydrogen research and development evaluation, and international hydrogen programs.

  8. 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.)

  9. Optical diode behavior of photonic crystal structure with asymmetric Kerr defect

    Institute of Scientific and Technical Information of China (English)


    Optical diode behavior of asymmetric one-dimensional photonic crystal with Kerr defect is numerically investigated using nonlinear transfer matrix method. In the linear case, the intensity and the phase of transmitted field are the same for the forward and backward operations. In the nonlinear case, however, the transmitted intensities are much different for the two operations, which display diode characteristic. Physical origin of the anisotropic transmission lies in the different localizations in the defect layer of the two operations.

  10. Manipulative Properties of Asymmetric Double Quantum Dots via Laser and Gate Voltage

    Institute of Scientific and Technical Information of China (English)

    ZHAO Shun-Cai; LIU Zheng-Dong


    We present a density matrix approach for the theoretical description of an asymmetric double quantum dot (QD) system. The results show that the properties of gain, absorption and dispersion of the double QD system, the population of the state with one hole in one dot and an electron in another dot transferred by tunneling can be manipulated by a laser pulse or gate voltage. Our scheme may demonstrate the possibility of electro-optical manipulation of quantum systems.

  11. Hydrogen and Storage Initiatives at the NASA JSC White Sands Test Facility (United States)

    Maes, Miguel; Woods, Stephen S.


    NASA WSTF Hydrogen Activities: a) Aerospace Test; b) System Certification & Verification; c) Component, System, & Facility Hazard Assessment; d) Safety Training Technical Transfer: a) Development of Voluntary Consensus Standards and Practices; b) Support of National Hydrogen Infrastructure Development.

  12. Dc SQUIDs with asymmetric shunt resistors

    Energy Technology Data Exchange (ETDEWEB)

    Rudolph, Matthias; Nagel, Joachim; Kemmler, Matthias; Koelle, Dieter; Kleiner, Reinhold [Physikalisches Institut - Experimentalphysik II and Center for Collective Quantum Phenomena in LISAplus, Universitaet Tuebingen (Germany); Meckbach, Johannes Maximilian; Ilin, Konstantin; Siegel, Michael [Institut fuer Mikro- und Nanoelektronische Systeme, Karlsruhe Institute of Technology, Karlsruhe (Germany)


    We have investigated asymmetrically shunted Nb/Al-AlO{sub x}/Nb dc SQUIDs. Simulations based on the coupled Langevin equations predict that the optimum energy resolution ε, and thus also the noise performance of such an asymmetric SQUID, can be 3-4 times better than that of its symmetric counterpart. While keeping the total resistance R identical to a comparable symmetric SQUID with R{sup -1} = R{sub 1}{sup -1} + R{sub 2}{sup -1}, we shunted only one of the two Josephson junctions with R = R{sub 1,2}/2. Both types of SQUIDs were characterized with respect to their transport and noise properties at temperature T = 4.2 K, and we compared the experimental results with numerical simulations. Experiments yielded ε ∼ 32 ℎ for an asymmetric SQUID with an inductance L = 22 pH, whereas a comparable symmetric device achieved ε = 110 ℎ.

  13. 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.

  14. Asymmetric gear rectifies random robot motion (United States)

    Li, He; Zhang, H. P.


    We experimentally study the dynamics of centimetric robots and their interactions with rotary gears through inelastic collisions. Under the impacts of self-propelled robots, a gear with symmetric teeth diffuses with no preferred direction of motion. An asymmetric gear, however, rectifies random motion of nearby robots which, in return, exert a torque on the gear and drive it into unidirectional motion. Rectification efficiency increases with the degree of gear asymmetry. Our work demonstrates that asymmetric environments can be used to rectify and extract energy from random motion of macroscopic self-propelled particles.

  15. Asymmetric catalysis with short-chain peptides. (United States)

    Lewandowski, Bartosz; Wennemers, Helma


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

  16. Asymmetric acoustic transmission in multiple frequency bands

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Hong-xiang, E-mail: [Research Center of Fluid Machinery Engineering and Technology, Jiangsu University, Zhenjiang 212013 (China); Laboratory of Modern Acoustics, Institute of Acoustics, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093 (China); State Key Laboratory of Acoustics, Institute of Acoustics, Chinese Academy of Sciences, Beijing 100190 (China); Yuan, Shou-qi, E-mail: [Research Center of Fluid Machinery Engineering and Technology, Jiangsu University, Zhenjiang 212013 (China); Zhang, Shu-yi [Laboratory of Modern Acoustics, Institute of Acoustics, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093 (China)


    We report both experimentally and numerically that the multi-band device of the asymmetric acoustic transmission is realized by placing two periodic gratings with different periods on both sides of two brass plates immersed in water. The asymmetric acoustic transmission can exist in four frequency bands below 1500 kHz, which arises from the interaction between various diffractions from the two gratings and Lamb modes in the brass plates immersed in water. The results indicate that the device has the advantages of multiple band, broader bandwidth, and simpler structure. Our finding should have great potential applications in ultrasonic devices.

  17. Integrated asymmetric vertical coupler pressure sensors (United States)

    Kiyat, Isa; Kocabas, Askin; Akcag, Imran; Aydinli, Atilla


    Design and analysis of a novel pressure sensor based on a silicon-on-insulator asymmetric integrated vertical coupler is presented. The coupler is composed of a single mode low index waveguide and a thin silicon slab. Wavelength selective optical modulation of asymmetric vertical coupler is examined in detail. Its potential for sensing applications is highlighted as an integrated optical pressure sensor which can be realized by standard silicon micro-fabrication. Sensitivity of transmission of such couplers on refractive index change of silicon slab ensures that they are good candidates for applications requiring high sensitivities.

  18. Asymmetric localization in disordered Landau bands

    Energy Technology Data Exchange (ETDEWEB)

    Nita, M [Institute of Physics and Technology of Materials, PO Box MG7, Bucharest-Magurele (Romania); Aldea, A [Institute of Physics and Technology of Materials, PO Box MG7, Bucharest-Magurele (Romania); Zittartz, J [Institute of Theoretical Physics, Cologne University, 50937 Cologne (Germany)


    We show that, due to band mixing, the eigenstate localization within the disordered Landau bands gets an asymmetric structure: the degree of localization increases in the lower part of the band and decreases in the upper one. The calculation is performed for a two-dimensional lattice with the Anderson disorder potential and we prove that this effect is related to the upper shift of the extended states within the band and is enhanced by the disorder strength. The asymmetric localization and the energy shift disappear when the interband coupling is switched off.

  19. 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.

  20. Palladium catalysed asymmetric alkylation of benzophenone Schiff base glycine esters in ionic liquids

    Indian Academy of Sciences (India)

    Dae Hyun Kim; Jin Kyu Im; Dae Won Kim; Minserk Cheong; Hoon Sik Kim; Deb Kumar Mukherjee


    Asymmetric alkyl substitution of various benzophenone Schiff base substrates under biphasic conditions proceeded using optically active Palladium(II) complexes. The corresponding products were obtained in high yields but with moderate enantiomeric excess (ee). Addition of specific ionic liquids to the reaction medium enhanced reactivity and selectivity for phase transfer catalytic (PTC) glycine alkylation. It has been found that there is an anionic influence of the ionic liquids that modify the steric environment around the enolate ion. A computer-assisted molecular design of enantioselective phase-transfer catalysis with the palladium complex and the ionic liquid has been done.