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Sample records for atom transfer reactions

  1. Hydrogen-Atom Transfer Reactions.

    Science.gov (United States)

    Wang, Liang; Xiao, Jian

    2016-04-01

    The cascade [1,n]-hydrogen transfer/cyclization, recognized as the tert-amino effect one century ago, has received considerable interest in recent decades, and great achievements have been made. With the aid of this strategy, the inert C(sp(3))-H bonds can be directly functionalized into C-C, C-N, C-O bonds under catalysis of Lewis acids, Brønsted acids, as well as organocatalysts, and even merely under thermal conditions. Hydrogen can be transferred intramolecularly from hydrogen donor to acceptor in the form of hydride, or proton, followed by cyclization to furnish the cyclic products in processes featuring high atom economy. Methylene/methine adjacent to heteroatoms, e.g., nitrogen, oxygen, sulfur, can be exploited as hydride donor as well as methylene/methine without heteroatom assistance. Miscellaneous electrophilic subunits or intermediates, e.g., alkylidene malonate, carbophilic metal activated alkyne or allene, α,β-unsaturated aldehydes/ketone, saturated aldehydes/iminium, ketenimine/carbodiimide, metal carbenoid, electron-withdrawing groups activated allene/alkyne, in situ generated carbocation, can serve as hydride acceptors. This methodology has shown preeminent power to construct 5-, 6-, or 7-membered heterocyclic as well as carbon rings. In this chapter, various hydrogen donors and acceptors are adequately discussed. PMID:27573142

  2. Two-nucleon transfer reactions uphold supersymmetry in atomic nuclei

    OpenAIRE

    Barea, J.; Bijker, R.; Frank, A.

    2004-01-01

    The spectroscopic strengths of two-nucleon transfer reactions constitute a stringent test for two-nucleon correlations in the nuclear wave functions. A comparison between the recently measured 198Hg(d,alpha)196Au reaction and the predictions from the nuclear quartet supersymmetry lends further support to the validity of supersymmetry in nuclear physics.

  3. In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes.

    Science.gov (United States)

    Lee, Juneyoung; Grandner, Jessica M; Engle, Keary M; Houk, K N; Grubbs, Robert H

    2016-06-01

    Ruthenium benzylidene complexes are well-known as olefin metathesis catalysts. Several reports have demonstrated the ability of these catalysts to also facilitate atom transfer radical (ATR) reactions, such as atom transfer radical addition (ATRA) and atom transfer radical polymerization (ATRP). However, while the mechanism of olefin metathesis with ruthenium benzylidenes has been well-studied, the mechanism by which ruthenium benzylidenes promote ATR reactions remains unknown. To probe this question, we have analyzed seven different ruthenium benzylidene complexes for ATR reactivity. Kinetic studies by (1)H NMR revealed that ruthenium benzylidene complexes are rapidly converted into new ATRA-active, metathesis-inactive species under typical ATRA conditions. When ruthenium benzylidene complexes were activated prior to substrate addition, the resulting activated species exhibited enhanced kinetic reactivity in ATRA with no significant difference in overall product yield compared to the original complexes. Even at low temperature, where the original intact complexes did not catalyze the reaction, preactivated catalysts successfully reacted. Only the ruthenium benzylidene complexes that could be rapidly transformed into ATRA-active species could successfully catalyze ATRP, whereas other complexes preferred redox-initiated free radical polymerization. Kinetic measurements along with additional mechanistic and computational studies show that a metathesis-inactive ruthenium species, generated in situ from the ruthenium benzylidene complexes, is the active catalyst in ATR reactions. Based on data from (1) H, (13)C, and (31)P NMR spectroscopy and X-ray crystallography, we suspect that this ATRA-active species is a RuxCly(PCy3)z complex.

  4. Single-collision studies of hot atom energy transfer and chemical reaction

    International Nuclear Information System (INIS)

    This report discusses research in the collision dynamics of translationally hot atoms, with funding with DOE for the project ''Single-Collision Studies of Hot Atom Energy Transfer and Chemical Reaction,'' Grant Number DE-FG03-85ER13453. The work reported here was done during the period September 9, 1988 through October 31, 1991. During this period this DOE-funded work has been focused on several different efforts: (1) experimental studies of the state-to-state dynamics of the H + RH → H2 R reactions where RH is CH4, C2H6, or C3H8, (2) theoretical (quasiclassical trajectory) studies of hot hydrogen atom collision dynamics, (3) the development of photochemical sources of translationally hot molecular free radicals and characterization of the high resolution CARS spectroscopy of molecular free radicals, (4) the implementation of stimulated Raman excitation (SRE) techniques for the preparation of vibrationally state-selected molecular reactants

  5. Electron transfer and multi-atom abstraction reactions between atomic metal anions and NO, NO2 and SO2

    Science.gov (United States)

    Butson, J. M.; Curtis, S.; Mayer, P. M.

    2016-05-01

    The atomic metal anions Fe-, Cs-, Cu- and Ag- were reacted with NO, NO2 and SO2 to form intact NO-, NO2- and SO2- with no fragmentation. Yields for the molecular anions ranged from 4 to 97% and were found to correlate to the exothermicity of the electron transfer process. Sequential oxygen atom extraction was found to take place between the metal anions and NO and NO2. Reactions between NO2 and Fe- resulted in FeO-, FeO2- and FeO3- while reactions of Cu- with NO2 resulted in CuO- and CuO2-. Reactions of Cu- and Ag- with NO resulted in CuO- and AgO- respectively.

  6. Electron transfer reactions

    CERN Document Server

    Cannon, R D

    2013-01-01

    Electron Transfer Reactions deals with the mechanisms of electron transfer reactions between metal ions in solution, as well as the electron exchange between atoms or molecules in either the gaseous or solid state. The book is divided into three parts. Part 1 covers the electron transfer between atoms and molecules in the gas state. Part 2 tackles the reaction paths of oxidation states and binuclear intermediates, as well as the mechanisms of electron transfer. Part 3 discusses the theories and models of the electron transfer process; theories and experiments involving bridged electron transfe

  7. In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes.

    Science.gov (United States)

    Lee, Juneyoung; Grandner, Jessica M; Engle, Keary M; Houk, K N; Grubbs, Robert H

    2016-06-01

    Ruthenium benzylidene complexes are well-known as olefin metathesis catalysts. Several reports have demonstrated the ability of these catalysts to also facilitate atom transfer radical (ATR) reactions, such as atom transfer radical addition (ATRA) and atom transfer radical polymerization (ATRP). However, while the mechanism of olefin metathesis with ruthenium benzylidenes has been well-studied, the mechanism by which ruthenium benzylidenes promote ATR reactions remains unknown. To probe this question, we have analyzed seven different ruthenium benzylidene complexes for ATR reactivity. Kinetic studies by (1)H NMR revealed that ruthenium benzylidene complexes are rapidly converted into new ATRA-active, metathesis-inactive species under typical ATRA conditions. When ruthenium benzylidene complexes were activated prior to substrate addition, the resulting activated species exhibited enhanced kinetic reactivity in ATRA with no significant difference in overall product yield compared to the original complexes. Even at low temperature, where the original intact complexes did not catalyze the reaction, preactivated catalysts successfully reacted. Only the ruthenium benzylidene complexes that could be rapidly transformed into ATRA-active species could successfully catalyze ATRP, whereas other complexes preferred redox-initiated free radical polymerization. Kinetic measurements along with additional mechanistic and computational studies show that a metathesis-inactive ruthenium species, generated in situ from the ruthenium benzylidene complexes, is the active catalyst in ATR reactions. Based on data from (1) H, (13)C, and (31)P NMR spectroscopy and X-ray crystallography, we suspect that this ATRA-active species is a RuxCly(PCy3)z complex. PMID:27186790

  8. Excited state intramolecular charge transfer reaction of 4-(morpholenyl) benzonitrile in solution: Effects of hetero atom in the donor moiety

    Indian Academy of Sciences (India)

    Tuhin Pradhan; Harun Al Rasid Gazi; Ranjit Biswas

    2010-07-01

    An intramolecular charge transfer (ICT) molecule with an extra hetero atom in its donor moiety has been synthesized in order to investigate how ICT reaction is affected by hetero atom replacement. Photo-physical and photo-dynamical properties of this molecule, 4-(morpholenyl)benzonitrile (M6C), have been studied in 20 different solvents. The correlation between the reaction driving force (- ) and activation barrier ( #) has been explored in order to understand the solvent effects (static and dynamic) on the photo-excited ICT reaction in this molecule. A Kramer’s model analysis of the experimentally observed reaction rate constants indicates a solvent-averaged activation barrier of ∼ 4 in the absence of solvent dynamical control. The reaction in M6C is therefore not a barrier-less reaction but close to the limit where conventional kinetics might break down.

  9. Synthesis, characterisation, and oxygen atom transfer reactions involving the first gold(I)-alkylperoxo complexes.

    Science.gov (United States)

    Collado, Alba; Gómez-Suárez, Adrián; Oonishi, Yoshihiro; Slawin, Alexandra M Z; Nolan, Steven P

    2013-11-25

    The synthesis of a new class of organogold species containing a peroxo moiety is reported. Complexes [Au(IPr)(OO(t)Bu)] and [Au(SIPr)(OO(t)Bu)] have been synthesised via a straightforward methodology using the parent gold(I) hydroxide complexes as synthons. These complexes have been successfully used in oxygen-transfer reactions to triphenylphosphine.

  10. Steric effect for proton, hydrogen-atom, and hydride transfer reactions with geometric isomers of NADH-model ruthenium complexes.

    Science.gov (United States)

    Cohen, Brian W; Polyansky, Dmitry E; Achord, Patrick; Cabelli, Diane; Muckerman, James T; Tanaka, Koji; Thummel, Randolph P; Zong, Ruifa; Fujita, Etsuko

    2012-01-01

    Two isomers, [Ru(1)]2+ (Ru = Ru(bpy)2, bpy = 2,2'-bipyridine, 1 = 2-(pyrid-2'-yl)-1-azaacridine) and [Ru(2)]2+ (2 = 3-(pyrid-2'-yl)-4-azaacridine), are bioinspired 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-C1 complexes and/or carbon dioxide. While it has been shown that the structural differences between the azaacridine ligands of [Ru(1)]2+ and [Ru(2)]2+ have a significant effect on the mechanism of formation of the hydride donors, [Ru(1HH)]2+ and [Ru(2HH)]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*-)] in aprotic and even protic media is slow compared to that of [Ru(1*-)]+. The net hydrogen-atom transfer between *[Ru(1)]2+ and hydroquinone (H2Q) proceeds by one-step EPT, rather than stepwise electron-proton transfer. Such a reaction was not observed for *[Ru(2)]2+ because the non-coordinated N atom is not easily available for an interaction with H2Q. Finally, the rate of the net hydride ion transfer from [Ru(1HH)]2+ to [Ph3C]+ is significantly slower than that of [Ru (2HH)]2+ owing to steric congestion at the donor site. PMID:22470971

  11. Novel ionic liquids as reaction medium for atom transfer radical polymerization of methyl methacrylate

    Institute of Scientific and Technical Information of China (English)

    Guo Qiao Lai; Fu Min Ma; Zi Qiang Hu; Hua Yu Qiu; Jian Xiong Jiang; Ji Rong Wu; Li Min Chen; Lian Bin Wu

    2007-01-01

    Atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) employing ethyl 2-bromoisobutyrate (EBiB)/CuBr as the initiating system was investigated at 50 ℃ in the absence of any additional ligand in the three room temperature ionic liquids (RTILs), 1-methyl-imidazolium acetate ([mim][CH3COO]), 1-methylimidazolium propionate ([mim][CH3CH2COO]) and 1-methylimidazolium butyrate ([mim] [CH3CH2CH2COO]), respectively. All the polymerization in the three RTILs proceeded in a well-controlled manner. The sequence of the apparent polymerization rate constants was kapp([mim][CH3COO]) > kapp([mim][CH3CH2COO]) > kapp ([mim][CH3CH2CH2COO]).

  12. Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium–arene complexes

    Directory of Open Access Journals (Sweden)

    Yannick Borguet

    2010-12-01

    Full Text Available The tandem catalysis of ring-closing metathesis/atom transfer radical reactions was investigated with the homobimetallic ruthenium–indenylidene complex [(p-cymeneRu(μ-Cl3RuCl(3-phenyl-1-indenylidene(PCy3] (1 to generate active species in situ. The two catalytic processes were first carried out independently in a case study before the whole sequence was optimized and applied to the synthesis of several polyhalogenated bicyclic γ-lactams and lactones from α,ω-diene substrates bearing trihaloacetamide or trichloroacetate functionalities. The individual steps were carefully monitored by 1H and 31P NMR spectroscopies in order to understand the intimate details of the catalytic cycles. Polyhalogenated substrates and the ethylene released upon metathesis induced the clean transformation of catalyst precursor 1 into the Ru(II–Ru(III mixed-valence compound [(p-cymeneRu(μ-Cl3RuCl2(PCy3], which was found to be an efficient promoter for atom transfer radical reactions under the adopted experimental conditions.

  13. Multinucleon transfer reactions

    International Nuclear Information System (INIS)

    Nuclear reactions induced by complex nuclei are studied. The description of the single neutron transfer is used to show some aspect of the theoretical treatment of transfer reactions and rules concerning the dependence of cross sections on quantum numbers of the initial and final channels are deduced. Strongly excited states of 20Ne, 19F, sup(16,17)0, 15N were studied experimentally by using different projectile-target combinations in the four-particle, eight-particle and ten-particle transfer reactions, leading to the some final nuclei. Obtained results are discussed. In addition, studies of the projectile break-up phenomenon were performed. The dissociation of 6Li and 7Li projectiles was investigated in reactions on Pb, Sn and Ni nuclei. These nuclei were chosen to allow measurements at one incident energy below, above and at the Coulomb barrier. The observed spectra indicate that the process proceeds primarily via the resonance level but the shape deviates from the shape which was calculated assuming isotropic decay of the excited 6Li in its center of mass system. The investigations of the elastic scattering turned out to be more fruitful and allowed to define better the Coulomb barrier for the 6Li-target system. (S.B.)

  14. 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.

    2012-01-01

    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.

  15. Mass Transfer with Chemical Reaction.

    Science.gov (United States)

    DeCoursey, W. J.

    1987-01-01

    Describes the organization of a graduate course dealing with mass transfer, particularly as it relates to chemical reactions. Discusses the course outline, including mathematics models of mass transfer, enhancement of mass transfer rates by homogeneous chemical reaction, and gas-liquid systems with chemical reaction. (TW)

  16. Efficient transfer of francium atoms

    Science.gov (United States)

    Aubin, Seth; Behr, John; Gorelov, Alexander; Pearson, Matt; Tandecki, Michael; Collister, Robert; Gwinner, Gerald; Shiells, Kyle; Gomez, Eduardo; Orozco, Luis; Zhang, Jiehang; Zhao, Yanting; FrPNC Collaboration

    2016-05-01

    We report on the progress of the FrPNC collaboration towards Parity Non Conservation Measurements (PNC) using francium atoms at the TRIUMF accelerator. We demonstrate efficient transfer (higher than 40%) to the science vacuum chamber where the PNC measurements will be performed. The transfer uses a downward resonant push beam from the high-efficiency capture magneto optical trap (MOT) towards the science chamber where the atoms are recaptured in a second MOT. The transfer is very robust with respect to variations in the parameters (laser power, detuning, alignment, etc.). We accumulate a growing number of atoms at each transfer pulse (limited by the lifetime of the MOT) since the push beam does not eliminate the atoms already trapped in the science MOT. The number of atoms in the science MOT is on track to meet the requirements for competitive PNC measurements when high francium rates (previously demonstrated) are delivered to our apparatus. The catcher/neutralizer for the ion beam has been tested reliably to 100,000 heating/motion cycles. We present initial tests on the direct microwave excitation of the ground hyperfine transition at 45 GHz. Support from NSERC and NRC from Canada, NSF and Fulbright from USA, and CONACYT from Mexico.

  17. The Molybdenum Active Site of Formate Dehydrogenase Is Capable of Catalyzing C-H Bond Cleavage and Oxygen Atom Transfer Reactions.

    Science.gov (United States)

    Hartmann, Tobias; Schrapers, Peer; Utesch, Tillmann; Nimtz, Manfred; Rippers, Yvonne; Dau, Holger; Mroginski, Maria Andrea; Haumann, Michael; Leimkühler, Silke

    2016-04-26

    Formate dehydrogenases (FDHs) are capable of performing the reversible oxidation of formate and are enzymes of great interest for fuel cell applications and for the production of reduced carbon compounds as energy sources from CO2. Metal-containing FDHs in general contain a highly conserved active site, comprising a molybdenum (or tungsten) center coordinated by two molybdopterin guanine dinucleotide molecules, a sulfido and a (seleno-)cysteine ligand, in addition to a histidine and arginine residue in the second coordination sphere. So far, the role of these amino acids in catalysis has not been studied in detail, because of the lack of suitable expression systems and the lability or oxygen sensitivity of the enzymes. Here, the roles of these active site residues is revealed using the Mo-containing FDH from Rhodobacter capsulatus. Our results show that the cysteine ligand at the Mo ion is displaced by the formate substrate during the reaction, the arginine has a direct role in substrate binding and stabilization, and the histidine elevates the pKa of the active site cysteine. We further found that in addition to reversible formate oxidation, the enzyme is further capable of reducing nitrate to nitrite. We propose a mechanistic scheme that combines both functionalities and provides important insights into the distinct mechanisms of C-H bond cleavage and oxygen atom transfer catalyzed by formate dehydrogenase. PMID:27054466

  18. Transfer reactions in nuclear astrophysics

    Science.gov (United States)

    Bardayan, D. W.

    2016-08-01

    To a high degree many aspects of the large-scale behavior of objects in the Universe are governed by the underlying nuclear physics. In fact the shell structure of nuclear physics is directly imprinted into the chemical abundances of the elements. The tranquility of the night sky is a direct result of the relatively slow rate of nuclear reactions that control and determines a star’s fate. Understanding the nuclear structure and reaction rates between nuclei is vital to understanding our Universe. Nuclear-transfer reactions make accessible a wealth of knowledge from which we can extract much of the required nuclear physics information. A review of transfer reactions for nuclear astrophysics is presented with an emphasis on the experimental challenges and opportunities for future development.

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

    International Nuclear Information System (INIS)

    Highlights: ► Both 1,1-diphenyl-2-picrylhydrazyl radical and its product measurement by HPLC. ► Lowest limit of detection by monitoring 1,1-diphenyl-2-picryl-hydrazine. ► Adsorption problem of the radical on HPLC parts have been pointed out. - Abstract: 1,1-Diphenyl-2-picrylhydrazyl (DPPH·) 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· 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· quenching rate and none of them permits to identify and measure 1,1-diphenyl-2-picryl-hydrazine (DPPH-H), the reduced product of DPPH· resulting from hydrogen atom transfer (HAT), which is the main mechanism of the reaction between DPPH· and AOs. We presently report an HPLC method devoted to the simultaneous measurement of DPPH· 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· onto materials of the HPLC system was pointed out. Consequently, the linearity range observed for DPPH· was restricted, thus a much lower limit of detection was obtained for DPPH-H than for DPPH· using standards (0.02 and 14 μM, respectively). The method was applied to three commonly used AOs, i.e. Trolox®, 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 higher selectivity than colorimetry, and (ii) its help to investigate the mechanisms occurring with the free radical.

  20. Kinetics of elementary atom and radical reactions

    International Nuclear Information System (INIS)

    During the past three years we have been working on four problems in the general area of gas phase kinetics and energy transfer of small molecules. These are: (1) measurements of the fine structure populations of ground state oxygen atoms produced in photodissociation reactions; (2) quenching of the Rydberg B (1Σ+) state of CO; (3) vibrational relaxation of highly excited molecules; and (4) kinetics of hydrogen molecules. The first two topics, which involve transitions between different electronic states of the parent molecule, are a departure from our previous research interests. In the accompanying renewal proposal we discuss plans to pursue these new topics vigorously during the coming year. The third topic is a continuation of our long interest in the energy dependence of the rates laws governing vibrational-to-translational energy transfer of molecules having large initial amounts of vibrational excitation. The final topic is a continuation of our studies of the reaction of O(3P) + H2. In this work we measured the rate constant for the reaction O(3P) with deuterium and also analyzed spectroscopically different sources of vibrationally excited hydrogen for possible future work. We discuss each of these four studies in the following sections

  1. 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: pierre.leroy@pharma.uhp-nancy.fr [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France)

    2012-01-20

    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

  2. Heavy atom isotope effects on enzymatic reactions

    Science.gov (United States)

    Paneth, Piotr

    1994-05-01

    The theory of isotope effects, which has proved to be extremely useful in providing geometrical details of transition states in a variety of chemical reactions, has recently found an application in studies of enzyme-catalyzed reactions. These reactions are multistep in nature with few steps being partially rate-limiting, thus interpretation of these isotope effects is more complex. The theoretical framework of heavy-atom isotope effects on enzymatic reactions is critically analyzed on the basis of recent results of: carbon kinetic isotope effects on carbonic anhydrase and catalytic antibodies; multiple carbon, deuterium isotope effects on reactions catalyzed by formate decarboxylase; oxygen isotope effects on binding processes in reactions catalyzed by pyruvate kinase; and equilibrium oxygen isotope effect on binding an inhibitor to lactate dehydrogenase. The advantages and disadvantages of reaction complexity in learning details of formal and molecular mechanisms are discussed in the examples of reactions catalyzed by phosphoenolpyruvate carboxylase, orotidine decarboxylase and glutamine synthetase.

  3. H原子与CO2分子碰撞的化学反应与能量转移%Chemical Reaction and Energy Transfer Between Hot H Atoms and CO2 Molecules

    Institute of Scientific and Technical Information of China (English)

    石从云; 任丽; 孔繁敖

    2006-01-01

    用时间分辨傅立叶红外发射光谱的方法对H原子与CO2分子的碰撞动力学进行了实验研究.用紫外激光光解的方法分别制备出三个不同平动能为174.7、241.0和306.2 kJ/mol的氢原子,并引发H+CO2→OH+CO反应.观察到了反应的产物,即振动激发的CO(v≤2).同时也看到了在H原子与CO2分子的碰撞中发生高效的T-V能量转移.CO2的反对称伸缩模的最高振动能级为v=4化学反应与能量转移的速率之比大约为10.%Collisions between hot H atoms and CO2 molecules were studied experimentally by time-resolved Fourier transform infrared emission spectroscopy. H atoms with three translational energies, 174.7, 241.0 and 306.2 kJ/mol respectively, were generated by UV laser photolysis to initiate a chemical reaction of H+CO2→OH+CO. Vibrationally excited CO (v≤2) was observed in the spectrum, where CO was the prod uct of the reaction. The highly efficient T-V energy transfer from the hot H atoms to the CO2 was verified too. The highest vibrational level of v=4 in CO2 (v3) was found. Rate ratio of the chemical reaction to the energy transfer was estimated as 10.

  4. Proton transfer reaction - mass spectrometry

    International Nuclear Information System (INIS)

    Proton transfer reaction mass spectrometry (PTR-MS) provides on-line monitoring of volatile organic compounds (VOCs) with a low detection threshold and a fast response time. Commercially available set-ups are usually based on quadrupole analysers but recently new instruments based on time-of-flight (PTR-ToF-MS) analysers have been proposed and commercialized. PTR-MS has been successfully applied to a variety of fields including environmental science, food science and technology, plant physiology and medical science. Many new challenges arise from the newly available PTR-ToF-MS instruments, ranging from mass calibration and absolute VOC concentration determination to data mining and sample classification. This thesis addresses some of these problems in a coherent framework. Moreover, relevant applications in food science and technology are presented. It includes twelve papers published in peer reviewed journals. Some of them address methodological issues regarding PTR-ToF-MS; the others contain applicative studies of PTR-ToF-MS to food science and technology. Among them, there are the first two published applications of PTR-ToF-MS in this field. (author)

  5. Action of Mercaptan and Disulfide in Hydrogen Atom Exchange Reactions

    International Nuclear Information System (INIS)

    Free- radical, photochemical, and high-energy radiation-induced reactions may be catalysed or inhibited by rapid hydrogen atom exchange reactions of mercaptans and disulfides. The radical-induced, light-initiated, and benzophenone-sensitized decarbonylations of aldehydes are catalysed by mercaptans. The chain-propagating hydrogen transfer reaction, R' + RCH = O -> RH + RC = O , is made more rapid by a similar sequence of hydrogen atom transfers involving the sulfur compound: R' + C6H5CH2SH -> RH + C6H5CH2S'; C6H5CH2S + RCH = 0 -> C6H5CH2SH + RC = 0. The photoreduction of benzophenone in 2-propanol leads to benzpinacol by a non-chain reaction via the radicals (C6H5)2C-OH and (CH3)2COH. The reaction is retarded and inhibited by mercaptan and disulfide, which reconvert the radicals to the starting materials by rapid hydrogen transfer reactions and are themselves regenerated in their alternate valence states, each molecule of sulfur compound negating the chemical consequences of many quanta: (C6H5)2C-OH + AS' -> (C6H5)2C = O + ASH; (CH3)2C-OH + ASH -> (CH3)2C = 0 + AS'. Proof of the mechanism is found in: equilibration of initially present mercaptan or disulfide during inhibition; in racemization of optically active alcohol during inhibition; in deuterium exchange during inhibition. Similar inhibition is seen when only one intermediate radical is formed, as in the benzophenone- benzhydrol and acetophenone-α-methyl-benzyl alcohol systems. Inhibition by sulfur compounds, by the same mechanism, is found in the 60Co γ-ray induced conversion of benzophenone to benzpinacol; naphthalene has no protecting effect on benzophenone in the 60Co system, while quenching the photochemical reaction. The protection by sulfur compounds of solutes against radiation damage thus results from hydrogen atom transfer reactions. The photoreduction of benzophenone in an ether is also inhibited by the sulfur compounds, by hydrogen atom transfer reactions. A mechanism exists in this system

  6. The atomic and molecular reaction statics

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    This work presents a new science called atomic and molecular reaction statics (AMRS). There are four parts for AMRS, i.e. the group theoretical derivation of molecular electronic states, the principle of microscopic reversibility, the principle of microscopic transitivity and the optimum energy process rule. AMRS has been developed for about twenty years.

  7. Primary reactions of recoiling germanium atoms

    International Nuclear Information System (INIS)

    75Ge recoils are made using the (n,2n) reaction. By analogy with Si recoils, two divalent species are suggested as intermediates in the recoil-germane reaction, one formed by H abstraction and the other formed by insertion only. A series of moderator and competition experiments were conducted. Of the noble gases, Kr is the most efficient moderator at removing kinetic energy from the recoils. Xe has a special effect due to its low ionization potential. A reaction scheme is proposed with two routes to digermane, one from a hot neutral atom and the other from a positive ion. 8 figures

  8. A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity.

    Science.gov (United States)

    Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

    2015-10-14

    While diabatic approaches are ubiquitous for the understanding of electron-transfer reactions and have been mooted as being of general relevance, alternate applications have not been able to unify the same wide range of observed spectroscopic and kinetic properties. The cause of this is identified as the fundamentally different orbital configurations involved: charge-transfer phenomena involve typically either 1 or 3 electrons in two orbitals whereas most reactions are typically closed shell. As a result, two vibrationally coupled electronic states depict charge-transfer scenarios whereas three coupled states arise for closed-shell reactions of non-degenerate molecules and seven states for the reactions implicated in the aromaticity of benzene. Previous diabatic treatments of closed-shell processes have considered only two arbitrarily chosen states as being critical, mapping these states to those for electron transfer. We show that such effective two-state diabatic models are feasible but involve renormalized electronic coupling and vibrational coupling parameters, with this renormalization being property dependent. With this caveat, diabatic models are shown to provide excellent descriptions of the spectroscopy and kinetics of the ammonia inversion reaction, proton transfer in N2H7(+), and aromaticity in benzene. This allows for the development of a single simple theory that can semi-quantitatively describe all of these chemical phenomena, as well as of course electron-transfer reactions. It forms a basis for understanding many technologically relevant aspects of chemical reactions, condensed-matter physics, chemical quantum entanglement, nanotechnology, and natural or artificial solar energy capture and conversion.

  9. Transferable basis sets of numerical atomic orbitals

    NARCIS (Netherlands)

    M.J. Louwerse; G. Rothenberg

    2012-01-01

    We show that numerical atomic orbital basis sets that are variationally optimized for specific compounds are biased and not fully transferable to other compounds. The situation improves when the basis sets are optimized for several compounds and a compromise is made. We demonstrate this for basis se

  10. Atom addition reactions in interstellar ice analogues

    CERN Document Server

    Linnartz, Harold; Fedoseev, Gleb

    2015-01-01

    This review paper summarizes the state-of-the-art in laboratory based interstellar ice chemistry. The focus is on atom addition reactions, illustrating how water, carbon dioxide and methanol can form in the solid state at astronomically relevant temperatures, and also the formation of more complex species such as hydroxylamine, an important prebiotic molecule, and glycolaldehyde, the smallest sugar, is discussed. These reactions are particularly relevant during the dark ages of star and planet formation, i.e., when the role of UV light is restricted. A quantitative characterization of such processes is only possible through dedicated laboratory studies, i.e., under full control of a large set of parameters such as temperature, atom-flux, and ice morphology. The resulting numbers, physical and chemical constants, e.g., barrier heights, reaction rates and branching ratios, provide information on the molecular processes at work and are needed as input for astrochemical models, in order to bridge the timescales t...

  11. Variation of kinetic isotope effect in multiple proton transfer reactions

    Indian Academy of Sciences (India)

    B Saritha; M Durga Prasad

    2012-01-01

    Recently, we had suggested that the motion along the promoter mode in the first part of the IRC of proton transfer reaction enhances the delocalization of electrons on the acceptor atom into the * orbital of the donor-hydrogen covalent bond, and as a consequence weakens it. This leads to a reduction of the barrier to the proton transfer as well as the stretching frequency of donor-hydrogen bond. An extension of this to the concerted multiple proton transfer reactions implies that the kinetic isotope effect in such reaction depends exponentially on the number of protons that are being transferred. Computational evidence on three systems, (HF)3, formic acid dimer, and (H2O) clusters is provided to support this assertion.

  12. Chain reaction. History of the atomic bomb

    International Nuclear Information System (INIS)

    Henri becquerel tracked down in 1896 a strange radiation, which was called radioactivity by Marie Curie. In the following centuries German scientists Max Planck, Albert Einstein and Werner Heisenberg presented fundamental contributions to understand processes in the atomic nucleus. At Goettingen, center of the international nuclear physics community, the American student J. Robert Oppenheimer admit to this physical research. In the beginning of 1939 the message of Otto Hahns' nuclear fission electrified researchers. The first step, unleashing atomic energy, was done. A half year later the Second World War begun. And suddenly being friend with and busily communicating physicians were devided into hostile power blocs as bearers of official secrets. The author tells in this exciting book the story of the first atomic bomb as a chain reaction of ideas, discoveries and visions, of friendships, jealousy and intrigues of scientists, adventurers and genius. (orig./GL)

  13. Thermally-generated reactive intermediates: Trapping of the parent ferrocene-based o-quinodimethane and reactions of diradicals generated by hydrogen-atom transfers

    International Nuclear Information System (INIS)

    Ferrocenocyclobutene is prepared by flash vacuum pyrolysis (FVP) of the N-amino-2-phenylaziridine hydrazone of 2-methylferrocenealdehyde. In the second section of this dissertation, a series of hydrocarbon rearrangements were observed. FVP of o-allyltoluene at 0.1 Torr (700--900 C) gives 2-methylindan and indene, accompanied by o-propenyltoluene. FVP of 2-methyl-2'-vinylbiphenyl gives 9-methyl-9,10-dihydrophenanthrene, which fits the proposed mechanism. However, FVP of 2-(o-methylbenzyl)styrene gives mainly anthracene and 1-methylanthracene. This cyclization reaction was also successful with o-allylphenol and o-(2-methylallyl)phenol

  14. Atoms of multistationarity in chemical reaction networks

    CERN Document Server

    Joshi, Badal

    2011-01-01

    Chemical reaction networks taken with mass-action kinetics are dynamical systems that arise in chemical engineering and systems biology. Deciding whether a chemical reaction network admits multiple positive steady states is to determine existence of multiple positive solutions to a system of polynomials with unknown coefficients. In this work, we consider the question of whether the minimal (in a precise sense) networks, which we propose to call `atoms of multistationarity,' characterize the entire set of multistationary networks. We show that if a subnetwork admits multiple nondegenerate positive steady states, then these steady states can be extended to establish multistationarity of a larger network, provided that the two networks share the same stoichiometric subspace. Our result provides the mathematical foundation for a technique used by Siegal-Gaskins et al. of establishing bistability by way of `network ancestry.' Here, our main application is for enumerating small multistationary continuous-flow stir...

  15. Radical and Atom Transfer Halogenation (RATH): A Facile Route for Chemical and Polymer Functionalization.

    Science.gov (United States)

    Han, Yi-Jen; Lin, Chia-Yu; Liang, Mong; Liu, Ying-Ling

    2016-05-01

    This work demonstrates a new halogenation reaction through sequential radical and halogen transfer reactions, named as "radical and atom transfer halogenation" (RATH). Both benzoxazine compounds and poly(2,6-dimethyl-1,4-phenylene oxide) have been demonstrated as active species for RATH. Consequently, the halogenated compound becomes an active initiator of atom transfer radical polymerization. Combination of RATH and sequential ATRP provides an convenient and effective approach to prepare reactive and crosslinkable polymers. The RATH reaction opens a new window both to chemical synthesis and molecular design and preparation of polymeric materials.

  16. Transfer reaction code with nonlocal interactions

    CERN Document Server

    Titus, L J; Nunes, F M

    2016-01-01

    We present a suite of codes (NLAT for nonlocal adiabatic transfer) to calculate the transfer cross section for single-nucleon transfer reactions, $(d,N)$ or $(N,d)$, including nonlocal nucleon-target interactions, within the adiabatic distorted wave approximation. For this purpose, we implement an iterative method for solving the second order nonlocal differential equation, for both scattering and bound states. The final observables that can be obtained with NLAT are differential angular distributions for the cross sections of $A(d,N)B$ or $B(N,d)A$. Details on the implementation of the T-matrix to obtain the final cross sections within the adiabatic distorted wave approximation method are also provided. This code is suitable to be applied for deuteron induced reactions in the range of $E_d=10-70$ MeV, and provides cross sections with $4\\%$ accuracy.

  17. Transfer reaction code with nonlocal interactions

    Science.gov (United States)

    Titus, L. J.; Ross, A.; Nunes, F. M.

    2016-10-01

    We present a suite of codes (NLAT for nonlocal adiabatic transfer) to calculate the transfer cross section for single-nucleon transfer reactions, (d , N) or (N , d) , including nonlocal nucleon-target interactions, within the adiabatic distorted wave approximation. For this purpose, we implement an iterative method for solving the second order nonlocal differential equation, for both scattering and bound states. The final observables that can be obtained with NLAT are differential angular distributions for the cross sections of A(d , N) B or B(N , d) A. Details on the implementation of the T-matrix to obtain the final cross sections within the adiabatic distorted wave approximation method are also provided. This code is suitable to be applied for deuteron induced reactions in the range of Ed =10-70 MeV, and provides cross sections with 4% accuracy.

  18. Soliton Atom Laser with Quantum State Transfer Property

    Institute of Scientific and Technical Information of China (English)

    LIU Xiong-Jun; JING Hui; GE Mo-Lin

    2006-01-01

    @@ We study the nonlinear effects in the quantum states transfer technique from photons to matter waves in the three-level case, which may provide the formation of a soliton atom laser with nonclassical atoms. The validity of quantum transfer mechanism is confirmed in the presence of the intrinsic nonlinear atomic interactions. The accompanied frequency chirp effect is shown to have no influence on the grey solitons formed by the output atom laser and the possible quantum depletion effect is also briefly discussed.

  19. Intramolecular energy transfer reactions in polymetallic

    Energy Technology Data Exchange (ETDEWEB)

    Petersen, J.

    1990-11-01

    This report is concerned with intramolecular, energy-transfer reactions. The concept of preparing synthetically a complex molecular species, capable of absorbing a photon at one metal center (antenna fragment), transferring that energy to a second metal center (reactive fragment) via a bridging ligand was first reported by our group in 1979. It is now apparent that a major emphasis in inorganic chemistry in the future will involve these types of molecular ensembles. Complexes discussed include Rh, Ru, and Cu complexes. 23 refs., 14 tabs.

  20. Reactions of Hot Tritiúm Atoms with Amino Acids

    International Nuclear Information System (INIS)

    In the existing literature there is a lack of systematic data on the interaction of tritium recoil atoms with amino acids, yet such data, in conjunction with results already obtained for organic acids and amines, could help in determining the mechanism of hot reactions in relation to the structure of compounds (chain length, functional substitutes). A study was made of the yields from the reaction of hot tritium atoms: (1) with amino acids having lengthened chains, and (2) with amino acids having a carbon chain of constant length, but with various functional substitutes. For this purpose mixtures of lithium carbonate and the acids under study were irradiated for 15 min with a slow neutron flux of 0.87 x 1013 cm2/s. Analysis was carried out on a gas chromatography unit with interchangeable columns (molecular sieves, and liquid petrolatum on kieselguhr) and with paper chromatography. Although the data obtained for the radiation survival capacity of amino acids as a function of carbon chain length were at variance with a basic tenet of radiation chemistry according to which the conservation of molecules increases in proportion to the length of their chains, the data can be explained in terms of an intramolecular transfer of energy along the carbon chain from the collision site of the hot atom to the hydroxyl group, and subsequent ''de-excitation''; on the other hand, although the energy, of tritium recoil atoms is greater than that of the chemical bond, the latter nevertheless exerts an influence on the radiation conservation of molecules with a carbon chain of constant length but with various substitutes. (author)

  1. Conformational Dependence of a Protein Kinase Phosphate Transfer Reaction

    CERN Document Server

    Henkelman, Graeme; Tung, Chang-Shung; Fenimore,, P W; McMahon, Benjamin H

    2004-01-01

    Atomic motions and energetics for a phosphate transfer reaction catalyzed by the cAMP-dependent protein kinase (PKA) are calculated by plane-wave density functional theory, starting from structures of proteins crystallized in both the reactant conformation (RC) and the transition-state conformation (TC). In the TC, we calculate that the reactants and products are nearly isoenergetic with a 0.2 eV barrier; while phosphate transfer is unfavorable by over 1.2 eV in the RC, with an even higher barrier. With the protein in the TC, the motions involved in reaction are small, with only P$_\\gamma$ and the catalytic proton moving more than 0.5 \\AA. Examination of the structures reveals that in the RC the active site cleft is not completely closed and there is insufficient space for the phosphorylated serine residue in the product state. Together, these observations imply that the phosphate transfer reaction occurs rapidly and reversibly in a particular conformation of the protein, and that the reaction can be gated by...

  2. Reaction studies of hot silicon, germanium and carbon atoms

    Energy Technology Data Exchange (ETDEWEB)

    Gaspar, P.P.

    1990-11-01

    The goal of this project was to increase the authors understanding of the interplay between the kinetic and electronic energy of free atoms and their chemical reactivity by answering the following questions: (1) what is the chemistry of high-energy carbon silicon and germanium atoms recoiling from nuclear transformations; (2) how do the reactions of recoiling carbon, silicon and germanium atoms take place - what are the operative reaction mechanisms; (3) how does the reactivity of free carbon, silicon and germanium atoms vary with energy and electronic state, and what are the differences in the chemistry of these three isoelectronic atoms This research program consisted of a coordinated set of experiments capable of achieving these goals by defining the structures, the kinetic and internal energy, and the charge states of the intermediates formed in the gas-phase reactions of recoiling silicon and germanium atoms with silane, germane, and unsaturated organic molecules, and of recoiling carbon atoms with aromatic molecules. The reactions of high energy silicon, germanium, and carbon atoms created by nuclear recoil were studied with substrates chosen so that their products illuminated the mechanism of the recoil reactions. Information about the energy and electronic state of the recoiling atoms at reaction was obtained from the variation in end product yields and the extent of decomposition and rearrangement of primary products (usually reactive intermediates) as a function of total pressure and the concentration of inert moderator molecules that remove kinetic energy from the recoiling atoms and can induce transitions between electronic spin states. 29 refs.

  3. Large-momentum-transfer Bragg interferometer with strontium atoms

    CERN Document Server

    Mazzoni, T; Del Aguila, R; Salvi, L; Poli, N; Tino, G M

    2015-01-01

    We report on the first atom interferometer based on Bragg diffraction in a fountain of alkaline-earth atoms, namely $^{88}$Sr. We demonstrate large momentum transfer to the atoms up to eight photon recoils and the use of the interferometer as a gravimeter with a sensitivity $\\delta g/g=4\\times 10^{-8}$. Thanks to the special characteristics of strontium atoms for precision measurements, this result opens a new way for experiments in fundamental and applied physics.

  4. Transfer to the continuum and Breakup reactions

    CERN Document Server

    Moro, A M

    2006-01-01

    A standard approach for the calculation of breakup reactions of exotic nuclei into two fragments is to consider inelastic excitations into the single particle continuum of the projectile. Alternatively one can also consider the transfer to the continuum of a system composed of the light fragment and the target. In this work we make a comparative study of the two approaches, underline the different inputs, and identify the advantages and disadvantages of each approach. Our test cases consist of the breakup of $^{11}$Be on a proton target at intermediate energies, and the breakup of $^8$B on $^{58}$Ni at energies around the Coulomb barrier.

  5. Atomic transfers between implanted bioceramics and tissues in orthopaedics surgery

    CERN Document Server

    Irigaray, J L; Guibert, G; Jallot, E; democrite-00023281, ccsd

    2004-01-01

    We study transfers of ions and debris from bioceramics implanted in bone sites. A contamination of surrounding tissues may play a major role in aseptic loosening of the implant. For these reasons, bioceramics require studies of biocompatibility and biofunctionality . So, in addition to in vitro studies of bioceramics, it is essential to implant them in vivo to know body reactions. We measured the concentration of mineral elements at different time intervals after implantation over a whole cross-section. We found a discontinuity of the mineral elements (Ca, P, Sr, Zn, Fe) at the interface between the implant and the receiver. The osseous attack is not global but, on the contrary, centripetal. Moreover, the fit of the concentration time course indicates that the kinetics of ossification is different for each atomic element and characterizes a distinct biological phenomenon

  6. Activation entropy of electron transfer reactions

    CERN Document Server

    Milischuk, A A; Newton, M D; Milischuk, Anatoli A.; Matyushov, Dmitry V.; Newton, Marshall D.

    2005-01-01

    We report microscopic calculations of free energies and entropies for intramolecular electron transfer reactions. The calculation algorithm combines the atomistic geometry and charge distribution of a molecular solute obtained from quantum calculations with the microscopic polarization response of a polar solvent expressed in terms of its polarization structure factors. The procedure is tested on a donor-acceptor complex in which ruthenium donor and cobalt acceptor sites are linked by a four-proline polypeptide. The reorganization energies and reaction energy gaps are calculated as a function of temperature by using structure factors obtained from our analytical procedure and from computer simulations. Good agreement between two procedures and with direct computer simulations of the reorganization energy is achieved. The microscopic algorithm is compared to the dielectric continuum calculations. We found that the strong dependence of the reorganization energy on the solvent refractive index predicted by conti...

  7. Effects of Nonlocality on Transfer Reactions

    CERN Document Server

    Titus, Luke J

    2016-01-01

    We solved the nonlocal scattering and bound state equations using the Perey-Buck type interaction, and compared to local equivalent calculations. Using the distorted wave Born approximation we construct the T-matrix for (p,d) transfer on 17O, 41Ca, 49Ca, 127Sn, 133Sn, and 209Pb at 20 and 50 MeV. Additionally we studied (p,d) reactions on 40Ca using the the nonlocal dispersive optical model. We have also included nonlocality consistently into the adiabatic distorted wave approximation and have investigated the effects of nonlocality on on (d,p) transfer reactions for deuterons impinged on 16O, 40Ca, 48Ca, 126Sn, 132Sn, 208Pb at 10, 20, and 50 MeV. We found that for bound states the Perry corrected wave functions resulting from the local equation agreed well with that from the nonlocal equation in the interior region, but discrepancies were found in the surface and peripheral regions. Overall, the Perey correction factor was adequate for scattering states, with the exception for a few partial waves. Nonlocality...

  8. Reactions the private life of atoms

    CERN Document Server

    Atkins, Peter

    2011-01-01

    Through an innovative, closely integrated design of images and text, and his characteristically clear, precise, and economical exposition, Peter Atkins explains the processes involved in chemical reactions. He begins by introducing a 'tool kit' of basic reactions, such as precipitation, corrosion, and catalysis, and concludes by showing how these building blocks are brought together in more complex processes such as photosynthesis.

  9. Molecular Beam Studies of Hot Atom Chemical Reactions: Reactive Scattering of Energetic Deuterium Atoms

    Science.gov (United States)

    Continetti, R. E.; Balko, B. A.; Lee, Y. T.

    1989-02-01

    A brief review of the application of the crossed molecular beams technique to the study of hot atom chemical reactions in the last twenty years is given. Specific emphasis is placed on recent advances in the use of photolytically produced energetic deuterium atoms in the study of the fundamental elementary reactions D + H{sub 2} -> DH + H and the substitution reaction D + C{sub 2}H{sub 2} -> C{sub 2}HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible.

  10. Do Spin State and Spin Density Affect Hydrogen Atom Transfer Reactivity?

    OpenAIRE

    Saouma, Caroline T.; Mayer, James M.

    2013-01-01

    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 t...

  11. Charge transfer reaction laser with preionization means

    Science.gov (United States)

    Lauderslager, J. B.; Pacala, T. J. (Inventor)

    1978-01-01

    A helium-nitrogen laser is described in which energy in the visible range is emitted as a result of charge transfer reaction between helium ions and nitrogen molecules. The helium and nitrogen are present in a gas mixture at several atmospheres pressure, with a nitrogen partial pressure on the order of a pair of main discharge electrodes, the gas mixture is preionized to prevent arcing when the discharge pulse is applied. The preionization is achieved by the application of a high voltage across a pair of secondary electrodes which are spaced apart in a direction perpendicular to the spacing direction of the main discharge electrodes and the longitudinal axis of the space in which the gas mixture is contained. Feedback, by means of a pair of appropriately spaced mirrors, is provided, to produce coherent energy pulses at a selected wavelength.

  12. Hydrolysis of 4-Acetoxystyrene Polymers Prepared by Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Chen, Xianyi; Jankova, Katja; Kops, Jørgen;

    1999-01-01

    Hydrolysis of 4-acetoxystyrene polymers prepared by atom transfer radical polymerization was carried out under various reaction conditions. It was found that hydrazinolysis of 4-acetoxystyrene homopolymers, random and block copolymers with styrene in 1,4-dioxane, afforded the corresponding narrow...

  13. Electron transfer in ion-atom collisions

    Energy Technology Data Exchange (ETDEWEB)

    Lin, C D

    1979-01-01

    Recent theoretical development in the understanding of electron transfer processes is reviewed. K-K electron transfer processes are studied for projectiles (nuclear charge Z/sub B/) and targets (nuclear charge Z/sub A/) in which Z/sub A/ and Z/sub B/ range from Z/sub A/ much greater than Z/sub B/ to Z/sub A/ approx. = Z/sub B/, over the energy range 0.1 < v/v/sub e/ < 2. (GHT)

  14. [Electron transfer, ionization, and excitation in atomic collisions]: Progress report

    International Nuclear Information System (INIS)

    The fundamental processes of electron transfer, ionization, and excitation in ion-atom collisions are being studied. These collision processes are treated in the context of simple one- or two-electron systems in order to provide unambiguous results and reveal more clearly the collisional mechanisms. As outlined in the original proposal, three coupled-state calculations are being carried out over the present three-year period: a Sturmian-pseudostate study of ionization in collisions between protons and the hydrogenic ions He+, Li2+, Be3+, ...; a triple-center, atomic-state study of ionization in collisions between α particles and H(ls) atoms and between protons and He+(ls) ions; and an atomic-state study of electron transfer and excitation in collisions between protons and neutral He atoms. 12 refs

  15. The mechanism of chemisorption of hydrogen atom on graphene: Insights from the reaction force and reaction electronic flux

    International Nuclear Information System (INIS)

    At the PBE-D3/cc-pVDZ level of theory, the hydrogen chemisorption on graphene was analyzed using the reaction force and reaction electronic flux (REF) theories in combination with electron population analysis. It was found that chemisorption energy barrier is mainly dominated by structural work (∼73%) associated to the substrate reconstruction whereas the electronic work is the greatest contribution of the reverse energy barrier (∼67%) in the desorption process. Moreover, REF shows that hydrogen chemisorption is driven by charge transfer processes through four electronic events taking place as H approaches the adsorbent surface: (a) intramolecular charge transfer in the adsorbent surface; (b) surface reconstruction; (c) substrate magnetization and adsorbent carbon atom develops a sp3 hybridization to form the σC-H bond; and (d) spontaneous intermolecular charge transfer to reach the final chemisorbed state

  16. The mechanism of chemisorption of hydrogen atom on graphene: Insights from the reaction force and reaction electronic flux

    Energy Technology Data Exchange (ETDEWEB)

    Cortés-Arriagada, Diego, E-mail: dcortesr@uc.cl; Gutiérrez-Oliva, Soledad; Herrera, Bárbara; Soto, Karla; Toro-Labbé, Alejandro [Nucleus Millennium Chemical Processes and Catalysis, Laboratorio de Química Teórica Computacional (QTC), Departamento de Química-Física, Facultad de Química, Pontificia Universidad Católica de Chile, Av. Vicuña Mackenna 4860, Macul, Santiago (Chile)

    2014-10-07

    At the PBE-D3/cc-pVDZ level of theory, the hydrogen chemisorption on graphene was analyzed using the reaction force and reaction electronic flux (REF) theories in combination with electron population analysis. It was found that chemisorption energy barrier is mainly dominated by structural work (∼73%) associated to the substrate reconstruction whereas the electronic work is the greatest contribution of the reverse energy barrier (∼67%) in the desorption process. Moreover, REF shows that hydrogen chemisorption is driven by charge transfer processes through four electronic events taking place as H approaches the adsorbent surface: (a) intramolecular charge transfer in the adsorbent surface; (b) surface reconstruction; (c) substrate magnetization and adsorbent carbon atom develops a sp{sup 3} hybridization to form the σC-H bond; and (d) spontaneous intermolecular charge transfer to reach the final chemisorbed state.

  17. Reactions of carbon atoms in pulsed molecular beams

    Energy Technology Data Exchange (ETDEWEB)

    Reisler, H. [Univ. of Southern California, Los Angeles (United States)

    1993-12-01

    This research program consists of a broad scope of experiments designed to unravel the chemistry of atomic carbon in its two spin states, P and D, by using well-controlled initial conditions and state-resolved detection of products. Prerequisite to the proposed studies (and the reason why so little is known about carbon atom reactions), is the development of clean sources of carbon atoms. Therefore, in parallel with the studies of its chemistry and reaction dynamics, the authors continuously explore new, state-specific and efficient ways of producing atomic carbon. In the current program, C({sup 3}P) is produced via laser ablation of graphite, and three areas of study are being pursued: (i) exothermic reactions with small inorganic molecules (e.g., O{sub 2}, N{sub 2}O, NO{sub 2}) that can proceed via multiple pathways; (ii) the influence of vibrational and translational energy on endothermic reactions involving H-containing reactants that yield CH products (e.g., H{sub 2}O H{sub 2}CO); (iii) reactions of C({sup 3}P) with free radicals (e.g., HCO, CH{sub 3}O). In addition, the authors plan to develop a source of C({sup 1}D) atoms by exploiting the pyrolysis of diazotetrazole and its salts in the ablation source. Another important goal involves collaboration with theoreticians in order to obtain relevant potential energy surfaces, rationalize the experimental results and predict the roles of translational and vibrational energies.

  18. Reaction of tungsten anion clusters with molecular and atomic nitrogen

    OpenAIRE

    Kim, Young Dok; Stolcic, Davor; Fischer, Matthias; Ganteför, Gerd

    2003-01-01

    Ultraviolet photoelectron spectra for WnN-2 (n=1 8) clusters produced by addition of atomic and molecular nitrogen on W anion clusters are presented. Evidence is provided that molecular chemisorption of N2 is more stable than the dissociative one on tungsten anion clusters consisting of eight atoms or less, which is completely different from the results on tungsten bulk surfaces. A general tendency toward molecular chemisorption for small clusters can be explained by reduced charge transfer f...

  19. Single-collision studies of energy transfer and chemical reaction

    Energy Technology Data Exchange (ETDEWEB)

    Valentini, J.J. [Columbia Univ., New York, NY (United States)

    1993-12-01

    The research focus in this group is state-to-state dynamics of reaction and energy transfer in collisions of free radicals such as H, OH, and CH{sub 3} with H{sub 2}, alkanes, alcohols and other hydrogen-containing molecules. The motivation for the work is the desire to provide a detailed understanding of the chemical dynamics of prototype reactions that are important in the production and utilization of energy sources, most importantly in combustion. The work is primarily experimental, but with an important and growing theoretical/computational component. The focus of this research program is now on reactions in which at least one of the reactants and one of the products is polyatomic. The objective is to determine how the high dimensionality of the reactants and products differentiates such reactions from atom + diatom reactions of the same kinematics and energetics. The experiments use highly time-resolved laser spectroscopic methods to prepare reactant states and analyze the states of the products on a single-collision time scale. The primary spectroscopic tool for product state analysis is coherent anti-Stokes Raman scattering (CARS) spectroscopy. CARS is used because of its generality and because the extraction of quantum state populations from CARS spectra is straightforward. The combination of the generality and easy analysis of CARS makes possible absolute cross section measurements (both state-to-state and total), a particularly valuable capability for characterizing reactive and inelastic collisions. Reactant free radicals are produced by laser photolysis of appropriate precursors. For reactant vibrational excitation stimulated Raman techniques are being developed and implemented.

  20. Study of Cold Potassium Atom - Calcium Ion Reactions

    Science.gov (United States)

    Egodapitiya, Kisra; Gang, Shu; Clark, Robert; Brown, Kenneth

    2016-05-01

    We report on our progress towards constructing a hybrid system for studying reactions between cold Potassium (K) atoms and cold Calcium (Ca+) ions. Ca+ ions will be trapped and Doppler-cooled inside a linear quadrupole ion trap. Cold K atoms will be created inside a magneto optical trap, such that the ion and the atoms are in an overlapping volume. Trapping and re-pumping beams for the Potassium MOT are derived from the same laser with wavelength 766 nm using two acousto optic modulators. The reaction products will be detected using a time-of- flight mass spectrometer that is designed to detect radially ejected ions. The main objective of this experiment is to study the rate coefficients, and identification of reaction channels between cold K atoms and Ca+ ions. Subsequently this setup will be used to study reactions between cold K atoms and sympathetically cooled molecular ions such as CaO+, and to study internal state quenching of molecular ions.

  1. Muon transfer from hot muonic hydrogen atoms to neon

    International Nuclear Information System (INIS)

    A negative muon beam has been directed on adjacent solid layers of hydrogen and neon. Three targets differing by their deuterium concentration were investigated. Muonic hydrogen atoms can drift to the neon layer where the muon is immediately transferred. The time structure of the muonic neon X-rays follows the exponential law with a disappearance rate corresponding to the one of μ-p atoms in each target. The rates λppμ and λpd can be extracted

  2. H atom transfer of collinear OH…O system

    Institute of Scientific and Technical Information of China (English)

    WU, Tao(吴韬); CHEN, Xian-Yang(陈先阳); PENG, Jian-Bo(彭建波); JU, Guan-Zhi(居冠之); JU, Guan-Zhi(居冠之)

    2000-01-01

    A quantum mechanical calculation was performed to study the hydrogen atom transfer of collinear OH…O/OD…O system,for which Delves ' coordinates and R-matrix propagation method were applied in a Melius-Blint potential energy surface. The calculation result showed that the state-state H atom transfer probability comported strong oscillation phenomena and collision delay time of the title system was in the fs-ps time scale. The kinetic isotope effect was calculated in this work too.

  3. Modulation transfer spectroscopy of ytterbium atoms in hollow cathode lamp

    International Nuclear Information System (INIS)

    We present the experimental study of modulation transfer spectroscopy of ytterbium atoms in a hollow cathode lamp. The dependences of its linewidth, slope and magnitude on the various experimental parameters are measured and fitted by the well-known theoretical expressions. The experimental results are in good agreement with the theoretical prediction. We have observed the Dicke narrowing effect by increasing the current of the hollow cathode lamp. It is also found that there are the optimal current and laser power to generate the better modulation transfer spectroscopy signal, which can be employed for locking the laser frequency to the atomic transition. (authors)

  4. Living atom transfer radical polymerization of 4-acetoxystyrene

    DEFF Research Database (Denmark)

    Gao, Bo; Chen, Xianyi; Ivan, Bela;

    1997-01-01

    Living atom transfer radical polymerization (ATRP) of 4-acetoxystyrene (1), a protected 4-vinylphenol, leading to poly(4-acetoxystyrene) with well-defined molecular weight and narrow molecular weight distribution was carried out in bulk with a,a'-dibromoxylene(2)/CuBr/2,2-bipyridine(bpy) as initi......Living atom transfer radical polymerization (ATRP) of 4-acetoxystyrene (1), a protected 4-vinylphenol, leading to poly(4-acetoxystyrene) with well-defined molecular weight and narrow molecular weight distribution was carried out in bulk with a,a'-dibromoxylene(2)/CuBr/2,2-bipyridine...

  5. Hydrated electron production by reaction of hydrogen atoms with hydroxide ions: A first-principles molecular dynamics study

    International Nuclear Information System (INIS)

    The solvated electron production by reaction between the H atom and the hydroxide anion was studied using Density Functional Theory based first-principles molecular dynamics. The simulation reveals a complex mechanism, controlled by proton transfers in the coordination sphere of the hydroxide and by the diffusion of the H atom in its solvent cavity. We formulate the hypothesis, based on a coupling between classical and first-principles molecular dynamics, that these two processes give rise to a lag time for the reaction that would explain the H atom extremely small reactivity compared to other radical species. Furthermore, the reaction observed gives an original insight in excess electron solvation. (authors)

  6. Preparation of End Grafted Polyacrylonitrile Brushes through Surface Confined Radical Chain Transfer Reaction

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    End grafted polyacrylonitrile (PAN) brush was prepared through surface initiated polymerization via the chain transfer process. The thiol-terminated monolayer and PAN brushes were characterized by FTIR, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and contact angle measurements ete. It is demonstrated that radical chain transfer reaction and surface initiated precipitate polymerization can be used to prepare end-grafted polymer brushes.

  7. Synthesis of Amphiphilic Copolymwers by Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Hansen, Natanya Majbritt Louie

    2007-01-01

    atom transfer radikal polymerisation (ATRP) blev anvendt til alle polymerisationerne. De reaktionskinetiske forhold samt de opnåelige materialestrukturer viste, at næsten alle anvendte monomer-kombinationer kan håndteres til fremstilling af fluorholdige polymermaterialer med velkontrolleret struktur...

  8. Photoredox Reaction of Triazidomercurate(II). Generation of Stable Mercury Atoms under Ambient Conditions

    OpenAIRE

    Kunkely, Horst; Vogler, Arnd

    1989-01-01

    Upon ligand-to-metal charge-transfer excitation the complex [Hg(N3)3]− in ethanol underwent a photoredox reaction (λirr = 254 nm; Ø = 0.02): [HgII(N3)3]− → Hg0+ 3N2 + N3−. Elemental mercury was released in the form of metal atoms which are stable under ambient conditions.

  9. Heavy ion transfer reactions: Status and perspectives

    Indian Academy of Sciences (India)

    L Corradi

    2010-07-01

    With the large solid angle magnetic spectrometer (PRISMA) coupled to the -array (CLARA), extensive investigations of nuclear structure and reaction dynamics have been carried out. In the present paper aspects of these studies will be presented, focussing more closely on the reaction mechanism, in particular on the properties of quasielastic and deep inelastic processes and on measurements at energies far below the Coulomb barrier.

  10. Intramolecular hydrogen transfer reaction: menthon from isopulegol.

    Science.gov (United States)

    Schaub, Thomas; Rüdenauer, Stefan; Weis, Martine

    2014-05-16

    The flavor menthon (isomeric mixture of (-)-menthon and (+)-isomenthon) was obtained in good yields and selectivities by a solventless ruthenium catalyzed isomerization of the homoallylic alcohol (-)-isopulegol. In contrast to most previous assumptions on such "isomerization" reactions, this reaction follows an intermolecular pathway, with menthol and pulegon being the central intermediates in this transformation. PMID:24779450

  11. Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs

    Directory of Open Access Journals (Sweden)

    Fabrice Chemla

    2013-02-01

    Full Text Available The formation of alkylidenezinc carbenoids by 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxyenoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at −30 °C and arises from a formal anti-selective carbozincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form.

  12. Electron transfer reactions of macrocyclic compounds of cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Heckman, R.A.

    1978-08-01

    The kinetics and mechanisms of reduction of H/sub 2/O/sub 2/, Br/sub 2/, and I/sub 2/ by various macrocyclic tetraaza complexes of cobalt(II), including Vitamin B/sub 12r/, were studied. The synthetic macrocycles studied were all 14-membered rings which varied in the degree of unsaturation,substitution of methyl groups on the periphery of the ring, and substitution within the ring itself. Scavenging experiments demonstrated that the reductions of H/sub 2/O/sub 2/ produce free hydroxyl radicals only in the case of Co((14)ane)/sup 2 +/ but with none of the others. In the latter instances apparently H/sub 2/O/sub 2/ simultaneously oxidizes the metal center and the ligand. The reductions of Br/sub 2/ and I/sub 2/ produce an aquohalocobalt(III) product for all reductants (except B/sub 12r/ + Br/sub 2/, which was complicated by bromination of the corrin ring). The mechanism of halogen reduction was found to involve rate-limiting inner-sphere electron transfer from cobalt to halogen to produce a dihalide anion coordinated to the cobalt center. This intermediate subsequently decomposes in rapid reactions to halocobalt(III) and halogen atom species or reacts with another cobalt(II) center to give two molecules of halocobalt(III). The reductions of halomethylcobaloximes and related compounds and diamminecobaloxime by Cr/sup 2 +/ were also studied. The reaction was found to be biphasic in all cases with the reaction products being halomethane (for the halomethylcobaloximes), Co/sup 2 +/ (in less than 100 percent yield), a Cr(III)-dimethylglyoxime species, a small amount of free dmgH/sub 2/, and a highly-charged species containing both cobalt and chromium. The first-stage reaction occurs with a stoichiometry of 1:1 producing an intermediate with an absorption maximum at 460 nm for all starting reagents. The results were interpreted in terms of inner-sphere coordination of the cobaloxime to the Cr(II) and electron transfer through the oxime N-O bond.

  13. Coherent Transfer of Electronic Wavepacket Motion Between Atoms

    Science.gov (United States)

    Zhou, Tao; Richards, B. G.; Jones, R. R.

    2016-05-01

    We have shown that electron correlations, induced by controlled dipole-dipole (DD) interactions, can enable the coherent transfer of electronic wavepacket motion from atoms to their neighbors. In the experiment, a 5 ns tunable dye laser excites Rb atoms in a MOT to the 25s state in a weak static electric field for which the tunable 25s 33 s 24p34p DD interaction is resonant. A picosecond THz pulse then further excites each Rydberg atom into a coherent superposition, of 25s and 24p states. The evolution of this mixed-parity wavepacket is characterized by time-dependent oscillations in the electric dipole moment, with a period of 2.9 ps. Approximately 5 ns after the wavepacket creation, a second 5 ns dye-laser promotes a second set of atoms from the 5p level into the 33s state. Because of the DD interaction, the second dye laser actually creates atom pairs whose electronic states are correlated via the resonant DD coupling. A 33 s + 34p wavepacket, oscillating with the same 2.9 ps period as the 25 s + 24p wavepacket, develops on the second set of atoms as a result of the correlation. A second, time-delayed ps THz pulse enables the detection of the coherent wavepacket motion on the two sets of atoms. This research has been supported by the NSF.

  14. Kinematical coincidence method in transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Acosta, L.; Amorini, F. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Auditore, L. [INFN Gruppo Collegato di Messina and Dipartimento di Fisica, Università di Messina (Italy); Berceanu, I. [Institute for Physics and Nuclear Engineering, Bucharest (Romania); Cardella, G., E-mail: cardella@ct.infn.it [INFN—Sezione di Catania, Via S. Sofia, 95123 Catania (Italy); Chatterjiee, M.B. [Saha Institute for Nuclear Physics, Kolkata (India); De Filippo, E. [INFN—Sezione di Catania, Via S. Sofia, 95123 Catania (Italy); Francalanza, L.; Gianì, R. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Dipartimento di Fisica e Astronomia, Università di Catania, Via S. Sofia, Catania (Italy); Grassi, L. [INFN—Sezione di Catania, Via S. Sofia, 95123 Catania (Italy); Rudjer Boskovic Institute, Zagreb (Croatia); Grzeszczuk, A. [Institut of Physics, University of Silesia, Katowice (Poland); La Guidara, E. [INFN—Sezione di Catania, Via S. Sofia, 95123 Catania (Italy); Centro Siciliano di Fisica Nucleare e Struttura della Materia, Catania (Italy); Lanzalone, G. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Facoltà di Ingegneria e Architettura, Università Kore, Enna (Italy); Lombardo, I. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Dipartimento di Scienze Fisiche, Università Federico II and INFN Sezione di Napoli (Italy); Loria, D.; Minniti, T. [INFN Gruppo Collegato di Messina and Dipartimento di Fisica, Università di Messina (Italy); Pagano, E.V. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Dipartimento di Fisica e Astronomia, Università di Catania, Via S. Sofia, Catania (Italy); and others

    2013-07-01

    A new method to extract high resolution angular distributions from kinematical coincidence measurements in binary reactions is presented. Kinematics is used to extract the center of mass angular distribution from the measured energy spectrum of light particles. Results obtained in the case of {sup 10}Be+p→{sup 9}Be+d reaction measured with the CHIMERA detector are shown. An angular resolution of few degrees in the center of mass is obtained. The range of applicability of the method is discussed.

  15. Kinematical coincidence method in transfer reactions

    CERN Document Server

    Acosta, L; Auditore, L; Berceanu, I; Cardella, G; Chatterjiee, M B; De Filippo, E; FrancalanzA, L; Gianì, R; Grassi, L; Grzeszczuk, A; La Guidara, E; Lanzalone, G; Lombardo, I; Loria, D; Minniti, T; Pagano, E V; Papa, M; Pirrone, S; Politi, G; Pop, A; Porto, F; Rizzo, F; Rosato, E; Russotto, P; Santoro, S; Trifirò, A; Trimarchi, M; Verde, G; Vigilante, M

    2012-01-01

    A new method to extract high resolution angular distributions from kinematical coincidence measurements in binary reactions is presented. Kinematic is used to extract the center of mass angular distribution from the measured energy spectrum of light particles. Results obtained in the case of 10Be+p-->9Be+d reaction measured with the CHIMERA detector are shown. An angular resolution of few degrees in the center of mass is obtained.

  16. Correlated energy transfer between two ultracold atomic species

    Science.gov (United States)

    Krönke, Sven; Knörzer, Johannes; Schmelcher, Peter

    2015-05-01

    We study a single atom as an open quantum system, which is initially prepared in a coherent state of low energy and oscillates in a one-dimensional harmonic trap through an interacting ensemble of NA bosons, held in a displaced trap [arXiv:1410.8676]. The non-equilibrium quantum dynamics of the total system is simulated by means of an ab-initio method, giving us access to all properties of the open system and its finite environment. In this talk, we focus on unraveling the interplay of energy exchange and correlations between the subsystems, which are coupled in such a spatio-temporally localized manner. We show that an inter-species interaction-induced level splitting accelerates the energy transfer between the atomic species for larger NA, which becomes less complete at the same time. System-environment correlations prove to be significant except for times when the excess energy distribution among the subsystems is highly imbalanced. These correlations result in incoherent energy transfer processes, which accelerate the early energy donation of the single atom. By analyzing correlations between intra-subsystem excitations, certain energy transfer channels are shown to be (dis-)favored depending on the instantaneous direction of transfer.

  17. Nucleon transfer reactions in D.W.B.A

    International Nuclear Information System (INIS)

    The DWBA for one nucleon transfer reaction is described as simply and completely as possible to show the possibilities and limits of this method. The extraction of spectroscopic factors is described in the appendix. (authors)

  18. Probing nucleon-nucleon correlations via heavy ion transfer reactions

    Directory of Open Access Journals (Sweden)

    Szilner S.

    2015-01-01

    Full Text Available The revival of transfer reaction studies benefited from the construction of the new generation large solid angle spectrometers, coupled to large γ arrays. The recent results of γ-particle coincident measurements demonstrate a strong interplay between single-particle and collective degrees of freedom that is pertinent to the reaction dynamics. By studies of transfer of pairs, valuable information on the component responsible for particle correlations has been derived.

  19. INVESTIGATION OF INNER AND OUTER SUBSHELLS VIA TRANSFER REACTIONS

    OpenAIRE

    Gales, S.

    1983-01-01

    Transfer reactions, investigated a high incident energy (from 100 to 300 MeV), have considerably increased our knowledge of the nuclear response function to a particular simple mode of excitation of the nucleus. These reactions are particularly well suited to the study of high spin inner and outer subshells. The advantages of such approach are illustrated using few characteristic examples. a) Strong selectivity in angular momentum transfer, determination of the spin J of the inner hole state ...

  20. The reaction dynamics of alkali dimer molecules and electronically excited alkali atoms with simple molecules

    Energy Technology Data Exchange (ETDEWEB)

    Hou, H [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

    1995-12-01

    This dissertation presents the results from the crossed molecular beam studies on the dynamics of bimolecular collisions in the gas phase. The primary subjects include the interactions of alkali dimer molecules with simple molecules, and the inelastic scattering of electronically excited alkali atoms with O2. The reaction of the sodium dimers with oxygen molecules is described in Chapter 2. Two reaction pathways were observed for this four-center molecule-molecule reaction, i.e. the formations of NaO2 + Na and NaO + NaO. NaO2 products exhibit a very anisotropic angular distribution, indicating a direct spectator stripping mechanism for this reaction channel. The NaO formation follows the bond breaking of O2, which is likely a result of a charge transfer from Na2 to the excited state orbital of O2-. The scattering of sodium dimers from ammonium and methanol produced novel molecules, NaNH3 and Na(CH3OH), respectively. These experimental observations, as well as the discussions on the reaction dynamics and the chemical bonding within these molecules, will be presented in Chapter 3. The lower limits for the bond dissociation energies of these molecules are also obtained. Finally, Chapter 4 describes the energy transfer between oxygen molecules and electronically excited sodium atoms.

  1. *H atom and *OH radical reactions with 5-methylcytosine.

    Science.gov (United States)

    Grand, A; Morell, C; Labet, V; Cadet, J; Eriksson, L A

    2007-09-20

    The reactions between either a hydrogen atom or a hydroxyl radical and 5-methylcytosine (5-MeCyt) are studied by using the hybrid kinetic energy meta-GGA functional MPW1B95. *H atom and *OH radical addition to positions C5 and C6 of 5-MeCyt, or *OH radical induced H-abstraction from the C5 methyl group, are explored. All systems are optimized in bulk solvent. The data presented show that the barriers to reaction are very low: ca. 7 kcal/mol for the *H atom additions and 1 kcal/mol for the reactions involving the *OH radical. Thermodynamically, the two C6 radical adducts and the *H-abstraction product are the most stable ones. The proton hyperfine coupling constants (HFCC), computed at the IEFPCM/MPW1B95/6-311++G(2d,2p) level, agree well with B3LYP results and available experimental and theoretical data on related thymine and cytosine radicals.

  2. Transfer reactions at the neutron dripline with triton target

    CERN Multimedia

    Two-neutron transfer to $^{9}$Li will populate the ground state of $^{11}$Li as well as low-lying resonances in a way that is complementary to studies of these states performed at higher beam energies. We aim at detecting the charged particles from the transfer reactions as well as neutrons coming from the decay of possible $^{11}$Li resonances.

  3. Reaction of iodine atoms with submicrometer squalane and squalene droplets: mechanistic insights into heterogeneous reactions.

    Science.gov (United States)

    Popolan-Vaida, Denisia M; Wilson, Kevin R; Leone, Stephen R

    2014-11-13

    The gas-phase reaction of iodine atoms with hydrocarbon molecules is energetically unfavorable, and there is no direct evidence for iodinated product formation by either H abstraction or I addition reactions at ambient temperature. Here we consider the possible heterogeneous reaction of I atoms with submicrometer droplets composed of a saturated alkane, squalane (Sq), and an unsaturated alkene, squalene (Sqe). The investigations are performed in an atmospheric pressure photochemical flow tube reactor in conjunction with a vacuum ultraviolet photoionization aerosol mass spectrometer and a scanning mobility particle sizer. Squalane, a branched alkane, is unreactive toward I atoms within the signal-to-noise, and an upper limit of the effective reactive uptake coefficient is estimated to be γI(Sq) ≤ 8.58 × 10(–7). In contrast, the reaction of I atoms with unsaturated submicrometer squalene droplets results in observable iodinated squalene products. The effective reactive uptake coefficient of I atom with squalene particles is determined to be γI(Sqe) = (1.20 ± 0.52) × 10(–4) at an average I concentration of 1.5 × 10(14) molecules·cm(–3).

  4. Theory of rotational transition in atom-diatom chemical reaction

    Science.gov (United States)

    Nakamura, Masato; Nakamura, Hiroki

    1989-05-01

    Rotational transition in atom-diatom chemical reaction is theoretically studied. A new approximate theory (which we call IOS-DW approximation) is proposed on the basis of the physical idea that rotational transition in reaction is induced by the following two different mechanisms: rotationally inelastic half collision in both initial and final arrangement channels, and coordinate transformation in the reaction zone. This theory gives a fairy compact expression for the state-to-state transition probability. Introducing the additional physically reasonable assumption that reaction (particle rearrangement) takes place in a spatially localized region, we have reduced this expression into a simpler analytical form which can explicitly give overall rotational state distribution in reaction. Numerical application was made to the H+H2 reaction and demonstrated its effectiveness for the simplicity. A further simplified most naive approximation, i.e., independent events approximation was also proposed and demonstrated to work well in the test calculation of H+H2. The overall rotational state distribution is expressed simply by a product sum of the transition probabilities for the three consecutive processes in reaction: inelastic transition in the initial half collision, transition due to particle rearrangement, and inelastic transition in the final half collision.

  5. Computational Approach to Electron Charge Transfer Reactions

    DEFF Research Database (Denmark)

    Jónsson, Elvar Örn

    The step from ab initio atomic and molecular properties to thermodynamic - or macroscopic - properties requires the combination of several theoretical tools. This dissertation presents constant temperature molecular dynamics with bond length constraints, a hybrid quantum mechanics...... to show general (or expected) properties. Properties such as in the physical and (semi-)chemical interface between classical and quantum systems and the effects of molecular bond length constraints on the temperature during simulations. As a second step the methodology is applied to the symmetric...... structure modes. This is for a large iridium-iridium dimer complex which shows a dramatic structural (and vibrational) change upon electronic excitation....

  6. Imaging population transfer in atoms with ultrafast electron pulses

    Science.gov (United States)

    Shao, Hua-Chieh; Starace, Anthony F.

    2016-05-01

    Ultrafast electron diffraction and microscopy have made significant progress recently in investigating atomic-scale structural dynamics in gas-phase and condensed materials. With these advances, direct imaging of electronic motions in atoms and molecules by ultrafast electron diffraction is anticipated. We propose imaging a laser-driven coherent population transfer in lithium atoms by femtosecond ultrafast electron pulses. Valuable information and insight can be obtained from studying such a system in order to refine ultrafast electron techniques and to interpret experimental results. Adiabatic passage by level crossing is used to transfer the electron population from the 2 s to the 2 p state. Our simulations demonstrate the ability of ultrafast electron diffraction to image this population transfer, as the time-dependent diffraction images reflect the electronic motion in the scattering intensity and angular distribution. Furthermore, asymmetric diffraction patterns indicate that even the relative phases of the electronic wave function can be resolved, provided there is sufficient temporal resolution. This work has been supported in part by DOE Award No. DE-SC0012193 [H.-C.S.] and by NSF Grant No. PHYS-1505492 [A.F.S.].

  7. Hydroxylation Reaction Mechanism for Nitrosodimethylamine by Oxygen Atom

    Institute of Scientific and Technical Information of China (English)

    LI Lan; LIN Xiao-yan; LI Zong-he

    2011-01-01

    The hydroxylation reaction mechanism of nitrosodimethylamine(NDMA)by oxygen atom was theoretically investigated at the B3LYP/6-31G** level.It has been found that the path of the oxydation of the C-H bond is easier than the path involving a Singlet/Triplet crossing.The study of the potential surface shows that both solvent effect at B3LYP/6-31G** level and different method at more credible MP2/6-311G** level in the gas phase have no effect on the hydroxylation reaction mechanism.The oxidation hydroxylation process of NDMA by O is exothermic reaction and easy to occur.

  8. Nitrogen Atom Transfer From High Valent Iron Nitrides

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Michael D. [New Mexico State Univ., Las Cruces, NM (United States); Smith, Jeremy M. [Indiana Univ., Bloomington, IN (United States)

    2015-10-14

    This report describes the synthesis and reactions of high valent iron nitrides. Organonitrogen compounds such as aziridines are useful species for organic synthesis, but there are few efficient methods for their synthesis. Using iron nitrides to catalytically access these species may allow for their synthesis in an energy-and atom-efficient manner. We have developed a new ligand framework to achieve these goals as well as providing a method for inducing previously unknown reactivity.

  9. Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst

    Science.gov (United States)

    Choi, Chang Hyuck; Kim, Minho; Kwon, Han Chang; Cho, Sung June; Yun, Seongho; Kim, Hee-Tak; Mayrhofer, Karl J. J.; Kim, Hyungjun; Choi, Minkee

    2016-01-01

    Maximum atom efficiency as well as distinct chemoselectivity is expected for electrocatalysis on atomically dispersed (or single site) metal centres, but its realization remains challenging so far, because carbon, as the most widely used electrocatalyst support, cannot effectively stabilize them. Here we report that a sulfur-doped zeolite-templated carbon, simultaneously exhibiting large sulfur content (17 wt% S), as well as a unique carbon structure (that is, highly curved three-dimensional networks of graphene nanoribbons), can stabilize a relatively high loading of platinum (5 wt%) in the form of highly dispersed species including site isolated atoms. In the oxygen reduction reaction, this catalyst does not follow a conventional four-electron pathway producing H2O, but selectively produces H2O2 even over extended times without significant degradation of the activity. Thus, this approach constitutes a potentially promising route for producing important fine chemical H2O2, and also offers opportunities for tuning the selectivity of other electrochemical reactions on various metal catalysts. PMID:26952517

  10. Vibrational control of electron-transfer reactions: a feasibility study for the fast coherent transfer regime.

    Science.gov (United States)

    Antoniou, P; Ma, Z; Zhang, P; Beratan, D N; Skourtis, S S

    2015-12-14

    Molecular vibrations and electron-vibrational interactions are central to the control of biomolecular electron and energy-transfer rates. The vibrational control of molecular electron-transfer reactions by infrared pulses may enable the precise probing of electronic-vibrational interactions and of their roles in determining electron-transfer mechanisms. This type of electron-transfer rate control is advantageous because it does not alter the electronic state of the molecular electron-transfer system or irreversibly change its molecular structure. For bridge-mediated electron-transfer reactions, infrared (vibrational) excitation of the bridge linking the electron donor to the electron acceptor was suggested as being capable of influencing the electron-transfer rate by modulating the bridge-mediated donor-to-acceptor electronic coupling. This kind of electron-transfer experiment has been realized, demonstrating that bridge-mediated electron-transfer rates can be changed by exciting vibrational modes of the bridge. Here, we use simple models and ab initio computations to explore the physical constraints on one's ability to vibrationally perturb electron-transfer rates using infrared excitation. These constraints stem from the nature of molecular vibrational spectra, the strengths of the electron-vibrational coupling, and the interaction between molecular vibrations and infrared radiation. With these constraints in mind, we suggest parameter regimes and molecular architectures that may enhance the vibrational control of electron transfer for fast coherent electron-transfer reactions.

  11. Construction of the isocopalane skeleton: application of a desulfinylative 1,7-hydrogen atom transfer strategy.

    Science.gov (United States)

    Xiao, Xiong; Xu, ZhongYu; Zeng, Qian-Ding; Chen, Xi-Bo; Ji, Wen-Hao; Han, Ying; Wu, PeiYing; Ren, Jiangmeng; Zeng, Bu-Bing

    2015-06-01

    Two attractive chirons, aldehyde 6 and chloride 7, exhibiting functionalized ent-spongiane-type tricyclic skeletons (ABC ring system), have been constructed and their absolute configurations have been studied by NMR spectroscopy and confirmed by single-crystal X-ray diffraction. Both of these chirons are derived from commercially available andrographolide in good yield. Aldehyde 6 is obtained through a novel K2 S2 O8 -catalyzed aquatic ring-closing reaction of allylic sodium sulfonate and intramolecular 1,7-hydrogen atom transfer process. Further mechanistic investigations demonstrate that the 1,7-hydrogen atom transfer is a free-radical process, whereby hydrogen migrates from C18 to C17, as evidenced by double-18- deuterium-labeled isotope experiments. Prospective applications of these two chiral sources are also discussed. PMID:25907201

  12. Path Sampling Methods for Enzymatic Quantum Particle Transfer Reactions.

    Science.gov (United States)

    Dzierlenga, M W; Varga, M J; Schwartz, S D

    2016-01-01

    The mechanisms of enzymatic reactions are studied via a host of computational techniques. While previous methods have been used successfully, many fail to incorporate the full dynamical properties of enzymatic systems. This can lead to misleading results in cases where enzyme motion plays a significant role in the reaction coordinate, which is especially relevant in particle transfer reactions where nuclear tunneling may occur. In this chapter, we outline previous methods, as well as discuss newly developed dynamical methods to interrogate mechanisms of enzymatic particle transfer reactions. These new methods allow for the calculation of free energy barriers and kinetic isotope effects (KIEs) with the incorporation of quantum effects through centroid molecular dynamics (CMD) and the full complement of enzyme dynamics through transition path sampling (TPS). Recent work, summarized in this chapter, applied the method for calculation of free energy barriers to reaction in lactate dehydrogenase (LDH) and yeast alcohol dehydrogenase (YADH). We found that tunneling plays an insignificant role in YADH but plays a more significant role in LDH, though not dominant over classical transfer. Additionally, we summarize the application of a TPS algorithm for the calculation of reaction rates in tandem with CMD to calculate the primary H/D KIE of YADH from first principles. We found that the computationally obtained KIE is within the margin of error of experimentally determined KIEs and corresponds to the KIE of particle transfer in the enzyme. These methods provide new ways to investigate enzyme mechanism with the inclusion of protein and quantum dynamics.

  13. Path Sampling Methods for Enzymatic Quantum Particle Transfer Reactions.

    Science.gov (United States)

    Dzierlenga, M W; Varga, M J; Schwartz, S D

    2016-01-01

    The mechanisms of enzymatic reactions are studied via a host of computational techniques. While previous methods have been used successfully, many fail to incorporate the full dynamical properties of enzymatic systems. This can lead to misleading results in cases where enzyme motion plays a significant role in the reaction coordinate, which is especially relevant in particle transfer reactions where nuclear tunneling may occur. In this chapter, we outline previous methods, as well as discuss newly developed dynamical methods to interrogate mechanisms of enzymatic particle transfer reactions. These new methods allow for the calculation of free energy barriers and kinetic isotope effects (KIEs) with the incorporation of quantum effects through centroid molecular dynamics (CMD) and the full complement of enzyme dynamics through transition path sampling (TPS). Recent work, summarized in this chapter, applied the method for calculation of free energy barriers to reaction in lactate dehydrogenase (LDH) and yeast alcohol dehydrogenase (YADH). We found that tunneling plays an insignificant role in YADH but plays a more significant role in LDH, though not dominant over classical transfer. Additionally, we summarize the application of a TPS algorithm for the calculation of reaction rates in tandem with CMD to calculate the primary H/D KIE of YADH from first principles. We found that the computationally obtained KIE is within the margin of error of experimentally determined KIEs and corresponds to the KIE of particle transfer in the enzyme. These methods provide new ways to investigate enzyme mechanism with the inclusion of protein and quantum dynamics. PMID:27497161

  14. Heating-Assisted Atom Transfer in the Scanning Tunneling Microscope

    CERN Document Server

    Grigorescu, M

    1998-01-01

    The effects of a voltage pulse on the localization probability for a Xe atom prepared in a pure state localized on the STM surface at 0 temperature is investigated by numerically integrating the time-dependent Schroedinger equation. In these calculations the environmental interactions are neglected, and voltage pulses of 20 and 7 ns with symmetric triangular and trapezoidal shapes are considered. The atom dynamics at an environmental temperature of 4 K is studied in the frame of a stochastic, non-linear Liouville equation for the density operator. It is shown that the irreversible transfer from surface to tip may be explained by thermal decoherence rather than by the driving force acting during the application of the voltage pulse.

  15. Theoretical studies on proton transfer reaction of 3(5)-substituted pyrazoles

    Indian Academy of Sciences (India)

    Alireza Najafi Chermahini; Abbas Teimouri

    2014-01-01

    The inter and intra molecular proton transfer reactions of a series of pyrazole derivatives have been studied by using density functional theory (DFT) andMP2 methods implementing 6-311++G(d,p) atomic basis set. The substituents have been selected to cover a wide range of electronic effects. Proton transfer process was studied for mechanisms including single proton transfer, double proton transfer and proton transfer assisted by a water or ammonia molecule. The results showed single proton transfer reactions for interconversion pyrazole derivatives need highest activation energies in the range of 45.7−51.59 and 49.4−53.96 kcal/mol at B3LYP and MP2 levels, respectively. It was found that for the 3-substituted pyrazoles, electron withdrawing groups form stronger dimers but in the 5-substituted tautomers electron donating groups form stronger hydrogen bond. The double proton transfer reactions between dimers were studied and transition states calculated. The ranges of activation energies were found to be 17.51−19.36 and 17.02−17.80 kcal/mol for the C → E and D → D reactions respectively. In addition, the activation energies for the proton transfer reaction assisted by water or ammonia molecules were found to be in the range of 26.62−31.78 and 17.25−22.46 kcal/mol, respectively, calculated at MP2/6-311++G(d,p) level of theory.

  16. Modulation transfer spectroscopy in a lithium atomic vapor cell.

    Science.gov (United States)

    Sun, Dali; Zhou, Chao; Zhou, Lin; Wang, Jin; Zhan, Mingsheng

    2016-05-16

    We have investigated modulation transfer spectroscopy of D2 transitions of 7Li atoms in a vapor cell. The role of the intensity of the probe beam in the spectrum is important, we have seen unique characteristics of the signal in the crossover peak. In order to find the best signal for laser locking, the slope and frequency offset of the zero-crossing signal are determined. The dependence of the modulation transfer spectra on polarizations of pump and probe beam is demonstrated. The residual amplitude modulation in the system is also considered, and the distortion of the spectra due to the modulation is analyzed. It was found that the crossover peak is more suitable for frequency stabilization due to its better residual amplitude modulation compensation. PMID:27409886

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

    OpenAIRE

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

    2008-01-01

    We study the mechanism of proton transfer (PT) between the photoacid 8-hydroxy-1,3, 6-pyrenetrisulfonic acid (HPTS) and the base chloroacetate in aqueous solution. We investigate both proton and deuteron transfer reactions in solutions with base concentrations ranging from 0.25M to 4M. Using femtosecond midinfrared spectroscopy, we probe the vibrational responses of HPTS, its conjugate photobase, the hydrated proton/deuteron, and chloroacetate. The measurement of these four resonances allows ...

  18. Mass transfer with complex reversible chemical reactions. II: Parallel reversible chemical reactions

    NARCIS (Netherlands)

    Versteeg, G.F.; Kuipers, J.A.M.; Beckum, van F.P.H.; Swaaij, van W.P.M.

    1990-01-01

    An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and co

  19. Tem holder for sample transfer under reaction conditions

    DEFF Research Database (Denmark)

    Damsgaard, Christian Danvad; Zandbergen, Henny W.; Wagner, Jakob Birkedal

    and temperature, which usually are far from the operando conditions of e.g. heterogeneous catalysis. Our efforts focus on bridging these gaps by establishing in situ sample transfer between complementary measurement techniques. To fully exploit the capabilities of ETEM complementary experiments...... transfer concept by use of a dedicated TEM transfer holder capable of enclosing the sample in a gaseous environment at temperatures up to approx. 900C. By oxidation and reduction experiments of Cu nanoparticles it is shown possible to keep the reaction conditions during transfer outside the microscope....... This opens up for the possibility to do complimentary in situ experiments of the exact same sample without changing the sample condition during transfer. As an example a commercially used methanol catalyst Cu/Zn/Al2O3 [6], was reduced at 1 bar in 2% H2 in He at 220C and in an in situ x-ray diffractometer...

  20. Electrochemical Reaction in Single Layer MoS2: Nanopores Opened Atom by Atom.

    Science.gov (United States)

    Feng, J; Liu, K; Graf, M; Lihter, M; Bulushev, R D; Dumcenco, D; Alexander, D T L; Krasnozhon, D; Vuletic, T; Kis, A; Radenovic, A

    2015-05-13

    Ultrathin nanopore membranes based on 2D materials have demonstrated ultimate resolution toward DNA sequencing. Among them, molybdenum disulfide (MoS2) shows long-term stability as well as superior sensitivity enabling high throughput performance. The traditional method of fabricating nanopores with nanometer precision is based on the use of focused electron beams in transmission electron microscope (TEM). This nanopore fabrication process is time-consuming, expensive, not scalable, and hard to control below 1 nm. Here, we exploited the electrochemical activity of MoS2 and developed a convenient and scalable method to controllably make nanopores in single-layer MoS2 with subnanometer precision using electrochemical reaction (ECR). The electrochemical reaction on the surface of single-layer MoS2 is initiated at the location of defects or single atom vacancy, followed by the successive removals of individual atoms or unit cells from single-layer MoS2 lattice and finally formation of a nanopore. Step-like features in the ionic current through the growing nanopore provide direct feedback on the nanopore size inferred from a widely used conductance vs pore size model. Furthermore, DNA translocations can be detected in situ when as-fabricated MoS2 nanopores are used. The atomic resolution and accessibility of this approach paves the way for mass production of nanopores in 2D membranes for potential solid-state nanopore sequencing. PMID:25928894

  1. Saponification reaction system: a detailed mass transfer coefficient determination.

    Science.gov (United States)

    Pečar, Darja; Goršek, Andreja

    2015-01-01

    The saponification of an aromatic ester with an aqueous sodium hydroxide was studied within a heterogeneous reaction medium in order to determine the overall kinetics of the selected system. The extended thermo-kinetic model was developed compared to the previously used simple one. The reaction rate within a heterogeneous liquid-liquid system incorporates a chemical kinetics term as well as mass transfer between both phases. Chemical rate constant was obtained from experiments within a homogeneous medium, whilst the mass-transfer coefficient was determined separately. The measured thermal profiles were then the bases for determining the overall reaction-rate. This study presents the development of an extended kinetic model for considering mass transfer regarding the saponification of ethyl benzoate with sodium hydroxide within a heterogeneous reaction medium. The time-dependences are presented for the mass transfer coefficient and the interfacial areas at different heterogeneous stages and temperatures. The results indicated an important role of reliable kinetic model, as significant difference in k(L)a product was obtained with extended and simple approach.

  2. Modelling of mass transfer in combination with radical reactions

    NARCIS (Netherlands)

    Hoorn, J. A. A.; Versteeg, G. F.

    2006-01-01

    The diffusion-reaction equations for different model versions have been solved using a finite-differencing technique. In all models a reactant A is transferred from the gas to the liquid phase and reacts in the liquid with B to form P. The calculations comprised a simple stoichiometric model, a syst

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

    Energy Technology Data Exchange (ETDEWEB)

    Brett Kimball Simpson

    2002-08-27

    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 MnO{sub 2} films] revealed that MnO{sub 2} 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 MnO{sub 2} 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 RuO{sub 2} films showed that the Fe(III)-doped RuO{sub 2}-film electrodes are applicable for anodic detection of sulfur compounds. The Fe(III) sites in the Fe-RuO{sub 2} films are speculated to act as adsorption sites for the sulfur species while the Ru(IV) sites function for anodic discharge of H{sub 2}O 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 Sb{sub 10}Sn{sub 20}Ti{sub 70}, Cu{sub 63}Ni{sub 37} and Cu{sub 25}Ni{sub 75} alloy electrodes exhibited improved activity for nitrate reduction as compared to their pure component metals. The Cu{sub 63}Ni{sub 37} 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 NO{sub 3}{sup -} at the Cu-Ni alloy electrode is superior to the response at the pure Cu and Ni electrodes. This is explained on the basis of the

  4. Neutron transfer reactions in the fp-shell region

    Energy Technology Data Exchange (ETDEWEB)

    Mahgoub, Mahmoud

    2008-06-26

    Neutron transfer reactions were used to study the stability of the magic number N=28 near {sup 56}Ni. On one hand the one-neutron pickup (d,p) reaction was used for precision spectroscopy of single-particle levels in {sup 55}Fe. On the other hand we investigated the two-neutron transfer mechanism into {sup 56}Ni using the pickup reaction {sup 58}Ni((vector)p,t){sup 56}Ni. In addition the reliability of inverse kinematics reactions at low energy to study exotic nuclei was tested by the neutron transfer reactions t({sup 40}Ar,p){sup 42}Ar and d({sup 54}Fe,p){sup 55}Fe using tritium and deuterium targets, respectively, and by comparing the results with those of the normal kinematics reactions. The experimental data, differential cross-section and analyzing powers, are compared to DWBA and coupled channel calculations utilizing the code CHUCK3. By performing the single-neutron stripping reaction ((vector)d,p) on {sup 54}Fe the 1f{sub 7/2} shell in the ground state configuration was found to be partly broken. The instability of the 1f{sub 7/2} shell and the magic number N=28 was confirmed once by observing a number of levels with J{sup {pi}} = 7/2{sup -} at low excitation energies, which should not be populated if {sup 54}Fe has a closed 1f{sub 7/2} shell, and also by comparing our high precision experimental data with a large scale shell model calculation using the ANTOINE code [5]. Calculations including a partly broken 1f{sub 7/2} shell show better agreement with the experiment. The instability of the 1f{sub 7/2} shell was confirmed also by performing the two-neutron pick-up reaction ((vector)p,t) on {sup 58}Ni to study {sup 56}Ni, where a considerable improvement in the DWBA calculation was observed after considering 1f{sub 7/2} as a broken shell. To prove the reliability of inverse kinematics transfer reactions at low energies ({proportional_to} 2 AMeV), the aforementioned single-neutron transfer reaction (d,p) was repeated using a beam of {sup 54}Fe ions and a

  5. Some Reactions of Recoil Atoms in Solid Inorganic Phosphorus Compounds

    International Nuclear Information System (INIS)

    In connection with our interest in the recoil chemistry of radiophosphorus it was considered worthwhile to investigate systems in which tritium recoils can be produced and subsequently react with inorganic anions of phosphorus. One purpose of this investigation was to evaluate the possibility for tritium recoils to replace (''displace'') either an oxygen or a hydrogen atom bound to phosphorus. For instance, oxygen replacement in an orthophosphate ion (PO4)-3 could lead to a (TPO3)-2 ion (phosphite), hydrogen replacement in hypophosphite could lead to (HTPO2). A number of lithium salts of orthophosphoric, phosphorous and hypophosphorous acid were irradiated with neutrons, the nuclear reaction Li6 (n, α)H3 serving as the source for the energetic tritium atoms. Through a step-wise oxidation procedure tritium bound to phosphorus was converted into HTO and radio-assayed by means of liquid scintillation counting. The results indicate that replacement of oxygen by tritium in orthophosphates is highly unlikely. When phosphites and hypophosphites are the target material, an appreciable percentage of the tritium recoils end up bound to phosphorus. The second purpose of this investigation was to determine to what extent the labelling of the tripolyphosphate - P32 anion, formed by recoiling P32 particles in a number of crystalline phosphates, deviates from a uniform distribution. A number of phosphates were irradiated with neutrons. The tripolyphosphate - P32 formed was separated by precipitation as the tris (ethylenediamine) cobalt (III) salt. By means of a step-wise degradation into orthophosphate the distribution of the P32 among the two possible positions in the anion was measured. One result of this study is that when anhydrous orthophosphates are the target material, there is as predicted, a strong preference for the tripolyphosphate - P32 formed to be labelled at the centre. These and other results are discussed in the light of current concepts of ''hot

  6. Mechanism of Photoinduced Metal-Free Atom Transfer Radical Polymerization: Experimental and Computational Studies.

    Science.gov (United States)

    Pan, Xiangcheng; Fang, Cheng; Fantin, Marco; Malhotra, Nikhil; So, Woong Young; Peteanu, Linda A; Isse, Abdirisak A; Gennaro, Armando; Liu, Peng; Matyjaszewski, Krzysztof

    2016-02-24

    Photoinduced metal-free atom transfer radical polymerization (ATRP) of methyl methacrylate was investigated using several phenothiazine derivatives and other related compounds as photoredox catalysts. The experiments show that all selected catalysts can be involved in the activation step, but not all of them participated efficiently in the deactivation step. The redox properties and the stability of radical cations derived from the catalysts were evaluated by cyclic voltammetry. Laser flash photolysis (LFP) was used to determine the lifetime and activity of photoexcited catalysts. Kinetic analysis of the activation reaction according to dissociative electron-transfer (DET) theory suggests that the activation occurs only with an excited state of catalyst. Density functional theory (DFT) calculations revealed the structures and stabilities of the radical cation intermediates as well as the reaction energy profiles of deactivation pathways with different photoredox catalysts. Both experiments and calculations suggest that the activation process undergoes a DET mechanism, while an associative electron transfer involving a termolecular encounter (the exact reverse of DET pathway) is favored in the deactivation process. This detailed study provides a deeper understanding of the chemical processes of metal-free ATRP that can aid the design of better catalytic systems. Additionally, this work elucidates several important common pathways involved in synthetically useful organic reactions catalyzed by photoredox catalysts. PMID:26820243

  7. Proton-Coupled Electron Transfer Reactions with Photometric Bases Reveal Free Energy Relationships for Proton Transfer.

    Science.gov (United States)

    Eisenhart, Thomas T; Howland, William C; Dempsey, Jillian L

    2016-08-18

    The proton-coupled electron transfer (PCET) oxidation of p-aminophenol in acetonitrile was initiated via stopped-flow rapid-mixing and spectroscopically monitored. For oxidation by ferrocenium in the presence of 7-(dimethylamino)quinoline proton acceptors, both the electron transfer and proton transfer components could be optically monitored in the visible region; the decay of the ferrocenium absorbance is readily monitored (λmax = 620 nm), and the absorbance of the 2,4-substituted 7-(dimethylamino)quinoline derivatives (λmax = 370-392 nm) red-shifts substantially (ca. 70 nm) upon protonation. Spectral analysis revealed the reaction proceeds via a stepwise electron transfer-proton transfer process, and modeling of the kinetics traces monitoring the ferrocenium and quinolinium signals provided rate constants for elementary proton and electron transfer steps. As the pKa values of the conjugate acids of the 2,4-R-7-(dimethylamino)quinoline derivatives employed were readily tuned by varying the substituents at the 2- and 4-positions of the quinoline backbone, the driving force for proton transfer was systematically varied. Proton transfer rate constants (kPT,2 = (1.5-7.5) × 10(8) M(-1) s(-1), kPT,4 = (0.55-3.0) × 10(7) M(-1) s(-1)) were found to correlate with the pKa of the conjugate acid of the proton acceptor, in agreement with anticipated free energy relationships for proton transfer processes in PCET reactions. PMID:27500804

  8. Mass transfer model for two-layer TBP oxidation reactions

    International Nuclear Information System (INIS)

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments. Three cases were investigated: (1) transfer of water into the TBP layer with sparging of both the aqueous and TBP layers, (2) transfer of water into the TBP layer with sparging of just the TBP layer, and (3) transfer of butanol into the aqueous layer with sparging of both layers. The TBP layer was comprised of 99% pure TBP (spiked with butanol for the butanol transfer experiments), and the aqueous layer was comprised of either water or an aluminum nitrate solution. The liquid layers were air sparged to simulate the mixing due to the evolution of gases generated by oxidation reactions. A plastic tube and a glass frit sparger were used to provide different size bubbles. Rates of mass transfer were measured using infrared spectrophotometers provided by SRTC/Analytical Development

  9. X-ray Crystal Structures Elucidate the Nucleotidyl Transfer Reaction of Transcript Initiation Using Two Nucleotides

    Energy Technology Data Exchange (ETDEWEB)

    M Gleghorn; E Davydova; R Basu; L Rothman-Denes; K Murakami

    2011-12-31

    We have determined the X-ray crystal structures of the pre- and postcatalytic forms of the initiation complex of bacteriophage N4 RNA polymerase that provide the complete set of atomic images depicting the process of transcript initiation by a single-subunit RNA polymerase. As observed during T7 RNA polymerase transcript elongation, substrate loading for the initiation process also drives a conformational change of the O helix, but only the correct base pairing between the +2 substrate and DNA base is able to complete the O-helix conformational transition. Substrate binding also facilitates catalytic metal binding that leads to alignment of the reactive groups of substrates for the nucleotidyl transfer reaction. Although all nucleic acid polymerases use two divalent metals for catalysis, they differ in the requirements and the timing of binding of each metal. In the case of bacteriophage RNA polymerase, we propose that catalytic metal binding is the last step before the nucleotidyl transfer reaction.

  10. Light induced electron transfer reactions of metal complexes

    International Nuclear Information System (INIS)

    Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed

  11. Understanding quark flow in high momentum transfer exclusive reactions

    International Nuclear Information System (INIS)

    This paper reports on a 5.9 GeV/c secondary beam of pions, kaons, and protons directed into a liquid hydrogen target that has been used to study high momentum transfer exclusive reactions of the form A + B → C + D. The high sensitivity of this experiment has allowed the differential cross section for 19 two body exclusive reactions to be measured around 90 degrees in the center of mass frame. These high statistic measurements confirm the conclusion of an earlier 10 GeV/c experiment which found that the relative magnitudes of the cross sections are consistent with the dominance of the quark interchange diagram

  12. Understanding quark flow in high momentum transfer exclusive reactions

    International Nuclear Information System (INIS)

    A 5.9 GeV/c secondary beam of pions, kaons, and protons directed into a liquid hydrogen target has been used to study high momentum transfer exclusive reactions of the form A + B → C + D. The high sensitivity of this experiment has allowed the differential cross section for 19 two body exclusive reactions to be measured around 90 degrees in the center of mass frame. These high statistic measurements confirm the conclusion of an earlier 10 GeV/c experiment which found that the relative magnitudes of the cross sections are consistent with the dominance of the quark interchange diagram. 6 refs., 4 fig., 1 tab

  13. Entanglement transfer between atoms in two distant cavities via an optical fibre

    Institute of Scientific and Technical Information of China (English)

    Xiao Xing; Fang Mao-Fa

    2009-01-01

    This paper presents a treatment of the entanglement transfer between atoms in two distant cavities coupled by an optical fibre. If the atoms resonantly and collectively interact with the local single-mode cavity fields and the dipoledipole interaction between the atoms is neglected, then it shows that a complete transfer of entanglement from one pair of atoms to another can be deterministieally realized. Furthermore, it also investigates the effects of dipole-dipole interaction on entanglement transfer on the condition that the interaction between the atoms and the cavity is much weaker than the coupling between the cavity and the fibre.

  14. O atom transfer from nitric oxide catalyzed by Fe(TPP).

    Science.gov (United States)

    Lin, R; Farmer, P J

    2001-02-14

    The reaction of NO-Fe(TPP) with low pressures of NO gas proceeds through three distinct transformations, the first of which we suggest is the formation of an N--N-coupled, (NO)(2) adduct intermediate. The subsequent formation of NO(NO(2))Fe(TPP), which under these conditions readily loses NO, suggests that it is formed by addition of free NO(2) to the starting nitrosyl. A mechanism is proposed which implies that the addition of a competitive O atom acceptor would lead to catalytic production of N(2)O. In agreement with the proposed mechanism, the formation of N(2)O is decoupled from the formation of the nitrite by using PPh(3) as the competitive acceptor. The mechanism of O atom transfer was examined by cross-labeling experiments, which show that both O atoms in the intermediate are equivalent, even under catalytic conditions. The formation of an intermediate was confirmed by IR spectroscopy of the heterogeneous reaction of an NO-Fe(TPP) film with gaseous NO, in which transient, isotope-sensitive nu(NO) bands are seen prior to NO(NO(2))Fe(TPP) formation. Mixed (14)N/(15)N label experiments demonstrate coupling between the two bound nitrosyls in the transient species. PMID:11456667

  15. Electron transfer reactions in chemistry. Theory and experiment

    OpenAIRE

    Marcus, Rudolph A.

    1997-01-01

    Since the late 1940s, the field of electron transfer processes has grown enormously, both in chemistry and biology. The development of the field, experimentally and theoretically, as well as its relation to the study of other kinds of chemical reactions, represents to us an intriguing history, one in which many threads have been brought together. In this lecture, some history, recent trends, and my own involvement in this research are described.

  16. Investigation of the unbound 21C nucleus via transfer reaction

    Directory of Open Access Journals (Sweden)

    Fukui Tokuro

    2014-03-01

    Full Text Available The cross section of the transfer reaction 20C(d,p21C at 30.0 MeV is investigated. The continuum-discretized coupled-channels method (CDCC is used in order to obtain the final state wave function. The smoothing procedure of the transition matrix and the channel-coupling effect on the cross section are discussed.

  17. Photo- and radiation chemical studies of intermediates involved in excited-state electron-transfer reactions

    International Nuclear Information System (INIS)

    Excited-state inter- and intramolecular electron-transfer reactions lie at the heart of the most photochemical solar energy conversion schemes. The authors research, which has utilized the techniques of continuous and pulsed photolysis and radiolysis, has focused on three general aspects of these reactions involving transition metal coordination complexes and electron donor-acceptor complexes: i) the effect of solution medium on the properties and quenching of the excited states; ii) the control of the quantum yields of formation of redox products; iii) the mechanism by which reduced species interact with water to yield H2 homogeneously and heterogeneously. EDTA is among the most popular sacrificial electron donors used in model systems. Its role is to scavenge the oxidized form of the photosensitizer in order to prevent its rapid reaction with the reduced form of the electron relay species that results from the electron-transfer quenching of the excited photosensitizer. In systems involving MV2+, the radicals resulting from the oxidation of EDTA can eventually lead to the generation of a second equivalent of MV+; the reducing agent is believed to be a radical localized on the carbon atom alpha to the carboxylate group. The reaction of radiolytically-generated OH/H with EDTA produces this radical directly via H-abstraction or indirectly via deprotonation of the carbon atom adjacent to the nitrogen radical site in the oxidized amine moiety; it reduces MV2+ with rate constants of 2.8 x 109, 7.6 x 109, and 8.5 x 106M-1s-1 at pH 12.5, 8.3, and 4.7, respectively. Degradative decarboxylation of EDTA-radicals and their back electron-transfer reactions are enhanced in acidic solution causing the yield of MV+ to be severely diminished

  18. Analysis of transfer reactions: determination of spectroscopic factors

    Energy Technology Data Exchange (ETDEWEB)

    Keeley, N. [CEA Saclay, Dept. d' Astrophysique, de Physique des Particules de Physique Nucleaire et de l' Instrumentation Associee (DSM/DAPNIA/SPhN), 91- Gif sur Yvette (France); The Andrzej So an Institute for Nuclear Studies, Dept. of Nuclear Reactions, Warsaw (Poland)

    2007-07-01

    An overview of the most popular models used for the analysis of direct reaction data is given, concentrating on practical aspects. The 4 following models (in order of increasing sophistication): the distorted wave born approximation (DWBA), the adiabatic model, the coupled channels born approximation, and the coupled reaction channels are briefly described. As a concrete example, the C{sup 12}(d,p)C{sup 13} reaction at an incident deuteron energy of 30 MeV is analysed with progressively more physically sophisticated models. The effect of the choice of the reaction model on the spectroscopic information extracted from the data is investigated and other sources of uncertainty in the derived spectroscopic factors are discussed. We have showed that the choice of the reaction model can significantly influence the nuclear structure information, particularly the spectroscopic factors or amplitudes but occasionally also the spin-parity, that we wish to extract from direct reaction data. We have also demonstrated that the DWBA can fail to give a satisfactory description of transfer data but when the tenets of the theory are fulfilled DWBA can work very well and will yield the same results as most sophisticated models. The use of global rather than fitted optical potentials can also lead to important differences in the extracted spectroscopic factors.

  19. Pickering emulsion templated interfacial atom transfer radical polymerization for microencapsulation.

    Science.gov (United States)

    Li, Jian; Hitchcock, Adam P; Stöver, Harald D H

    2010-12-01

    This Article describes a new microencapsulation method based on a Pickering emulsion templated interfacial atom transfer radical polymerization (PETI-ATRP). Cationic LUDOX CL nanoparticles were coated electrostatically with an anionic polymeric ATRP initiator, poly(sodium styrene sulfonate-co-2-(2-bromoisobutyryloxy)ethyl methacrylate) (PSB), prepared by radical copolymerization of sodium styrene sulfonate and 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM). The resulting PSB-modified CL particles were surface active and could be used to stabilize oil-in-water Pickering emulsions. ATRP of water-soluble cross-linking monomers, confined to the oil-water interface by the surface-bound PSB, then led to nanoparticle/polymer composite shells. This method allowed encapsulation of core solvents (xylene, hexadecane, perfluoroheptane) with different solubility parameters. The microcapsule (MC) wall chemistry could accommodate different monomers, demonstrating the versatility of this method. Double-walled MCs were formed by sequentially carrying out PETI-ATRP and in situ polymerization of encapsulated monomers. The double-walled structure was verified by both transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM).

  20. Explicit inclusion of nonlocality in (d,p) transfer reactions

    CERN Document Server

    Titus, L J; Potel, G

    2016-01-01

    Background: Traditionally, nucleon-nucleus optical potentials are made local for convenience. In recent work we studied the effects of including nonlocal interactions explicitly in the final state for (d,p) reactions, within the distorted wave Born approximation. Purpose: Our goal in this work is to develop an improved formalism for nonlocal interactions that includes deuteron breakup and to use it to study the effects of including nonlocal interactions in transfer (d,p) reactions, in both the deuteron and the proton channel. Method: We extend the finite-range adiabatic distorted wave approximation to include nonlocal nucleon optical potentials. We apply our method to (d,p) reactions on 16O, 40Ca, 48Ca, 126Sn, 132Sn, and 208Pb at 10, 20 and 50 MeV. Results: We find that nonlocality in the deuteron scattering state reduces the amplitude of the wave function in the nuclear interior, and shifts the wave function outward. In many cases, this has the effect of increasing the transfer cross section at the first pea...

  1. The reaction efficiency of thermal energy oxygen atoms with polymeric materials

    Science.gov (United States)

    Koontz, S. L.; Nordine, Paul

    1990-01-01

    The reaction efficiency of several polymeric materials with thermal-energy (0.04 eV translational energy), ground-state (O3P) oxygen atoms was determined by exposing the materials to a room temperature gas containing a known concentration of atomic oxygen. The reaction efficiency measurements were conducted in two flowing afterglow systems of different configuration. Atomic oxygen concentration measurements, flow, transport and surface dose analysis is presented in this paper. The measured reaction efficiencies of Kapton, Mylar, polyethylene, D4-polyethylene and Tedlar are .001 to .0001 those determined with high-energy ground-state oxygen atoms in low earth orbit or in a high-velocity atom beam. D4-polyethylene exhibits a large kinetic isotope effect with atomic oxygen at thermal but not hyperthermal atom energies.

  2. A New Reaction-controlled Phase-transfer Catalyst System

    Institute of Scientific and Technical Information of China (English)

    Ming Qiang LI; Xi Gao JIAN; Gui Mei WANG; Yan YU

    2004-01-01

    A new reaction-controlled phase-transfer catalyst system was designed and synthesized. In this system, heteropolytungstate [C7H7N(CH3)3]9PW9O34 was used for catalytic epoxidation of cyclohexene with H2O2 as the oxidant. The conversion of H2O2 was 100% and the yield of cyclohexene oxide was 87.1% based on cyclohexene. Infrared spectra showed that both fresh catalyst and the recovered catalyst do have completely same absorption peak, indicating the structure of catalyst is very stability and can be recycled.

  3. Pentanidium-catalyzed enantioselective phase-transfer conjugate addition reactions

    KAUST Repository

    Ma, Ting

    2011-03-09

    A new chiral entity, pentanidium, has been shown to be an excellent chiral phase-transfer catalyst. The enantioselective Michael addition reactions of tert-butyl glycinate-benzophenone Schiff base with various α,β- unsaturated acceptors provide adducts with high enantioselectivities. A successful gram-scale experiment at a low catalyst loading of 0.05 mol % indicates the potential for practical applications of this methodology. Phosphoglycine ester analogues can also be utilized as the Michael donor, affording enantioenriched α-aminophosphonic acid derivatives and phosphonic analogues of (S)-proline. © 2011 American Chemical Society.

  4. Quantum Transition State Theory for proton transfer reactions in enzymes

    CERN Document Server

    Bothma, Jacques P; McKenzie, Ross H

    2009-01-01

    We consider the role of quantum effects in the transfer of hyrogen-like species in enzyme-catalysed reactions. This study is stimulated by claims that the observed magnitude and temperature dependence of kinetic isotope effects imply that quantum tunneling below the energy barrier associated with the transition state significantly enhances the reaction rate in many enzymes. We use a path integral approach which provides a general framework to understand tunneling in a quantum system which interacts with an environment at non-zero temperature. Here the quantum system is the active site of the enzyme and the environment is the surrounding protein and water. Tunneling well below the barrier only occurs for temperatures less than a temperature $T_0$ which is determined by the curvature of potential energy surface near the top of the barrier. We argue that for most enzymes this temperature is less than room temperature. For physically reasonable parameters quantum transition state theory gives a quantitative descr...

  5. Deuteron-proton charge exchange reaction at small transfer momentum

    CERN Document Server

    Ladygina, N B

    2004-01-01

    The charge-exchange reaction pd -> npp at 1 GeV projectile proton energy is studied. This reaction is considered in a special kinematics, when the transfer momentum from the beam proton to fast outgoing neutron is close to zero. Our approach is based on the Alt-Grassberger-Sandhas formulation of the multiple-scattering theory for the three-nucleon system. The matrix inversion method has been applied to take account of the final state interaction (FSI) contributions. The differential cross section, tensor analyzing power $C_{0,yy}$, vector-vector $C_{y,y}$ and vector-tensor $C_{y,xz}$ spin correlation parameters of the initial particles are presented. It is shown, that the FSI effects play a very important role under such kinematical conditions. The high sensitivity of the considered observables to the elementary nucleon-nucleon amplitudes has been obtained.

  6. Electron transfer pathway analysis in bacterial photosynthetic reaction center

    CERN Document Server

    Kitoh-Nishioka, Hirotaka

    2016-01-01

    A new computational scheme to analyze electron transfer (ET) pathways in large biomolecules is presented with applications to ETs in bacterial photosynthetic reaction center. It consists of a linear combination of fragment molecular orbitals and an electron tunneling current analysis, which enables an efficient first-principles analysis of ET pathways in large biomolecules. The scheme has been applied to the ET from menaquinone to ubiquinone via nonheme iron complex in bacterial photosynthetic reaction center. It has revealed that not only the central Fe$^{2+}$ ion but also particular histidine ligands are involved in the ET pathways in such a way to mitigate perturbations that can be caused by metal ion substitution and depletion, which elucidates the experimentally observed insensitivity of the ET rate to these perturbations.

  7. Kinetics and Mechanism of the Gas-Phase Reaction of Selected Carbonyls with Cl Atoms between 250 and 340 K

    Science.gov (United States)

    Hasson, A. S.; Algrim, L.; Abdelhamid, A.; Tyndall, G. S.; Orlando, J. J.

    2013-12-01

    Carbonyls are important products from the gas phase degradation of most volatile organic compounds. Their atmospheric reactions therefore have a significant impact on atmospheric composition, particularly in aged air masses. While the reactions of short-chain linear carbonyls are well understood, the chemistry of larger (> C6) and branched carbonyl is more uncertain. To provide insight into these reactions, the reactions of three carbonyls (methyl isopropyl ketone, MIK; di-isopropyl ketone, DIK; and diethyl ketone, DEK) with chlorine atoms were investigated between 250 and 340 K and 1 atm in the presence and absence of NOx and an HO2 source (methanol). Experiments were performed in a photochemical reactor using a combination of long-path Fourier transform infra-red spectroscopy, proton transfer reaction mass spectrometry and gas chromatography with flame ionization detection. The kinetics were studied using the relative rate technique with butanone and isopropanol as the reference compounds. The Arrhenius expression for the three rate coefficients was determined to be k(DEK+Cl) = 3.87 x 10-11e(2 × 7 kJ/mol)/RT cm3 molecules-1 s-1 , k(MIPK+Cl) = 7.20 x 10-11e(0.2× 8 kJ/mol)/RT cm3 molecules-1 s-1 , and k(DIPK+Cl) = 3.33 x 10-10e(-3× 8 kJ/mol)/RT cm3 molecules-1 s-1 . Measured reaction products accounted for 38-72 % of the reacted carbon and were consistent with strong deactivation of the carbon atom adjacent to the carbonyl group with respect to H-atom abstraction by Cl atoms. The product distributions also provide insight into radical recycling from the organic peroxy + HO2 reaction, and the relative rates of isomerization, fragmentation and reaction with O2 for carbonyl-containing alkoxy radicals. Implications of these results will be discussed.

  8. Reaction Mechanism of Oxygen Atoms with Unsaturated Hydrocarbons by the Crossed-Molecular-Beams Method

    Science.gov (United States)

    Buss, R. J.; Baseman, R. J.; Guozhong, H.; Lee, Y. T.

    1982-04-01

    From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

  9. A computational study of the phosphoryl transfer reaction between ATP and Dha in aqueous solution.

    Science.gov (United States)

    Bordes, I; Ruiz-Pernía, J J; Castillo, R; Moliner, V

    2015-10-28

    Phosphoryl transfer reactions are ubiquitous in biology, being involved in processes ranging from energy and signal transduction to the replication genetic material. Dihydroxyacetone phosphate (Dha-P), an intermediate of the synthesis of pyruvate and a very important building block in nature, can be generated by converting free dihydroxyacetone (Dha) through the action of the dihydroxyacetone kinase enzyme. In this paper the reference uncatalyzed reaction in solution has been studied in order to define the foundations of the chemical reaction and to determine the most adequate computational method to describe this electronically complex reaction. In particular, the phosphorylation reaction mechanism between adenosine triphosphate (ATP) and Dha in aqueous solution has been studied by means of quantum mechanics/molecular mechanics (QM/MM) Molecular Dynamics (MD) simulations with the QM subset of atoms described with semi-empirical and DFT methods. The results appear to be strongly dependent on the level of calculation, which will have to be taken into account for future studies of the reaction catalyzed by enzymes. In particular, PM3/MM renders lower free energy barriers and a less endergonic process than AM1d/MM and PM6/MM methods. Nevertheless, the concerted pathway was not located with the former combination of potentials. PMID:26303076

  10. Momentum Transfer of an Atom Moving in an Optical Cavity

    Institute of Scientific and Technical Information of China (English)

    张敬涛; 徐至展

    2001-01-01

    When an atom moves in an optical cavity, the total momentum of the atom does not remain constant. We study a two-level atom moving slowly in an optical cavity, and give the time dependence of its mean momentum. It is found that when the initial momentum of the atom is larger than that of the photon, the mean momentum oscillates around a value less than the initial value. But, if the initial momentum is less than the momentum of the photon, the mean momentum of the atom is greater than its initial value in most cases.

  11. Chemical reactions of excited nitrogen atoms for short wavelength chemical lasers. Final technical report

    Energy Technology Data Exchange (ETDEWEB)

    1989-12-15

    Accomplishments of this program include the following: (1) Scalable, chemical generation of oxygen atoms by reaction of fluorine atoms and water vapor. (2) Production of nitrogen atom densities of 1 {times} 10{sup 1}5 cm{sup {minus}3} with 5% electrical efficiency by injecting trace amounts of fluorine into microwave discharged nitrogen. (3) Production of cyanide radicals by reaction of high densities of N atoms with cyanogen. (4) Production of carbon atoms by reaction of nitrogen atoms with cyanogen or with fluorine atoms and hydrogen cyanide. (5) Confirmation that the reaction of carbon atoms and carbonyl sulfide produces CS(a{sup 3} {Pi}{sub r}), as predicted by conservation of electron spin and orbital angular momenta and as proposed by others under another SWCL program. (6) Production of cyanide radicals by injection of cyanogen halides into active nitrogen and use as spectroscopic calibration source. (7) Demonstration that sodium atoms react with cyanogen chloride, bromide and iodide and with cyanuric trifluoride to produce cyanide radicals. (8) Demonstration of the potential utility of the fluorine atom plus ammonia reaction system in the production of NF(b{sup l}{Sigma}{sup +}) via N({sup 2}D) + F{sub 2}.

  12. Oxygen Atom Exchange Mechanism in Reaction of OH Radical with AsO

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Oxygen atom exchange reaction mechanism in the reaction of OH radicals with AsO was investigated by means of the density functional theory (DFT) with 6-311++G(3df,3pd) and 6-311++G(d,p) basis sets. The calculated results suggest that the reaction between OH and AsO should make the oxygen atoms exchange rapidly because the barrier to isomerization is significantly less than the HO-AsO bond dissociation energy.

  13. Single-nucleon transfer reactions on 18F

    International Nuclear Information System (INIS)

    Simultaneous measurement of the proton-transfer 18F(d, n)19Ne and neutron-transfer 18F(d, p)19F reactions were performed with a 18F radioactive beam at the Holifield Radioactive Ion Beam Facility at Oak Ridge National Laboratory. The experiments clarify the nuclear structure of 19Ne near the proton threshold, which is relevant for understanding the rates of proton-induced reactions on 18F in novae. Analogs for several states in the mirror nucleus 19F have not yet been identified in 19Ne, indicating that the level structure of 19Ne in this region is incomplete. We observed 15 levels in 19Ne from the 18F(d, n)19Ne measurement and 18 levels in 19F from the 18F(d, p)19F measurement. Angular distributions were extracted for all strongly populated states and compared to distorted-wave Born approximation calculations. The angular distributions for all the known states in the two nuclei determined in this work are consistent with their previously assigned spins and parities. The spectroscopic factors determined for these levels in the two nuclei are reported.

  14. Three-Body Model Analysis of Subbarrier alpha Transfer Reaction

    CERN Document Server

    Fukui, Tokuro; Yahiro, Masanobu

    2011-01-01

    Subbarrier alpha transfer reaction 13C(6Li,d)17O(6.356 MeV, 1/2+) at 3.6 MeV is analyzed with a alpha + d + 13C three-body model, and the asymptotic normalization coefficient (ANC) for alpha + 13C --> 17O(6.356 MeV, 1/2+), which essentially determines the reaction rate of 13C(alpha,n)16O, is extracted. Breakup effects of 6Li in the initial channel and those of 17O in the final channel are investigated with the continuum-discretized coupled-channels method (CDCC). The former is found to have a large back-coupling to the elastic channel, while the latter turns out significantly small. The transfer cross section calculated with Born approximation to the transition operator, including breakup states of 6Li, gives (C_{alpha 13C}{17O*})^2 =1.03 \\pm 0.29 fm^{-1}. This result is consistent with the value obtained by the previous DWBA calculation.

  15. Surface modification of nanoporous 1,2-polybutadiene by atom transfer radical polymerization or click chemistry.

    Science.gov (United States)

    Guo, Fengxiao; Jankova, Katja; Schulte, Lars; Vigild, Martin E; Ndoni, Sokol

    2010-02-01

    Surface-initiated atom transfer radical polymerization (ATRP) and click chemistry were used to obtain functional nanoporous polymers based on nanoporous 1,2-polybutadiene (PB) with gyroid morphology. The ATRP monolith initiator was prepared by immobilizing bromoester initiators onto the pore walls through two different methodologies: (1) three-step chemical conversion of double bonds of PB into bromoisobutyrate, and (2) photochemical functionalization of PB with bromoisobutyrate groups. Azide functional groups were attached onto the pore walls before click reaction with alkynated MPEG. Following ATRP-grafting of hydrophilic polyacrylates and click of MPEG, the originally hydrophobic samples transformed into hydrophilic nanoporous materials. The successful modification was confirmed by infrared spectroscopy, contact angle measurements and measurements of spontaneous water uptake, while the morphology was investigated by small-angle X-ray scattering and transmission electron microscopy. PMID:20099923

  16. Synthesis of Dumbbell-shaped Hyperbranched Amphiphilic Block Copolymer by Controlled Atom Transfer Radical Polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Kim, In Kyoung; An, Sung Guk; Cho, Chang Gi [Center for Advanced Functional Polymers, Department of Fiber and Polymer Science, Hanyang University, Seoul (Korea); Noh, Si Tae [Department of Chemical Engineering, Hanyang University, Ansan (Korea)

    2001-04-01

    Amphiphilic block copolymers containing hydrophilic ethylene glycol core and hyperbranched polystyrene (PS) arm were synthesized by atom transfer radical polymerization using hydrophilic macroinitiator and p-chloromethyl styrene (CMS) as AB type monomer. Hydrophilic poly(ethylene glycol)(PEG) macroinitiators with difuntional groups were synthesized by reacting PEG and 2-bromopropionyl bromide. The chemical structure, molecular weight, and polydispersity index of the amphiphilic block copolymer were characterized by {sup 1}H-NMR spectroscopy and GPC analysis. The molecular weight increased as the reaction time increased. Polydispersity index of the obtained polymer was relatively narrow (below 1.39). To control chain density of the hyperbranched PS, styrene and CMS were copolymerized. It was found that amphiphilic block copolymer molecule underwent conformational change in different solvents based on the result for {sup 1}H-NMR spectroscopic analysis. 29 refs., 8 figs., 2 tabs.

  17. Surface-initiated atom transfer radical polymerization of methyl methacrylate from magnetite nanoparticles at ambient temperature.

    Science.gov (United States)

    Raghuraman, G K; Dhamodharan, R

    2006-07-01

    The synthesis of methyl methacrylate (MMA) brush from the surface of magnetite nanoparticles (core-shell structure), from initiator moieties anchored covalently to the nanoparticles, via room temperature atom transfer radical polymerization (ATRP) is described. The surface-initiated polymerization was carried out from a surface-confined initiator containing a 2-bromoisobutyrate moiety with Cu(I)Br/PMDETA catalytic system. The initiator moiety was covalently anchored to the nanoparticles via a two step modification reaction scheme. Controlled polymerization was observed if ethyl-2-bromoisobutyrate (2-EiBrB) was added as a free/sacrificial initiator. A linear increase of molecular weight and a narrow molecular weight distribution of the PMMA formed in solution, provide evidence for a controlled surface-initiated polymerization, leading to surface-attached polymer brushes under mild conditions. The grafted PMMA provides good stability and dispersibility for the nanoparticles in organic solvents.

  18. Nonadiabatic effects on population transfer of two Bose-Einstein condensates induced by atomic interaction

    Institute of Scientific and Technical Information of China (English)

    胡正峰; 杜春光; 李师群

    2003-01-01

    We investigate the stimulated Raman adiabatic passage for Bose-Einstein condensate (BEG) states which are trapped in different potential wells or two ground states of BEG in the same trap. We consider that lasers are nearly resonant with the atomic transitions. The difference of population transfer processes between BEG atoms and usual atoms is that the atomic interaction of the BEG atoms can cause some nonadiabatic effects, which may degrade the process. But with suitable detunings of laser pulses, the effects can be remedied to some extent according to different atomic interactions.

  19. Probing the pairing interaction through two-neutron transfer reactions

    Directory of Open Access Journals (Sweden)

    Margueron J.

    2012-12-01

    Full Text Available The treatment of the pairing interaction in mean-field-based models is addressed. In particular, the possibility to use pair transfers as A tool to better constrain this interaction is discussed. First, pairing inter-actions with various density dependencies (surface/volume mixing are used in the microscopic Hartree-Fock-Bogoliubov + quasiparticle random-phase approximation model to generate the form factors to be used in reaction calculations. Cross sections for (p,t two-neutron transfer reactions are calculated in the one-step zero-range distorted-wave Born approximation for some Tin isotopes and for incident proton energies from 15 to 35 MeV. Three different surface/volume mixings of A zero-range density-dependent pairing interaction are employed in the microscopic calculations and the sensitivity of the cross sections to the different mixings is analyzed. Differences among the three different theoretical predictions are found espacially for the nucleus 136Sn and they are more important at the incident proton energy of 15 MeV. We thus indicate (p,t two-neutron transfer reactions with very neutron-rich Sn isotopes and at proton energies around 15 MeV as good experimental cases where the surface/volume mixing of the pairing interaction may be probed. In the second part of the manuscript, ground-state to ground-state transitions are investigated. Approximations made to estimate two-nucleon transfer probabilities in ground-state to ground-state transitions and the physical interpretation of these probabilities are discussed. Probabilities are often calculated by approximating both ground states of the initial nucleus A and of the final nucleus A±2 by the same quasiparticle vacuum. We analyze two improvements of this approach. First, the effect of using two different ground states with average numbers of particles A and A±2 is quantified. Second, by using projection techniques, the role of particle number restoration is analyzed. Our analysis

  20. Skeletal Isomerization and Inter-molecular Hydrogen Transfer Reactions in Catalytic Cracking

    Institute of Scientific and Technical Information of China (English)

    Gao Yongcan; Zhang Jiushun; Xie Chaogang; Long Jun

    2002-01-01

    Bimolecular hydrogen transfer and skeletal isomerization are the important secondary reac tions among catalytic cracking reactions, which affect product yield distribution and product quality.Catalyst properties and operating parameters have great impact on bimolecular hydrogen transfer and skeletal isomerization reactions. Bimolecular hydrogen transfer activity and skeletal isomerization activity of USY-containing catalysts are higher than that of ZSM-5-containing catalyst. Coke deposition on the active sites of catalyst may suppress bimolecular hydrogen transfer activity and skeletal isomerization activity of catalyst in different degrees. Short reaction time causes a decrease of hydrogen trans fer reaction, but an increase of skeletal isomerization reaction compared to cracking reaction in catalytic cracking process.

  1. On the nuclear $(n;t)-$reaction in the three-electron ${}^{6}$Li atom

    CERN Document Server

    Frolov, Alexei M

    2012-01-01

    The nuclear $(n;t)-$reaction of the three-electron ${}^{6}$Li atom with thermal/slow neutrons is considered. An effective method has been developed for determining the probabilities of formation of various atoms and ions in different bound states. We discuss a number of fundamental questions directly related to numerical computations of the final state atomic probabilities. A few appropriate variational expansions for atomic wave functions of the incident lithium atom and final helium atom and/or tritium negatively charged ion are discussed. It appears that the final ${}^4$He atom arising during the nuclear $(n,{}^{6}$Li; ${}^4$He$,t)$-reaction in the three-electron Li atom can also be created in its triplet states. The formation of the quasi-stable three-electron $e^{-}_3$ during the nuclear $(n; t)-$reaction at the Li atom is briefly discussed. Bremsstrahlung emitted by atomic electrons accelerated by the rapidly moving fragments from this reaction is analyzed. The frequency spectrum of the emitted radiatio...

  2. Study of the Ne(^3P_2) + CH_3F Electron Transfer Reaction below 1 Kelvin

    CERN Document Server

    Jankunas, Justin; Osterwalder, Andreas

    2014-01-01

    Relatively little is known about the dynamics of electron transfer reactions at low collision energy. We present a study of Penning ionization of ground state methyl fluoride molecules by electronically excited neon atoms in the 13 $\\mu$eV--4.8 meV (150 mK--56 K) collision energy range, using a neutral-neutral merged beam setup. Relative cross sections have been measured for three Ne($^3P_2$)+ CH$_3$F reaction channels by counting the number of CH$_3$F$^+$, CH$_2$F$^+$, and CH$_3^+$ product ions, as a function of relative velocity between the neon and methyl fluoride molecular beams. Experimental cross sections markedly deviate from the Langevin capture model at collision energies above 20 K. The branching ratios are constant. In other words, the chemical shape of the CH$_3$F molecule, as seen by Ne($^3P_2$) atom, appears not to change as the collision energy is varied, in contrast to related Ne($^3P_J$) + CH$_3$X (X=Cl and Br) reactions at higher collision energies.

  3. HYDROPHILIC MODIFICATION OF PPESK POROUS MEMBRANES VIA AQUEOUS SURFACE-INITIATED ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Zhuan Yi; You-yi Xu; Li-ping Zhu; Han-bang Dong; Bao-ku Zhu

    2009-01-01

    Hydrophilic surface modification of poly(phthalazinone ether sulfone ketone)(PPESK)porous membranes was achieved via surface-initiated atom transfer radical polymerization(ATRP)in aqueous medium.Prior to ATRP,chloromethyl groups were introduced onto PPESK main chains by chloromethylation.Chloromethylated PPESK(CMPPESK)was fabricated into porous membrane through phase inversion technique.Hydrophilic poly(poly(ethylene glycol)methyl ether methacrylate)(P(PEGMA))brushes were grafted from CMPPESK membrane under the initiation of benzyl chloride groups on membrane surface.The results of Fourier transform infrared(FT-IR)spectroscopy and X-ray photoelectron spectroscopy (XPS)confirmed the grafting of P(PEGMA)chains.Water contact angle measurements and protein adsorption experiments suggested that the hydrophilicity and anti-fouling ability of PPESK membrane were remarkably improved after the grafting of P(PEGMA)brushes.The addition of small amount of water in the reaction solvent apparently accelerated the progress of the grafting reaction.The use of CuCl2 in the catalyst system promoted the controllability of the ATRP reaction.

  4. A scheme for transferring an unknown atomic entangled state via cavity quantum electrodynamics

    Institute of Scientific and Technical Information of China (English)

    Wu Tao; Ye Liu; Ni Zhi-Xiang

    2006-01-01

    In this paper, we propose a scheme for transferring an unknown atomic entangled state via cavity quantum electrodynamics (QED). This scheme, which has a successful probability of 100 percent, does not require Bell-state measurement and performing any operations to reconstruct an initial state. Meanwhile, the scheme only involves atomfield interaction with a large detuning and does not require the transfer of quantum information between the atoms and cavity. Thus the scheme is insensitive to the cavity field states and cavity decay. This scheme can also be extended to transfer ring an entangled state of n-atom.

  5. Synthesis and characterization of poly(2-ethylhexyl acrylate) prepared via atom transfer radical polymerization, reverse atom transfer radical polymerization and radical polymerization

    Indian Academy of Sciences (India)

    Dhruba Jyoti Haloi; Bishnu Prasad Koiry; Prithwiraj Mandal; Nikhil Kumar Singha

    2013-07-01

    This investigation reports a comparative study of poly(2-ethylhexyl acrylate) (PEHA) prepared via atom transfer radical polymerization (ATRP), reverse atom transfer radical polymerization (RATRP) and conventional free radical polymerization (FRP). The molecular weights and the molecular weight distributions of the polymers were measured by gel permeation chromatography (GPC) analysis. Structural characterization of the polymers was carried out by 1H NMR and MALDI-TOF-MS analyses. Thermal properties of the polymers were evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The polymerization results and the thermal properties of PEHAs prepared via ATRP, RATRP and FRP were compared.

  6. Charge transfer reaction of multi-charged oxygen ions with O2

    Science.gov (United States)

    Holzscheiter, H. M.; Church, D. A.

    1981-10-01

    The reaction rates for charge transfer from O2 to doubly and triply charged oxygen atoms are measured in a demonstration of the measurement capabilities of a system at ultrahigh vacuum with low-energy magnetically confined ions. Ions were produced by electron impact ionization of gas within a Penning-type ion trap, with selective removal of unwanted ionization states by radio-frequency resonant excitation. Ion number mass-to-charge ratio spectra obtained at partial pressures of O2 from 9.9 x 10 to the -9th to 1.5 x 10 to the -7th torr yield rate constants of 1.0 x 10 to the -9th cu cm/sec and 2.5 x 10 to the -9th cu cm/sec for the O(2+) and O(3+) reactions, respectively. Measurements made at a 30% increase of the effective axial well depth of the trap demonstrate that the rate constant is essentially energy independent in the energy range studies, implying that the O(2+) cross section for charge transfer has an inverse velocity dependence of the Langevin type, despite a reaction rate lower than the Langevin valve.

  7. Mass transfer in porous media with heterogeneous chemical reaction

    Directory of Open Access Journals (Sweden)

    Souza S.M.A.G.Ulson de

    2003-01-01

    Full Text Available In this paper, the modeling of the mass transfer process in packed-bed reactors is presented and takes into account dispersion in the main fluid phase, internal diffusion of the reactant in the pores of the catalyst, and surface reaction inside the catalyst. The method of volume averaging is applied to obtain the governing equation for use on a small scale. The local mass equilibrium is assumed for obtaining the one-equation model for use on a large scale. The closure problems are developed subject to the length-scale constraints and the model of a spatially periodic porous medium. The expressions for effective diffusivity, hydrodynamic dispersion, total dispersion and the Darcy's law permeability tensors are presented. Solution of the set of final equations permits the variations of velocity and concentration of the chemical species along the packed-bed reactors to be obtained.

  8. Large momentum transfer atom interferometry with Coriolis force compensation

    Science.gov (United States)

    Kuan, Pei-Chen; Lan, Shau-Yu; Estey, Brian; Haslinger, Philipp; Mueller, Holger

    2012-06-01

    Light-pulse atom interferometers use atom-photon interactions to coherently split, guide, and recombine freely falling matter-waves. Because of Earth's rotation, however, the matter-waves do not recombine precisely, which causes severe loss of contrast in large space-time atom interferometers. I will present our recent progress in using a tip-tilt mirror to remove the influence of the Coriolis force from Earth's rotation. Therefore, we improve the contrast and suppress systematic effects, also reach what is to our knowledge the largest spacetime area.

  9. Heat transfer analysis of atomized droplets during high velocity arc spraying

    Institute of Scientific and Technical Information of China (English)

    ZHU Zi-xin; LIU Yan; CHEN Yong-xiong; XU Bin-shi; ZHANG Wei

    2004-01-01

    The heat transfer problem of the atomized droplets during high velocity arc spraying (HVAS) was modeled and solved by a numerical method using a Fe-Al alloy, and the influences of several important process parameters on the heat transfer behaviors of the atomized droplets were analyzed. The results show that the initial cooling rates of different size droplets range from 105 to 107 K/s, thus producing the coating microstructure with the features of rapid solidification. The droplet size, atomization gas pressure and droplet superheat have great influences on the heat transfer behavior of the droplet. The droplet temperature and cooling rate are much sensitive to the droplet sizes, but insensitive to the atomization gas pressure and droplet superheat. It can be predicted that the properties of HVAS coatings will be improved by decreasing droplet size as well as increasing atomization gas pressure and droplet superheat in certain extents.

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

    Indian Academy of Sciences (India)

    K Chakrabarti

    2002-03-01

    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.

  11. Multinucleon transfer in the 136Xe+208Pb reaction

    Science.gov (United States)

    Li, Cheng; Zhang, Fan; Li, Jingjing; Zhu, Long; Tian, Junlong; Wang, Ning; Zhang, Feng-Shou

    2016-01-01

    The dynamic mechanics in the multinucleon transfer reaction 136Xe+208Pb at an incident energy of Ec .m .=450 MeV is investigated by using the improved quantum molecular dynamics model (ImQMD). The lifetime of the neck directly influences the nucleon exchange and energy dissipation between the projectile and the target. The total-kinetic-energy-mass distributions and excitation energy division of primary binary fragments and the mass distributions of primary fragments at different impact parameters are calculated. The thermal equilibrium between two reaction partners has been observed at the lifetime of a neck larger than 480 fm /c . By using the statistical decay code gemini to describe the de-excitation process of the primary fragments, the isotope production cross sections from Pt to At are compared with the prediction by the dinuclear system and GRAZING model. The calculations indicate that the GRAZING model is suitable for estimating the isotope production cross sections only for Δ Z =-1 to +2; the DNS + gemini calculations underestimate the cross sections in the neutron-rich and neutron-deficient regions; and the ImQMD + gemini calculations give reasonable predictions of the isotope production cross sections for Δ Z =-3 to 0.

  12. Ab initio Mechanism Study on the Reaction of Chlorine Atom with Formic Acid

    Institute of Scientific and Technical Information of China (English)

    于海涛; 付宏刚; 等

    2003-01-01

    The potential energy surface(PES) for the reaction of Cl atom with HCOOH is predicted using ab initio molecular orbital calculation methods at UQCIDS(T,full)6-311++G(3df,2p)//UMP2(full)/6-311+G(d,P) level of theory with zero-point vibrational energy (ZPVE) correction.The calculated results show that the reaction mechanism of Cl atom with formic acid is a C-site hydrogen abstraction reaction from cis-HOC(H)O molecule by Cl atom with a 3.73kJ/mol reaction barrier height,leading to the formation of cis-HOCO radical which will reacts with Cl atom or other molecules in such a reaction system.Because the reaction barrier height of O-site hydrogen abstraction reaction from cis-HOC(H)O molecule by Cl atom which leads to the formation of HCO2 radical is 67.95kJ/mol,it is a secondary reaction channel in experiment,This is in good agreement with the prediction based on the previous experiments.

  13. Pulse radiolysis studies of the reactions of bromine atoms and dimethyl sulfoxide-bromine atom complexes with alcohols

    International Nuclear Information System (INIS)

    Dimethylsulfoxide (DMSO)-Br complexes were generated by pulse radiolysis of DMSO/bromomethane mixtures and the formation mechanism and spectral characteristics of the formed complexes were investigated in detail. The rate constant for the reaction of bromine atoms with DMSO and the extinction coefficient of the complex were obtained to be 4.6x109 M-1 s-1 and 6300 M-1 cm-1 at the absorption maximum of 430 nm. Rate constants for the reaction of bromine atoms with a series of alcohols were determined in CBrCl3 solutions applying a competitive kinetic method using the DMSO-Br complex as the reference system. The obtained rate constants were ∼108 M-1 s-1, one or two orders larger than those reported for highly polar solvents. Rate constants of DMSO-Br complexes with alcohols were determined to be ∼ 107 M-1 s-1. A comparison of the reactivities of Br atoms and DMSO-Br complexes with those of chlorine atoms and chlorine atom complexes which are ascribed to hydrogen abstracting reactants strongly indicates that hydrogen abstraction from alcohols is not the rate determining step in the case of Br atoms and DMSO-Br complexes

  14. Comparative Study of Cl-Atom Reactions in Solution Using Time-Resolved Vibrational Spectroscopy.

    Science.gov (United States)

    Shin, Jae Yoon; Case, Amanda S; Crim, F Fleming

    2016-04-28

    A Cl atom can react with 2,3-dimethylbutane (DMB), 2,3-dimethyl-2-butene (DMBE), and 2,5-dimethyl-2,4-hexadiene (DMHD) in solution via a hydrogen-abstraction reaction. The large exoergicity of the reaction between a Cl atom and alkenes (DMBE and DMHD) makes vibrational excitation of the HCl product possible, and we observe the formation of vibrationally excited HCl (v = 1) for both reactions. In CCl4, the branching fractions of HCl (v = 1), Γ (v = 1), for the Cl-atom reactions with DMBE and DMHD are 0.14 and 0.23, respectively, reflecting an increased amount of vibrational excitation in the products of the more exoergic reaction. In addition, Γ (v = 1) for both reactions is larger in the solvent CDCl3, being 0.23 and 0.40, as the less viscous solvent apparently dampens the vibrational excitation of the nascent HCl less effectively. The bimolecular reaction rates for the Cl reactions with DMB, DMBE, and DMHD in CCl4 are diffusion limited (having rate constants of 1.5 × 10(10), 3.6 × 10(10), and 17.5 × 10(10) M(-1) s(-1), respectively). In fact, the bimolecular reaction rate for Cl + DMHD exceeds a typical diffusion-limited reaction rate, implying that the attractive intermolecular forces between a Cl atom and a C═C bond increase the rate of favorable encounters. The 2-fold increase in the reaction rate of the Cl + DMBE reaction from that of the Cl + DMB reaction likely reflects the effect of the C═C bond, while both the number of C═C bonds and the molecular geometry likely play a role in the large reaction rate of the Cl + DMHD reaction.

  15. Universal four-boson system: dimer-atom-atom Efimov effect and recombination reactions

    CERN Document Server

    Deltuva, A

    2013-01-01

    Recent theoretical developments in the four-boson system with resonant interactions are described. Momentum-space scattering equations for the four-particle transition operators are used. The properties of unstable tetramers with approximate dimer-atom-atom structure are determined. In addition, the three- and four-cluster recombination processes in the four-boson system are studied.

  16. Photon exchange and correlation transfer in atom-atom entanglement dynamics

    OpenAIRE

    León García, Juan José; Sabín, Carlos

    2009-01-01

    We analyze the entanglement dynamics of a system composed by a pair of neutral two-level atoms that are initially entangled, and the electromagnetic field, initially in the vacuum state, within the formalism of perturbative quantum field theory up to the second order. We show that entanglement sudden death and revival can occur while the atoms remain spacelike-separated and therefore cannot be related with photon exchange between the atoms. We interpret these phenomena as the consequence of a...

  17. Hot reactions between tritium atoms and inorganic compounds (H2O,H2S,NH3)

    International Nuclear Information System (INIS)

    Hot atom chemical reactions of tritium from nuclear reactions 3He(n,p)T and 6Li(n,α)T or from an accelerator with H2O,D2O,H2S,NH3,ND3 are studied in gaseous and liquid phases. Hot reactive collisions produce mainly HT or DT and the synthesis of the initial tritiated compound HTO, DTO, HTS, NH2T or ND2T. In ND3 the analysis of the conjugated action of scavengers and moderators allows the determination of integral reactivity corresponding to the different hot reactions. Influence of gas pressure or gas-liquid transition is interpreted by the competition between monomolecular decomposition of tritiated compounds and their stabilization by intermolecular energy transfer. Slight isotopic effects measured show a compensation between chemical reactivity and moderating power of H2O and D2O or NH3 and ND3 molecules. 99 refs

  18. Controlled Reactions between Ultracold Alkali and Metastable Helium Atoms

    CERN Document Server

    Flores, Adonis Silva; Knoop, Steven

    2016-01-01

    In an ultracold, optically trapped mixture of $^{87}$Rb and metastable triplet $^4$He atoms we have studied trap loss for different spin-state combinations, for which interspecies Penning ionization is the main two-body loss process. We observe long trapping lifetimes for the purely quartet spin-state combination, indicating strong suppression of Penning ionization loss by at least two orders of magnitude. For the other spin-mixtures we observe short lifetimes that depend linearly on the doublet character of the entrance channel. We compare the extracted loss rate coefficient with recent predictions of multichannel quantum-defect theory for reactive collisions involving a strong exothermic loss channel and find near-universal loss for doublet scattering. Our work demonstrates control of reactive collisions by internal atomic state preparation, which also implies magnetic field tunability.

  19. High energy halogen atom reactions activated by nuclear transformations

    International Nuclear Information System (INIS)

    This program, which has been supported for twenty-four years by the Us Atomic Energy Commission and its successor agencies, has produced significant advances in the understanding of the mechanisms of chemical activation by nuclear processes; the stereochemistry of radioactivity for solution of specific problems. This program was contributed to the training of approximately seventy scientists at various levels. This final report includes a review of the areas of research and chronological tabulation of the publications

  20. Modulation Transfer Spectroscopy of Ytterbium Atoms in a Hollow Cathode Lamp

    International Nuclear Information System (INIS)

    We present the experimental study of modulation transfer spectroscopy of ytterbium atoms in a hollow cathode lamp. The dependences of its linewidth, slope and magnitude on the various experimental parameters are measured and fitted by the well-known theoretical expressions. The experimental results are in good agreement with the theoretical prediction. We have observed the Dicke narrowing effect by increasing the current of the hollow cathode lamp. It is also found that there are the optimal current and laser power to generate the better modulation transfer spectroscopy signal, which can be employed for locking the laser frequency to the atomic transition. (atomic and molecular physics)

  1. Synergistic oxygen atom transfer by ruthenium complexes with non-redox metal ions.

    Science.gov (United States)

    Lv, Zhanao; Zheng, Wenrui; Chen, Zhuqi; Tang, Zhiming; Mo, Wanling; Yin, Guochuan

    2016-07-28

    Non-redox metal ions can affect the reactivity of active redox metal ions in versatile biological and heterogeneous oxidation processes; however, the intrinsic roles of these non-redox ions still remain elusive. This work demonstrates the first example of the use of non-redox metal ions as Lewis acids to sharply improve the catalytic oxygen atom transfer efficiency of a ruthenium complex bearing the classic 2,2'-bipyridine ligand. In the absence of Lewis acid, the oxidation of ruthenium(ii) complex by PhI(OAc)2 generates the Ru(iv)[double bond, length as m-dash]O species, which is very sluggish for olefin epoxidation. When Ru(bpy)2Cl2 was tested as a catalyst alone, only 21.2% of cyclooctene was converted, and the yield of 1,2-epoxycyclooctane was only 6.7%. As evidenced by electronic absorption spectra and EPR studies, both the oxidation of Ru(ii) by PhI(OAc)2 and the reduction of Ru(iv)[double bond, length as m-dash]O by olefin are kinetically slow. However, adding non-redox metal ions such as Al(iii) can sharply improve the oxygen transfer efficiency of the catalyst to 100% conversion with 89.9% yield of epoxide under identical conditions. Through various spectroscopic characterizations, an adduct of Ru(iv)[double bond, length as m-dash]O with Al(iii), Ru(iv)[double bond, length as m-dash]O/Al(iii), was proposed to serve as the active species for epoxidation, which in turn generated a Ru(iii)-O-Ru(iii) dimer as the reduced form. In particular, both the oxygen transfer from Ru(iv)[double bond, length as m-dash]O/Al(iii) to olefin and the oxidation of Ru(iii)-O-Ru(iii) back to the active Ru(iv)[double bond, length as m-dash]O/Al(iii) species in the catalytic cycle can be remarkably accelerated by adding a non-redox metal, such as Al(iii). These results have important implications for the role played by non-redox metal ions in catalytic oxidation at redox metal centers as well as for the understanding of the redox mechanism of ruthenium catalysts in the oxygen atom

  2. Coherent population transfer in Rydberg potassium atom by a single frequency-chirped laser pulse

    Institute of Scientific and Technical Information of China (English)

    Zhang Xian-Zhou; Ma Qiao-Zhi; Li Xiao-Hong

    2006-01-01

    By using the time-dependent multilevel approach, we have calculated the coherent population transfer among the quantum states of potassium atom by a single frequency-chirped laser pulse. The results show that the population can be efficiently transferred to a target state and be trapped there by using an ‘intuitive’ or a ‘counter-intuitive’ frequency sweep laser pulse in the case of ‘narrowband’ frequency-chirped laser pulse. It is also found that a pair of sequential ‘broadband’ frequency-chirped laser pulses can efficiently transfer population from one ground state of the A atom to the other one.

  3. Chemisorption and reactions on clusters of nickel atoms

    Science.gov (United States)

    Waber, J. T.; Adachi, H.; Yu, T.

    1982-01-01

    The nucleation and growth of metallic clusters on a substantially amorphous substrate are discussed with emphasis on the geometrical and electronic structure of the clusters. Several clusters of different symmetry containing five to nine nickel atoms were studied. It was found that the energy range of primary d-like states is not significantly different from the width of the d-band states in nickel metal, as long as the interatomic distance is comparable to that in the bulk metal. The approach of one or more molecules to the cluster is examined using at the hydrogenation of acetylene and the dehydrogenation of ethylene as examples.

  4. Single-Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions.

    Science.gov (United States)

    Yang, Sungeun; Kim, Jiwhan; Tak, Young Joo; Soon, Aloysius; Lee, Hyunjoo

    2016-02-01

    As a catalyst, single-atom platinum may provide an ideal structure for platinum minimization. Herein, a single-atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single-atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single-atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen-reduction reaction toward a two-electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single-atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity.

  5. A general theoretical model for electron transfer reactions in complex systems.

    Science.gov (United States)

    Amadei, Andrea; Daidone, Isabella; Aschi, Massimiliano

    2012-01-28

    In this paper we present a general theoretical-computational model for treating electron transfer reactions in complex atomic-molecular systems. The underlying idea of the approach, based on unbiased first-principles calculations at the atomistic level, utilizes the definition and the construction of the Diabatic Perturbed states of the involved reactive partners (i.e. the quantum centres in our perturbation approach) as provided by the interaction with their environment, including their mutual interaction. In this way we reconstruct the true Adiabatic states of the reactive partners characterizing the electron transfer process as the fluctuation of the electronic density due to the fluctuating perturbation. Results obtained by using a combination of Molecular Dynamics simulation and the Perturbed Matrix Method on a prototypical intramolecular electron transfer (from 2-(9,9'-dimethyl)fluorene to the 2-naphthalene group separated by a steroidal 5-α-androstane skeleton) well illustrate the accuracy of the method in reproducing both the thermodynamics and the kinetics of the process. PMID:22158942

  6. Intramolecular proton transfer and tunnelling reactions of hydroxyphenylbenzoxazole derivatives in Xenon at 15 K

    Energy Technology Data Exchange (ETDEWEB)

    Walla, Peter J. [Max-Planck-Institute for Biophysical Chemistry, Department 010, Spectroscopy and Photochemical Kinetics, Am Fassberg 11, D-37077 Goettingen (Germany) and Department for Biophysical Chemistry, Technical University of Brunswick, Institute for Physical and Theoretical Chemistry, Hans-Sommerstr. 10, D-38106 Braunschweig (Germany)]. E-mail: pwalla@gwdg.de; Nickel, Bernhard [Max-Planck-Institute for Biophysical Chemistry, Department 010, Spectroscopy and Photochemical Kinetics, Am Fassberg 11, D-37077 Goettingen (Germany)

    2005-06-06

    We investigated the site dependence and the tunnelling processes of the intramolecular proton and deuteron transfer in the triplet state of the compounds 2-(2'-hydroxy-4'-methylphenyl)benzoxazole (m-MeHBO) and 2-(2'-hydroxy-3'-methylphenyl)benzoxazoles (o-MeHBO) and their deuterio-oxy analogues in a solid xenon matrix. After singlet excitation there occurs an ultrafast intramolecular enol {yields} keto proton transfer and subsequent intersystem crossing mainly to the keto triplet state. In the triplet state of m-MeHBO, the proton transfer back to the lower enol triplet state is governed by tunnelling processes. In o-MeHBO, however, the enol triplet state is higher and therefore normally no tunnel reaction can be observed. Because of the external heavy atom-effect in a xenon matrix, we were able to investigate the reverse enol-keto-tunnelling after exciting directly the enol triplet state of deuterated o-MeHBO. The time constants of the reverse enol-keto tautomerization are similar to those of the normal keto-enol tautomerization. In a xenon matrix, the observed site-selective phosphorescence spectra are very well-resolved vibrationally. This allowed the study of the tunnel rates in different well-defined sites. The vibrational energies obtained in the spectra are in good agreement with vibrational energies found in resonant Raman and IR spectra of 2-(2'-hydroxyphenyl)benzoxazole (HBO)

  7. Deformylation Reaction by a Nonheme Manganese(III)-Peroxo Complex via Initial Hydrogen-Atom Abstraction.

    Science.gov (United States)

    Barman, Prasenjit; Upadhyay, Pranav; Faponle, Abayomi S; Kumar, Jitendra; Nag, Sayanta Sekhar; Kumar, Devesh; Sastri, Chivukula V; de Visser, Sam P

    2016-09-01

    Metal-peroxo intermediates are key species in the catalytic cycles of nonheme metalloenzymes, but their chemical properties and reactivity patterns are still poorly understood. The synthesis and characterization of a manganese(III)-peroxo complex with a pentadentate bispidine ligand system and its reactivity with aldehydes was studied. Manganese(III)-peroxo can react through hydrogen-atom abstraction reactions instead of the commonly proposed nucleophilic addition reaction. Evidence of the mechanism comes from experiments which identify a primary kinetic isotope effect of 5.4 for the deformylation reaction. Computational modeling supports the established mechanism and identifies the origin of the reactivity preference of hydrogen-atom abstraction over nucleophilic addition.

  8. Entanglement and quantum state transfer between two atoms trapped in two indirectly coupled cavities

    Science.gov (United States)

    Zheng, Bin; Shen, Li-Tuo; Chen, Ming-Feng

    2016-05-01

    We propose a one-step scheme for implementing entanglement generation and the quantum state transfer between two atomic qubits trapped in two different cavities that are not directly coupled to each other. The process is realized through engineering an effective asymmetric X-Y interaction for the two atoms involved in the gate operation and an auxiliary atom trapped in an intermediate cavity, induced by virtually manipulating the atomic excited states and photons. We study the validity of the scheme as well as the influences of the dissipation by numerical simulation and demonstrate that it is robust against decoherence.

  9. A Fluorogenic Reaction Based on Heavy-Atom Removal for Ultrasensitive DNA Detection

    NARCIS (Netherlands)

    Prusty, Deepak K.; Herrmann, Andreas

    2010-01-01

    Fluorogenic reactions have recently emerged as a powerful tool for detection, diagnostics, and biosensing applications in a chemical and biological context. However, conventional fluorogenic systems reported to date rely on energy- or photoinduced electron transfer within the probes. Our communicati

  10. Characterization of hot hydrogen-atom reactions by kinetic spectrography.

    Science.gov (United States)

    Tomalesky, R. E.; Sturm, J. E.

    1971-01-01

    The flash photolysis of hydrogen iodide in the presence of nitrous oxide, carbon dioxide, and water has been investigated by kinetic spectroscopy. Although the fraction of hydrogen iodide dissociated was very large, the only observable intermediate was imidogen. It was demonstrated that the rapid removal of imidogen and the apparent absence of hydroxyl radicals in each case is a result of the following two reactions, respectively: (1) NH + HI yields NH2 + I; and (2) OH + HI yields H2O + I.

  11. Ultra-Low-Temperature Reactions of Carbon Atoms with Hydrogen Molecules

    CERN Document Server

    Krasnokutski, S A; Renzler, M; Jäger, C; Henning, Th; Scheier, P

    2016-01-01

    The reactions of carbon atoms with dihydrogen have been investigated in liquid helium droplets at $T$ = 0.37 K. A calorimetric technique was applied to monitor the energy released in the reaction. The barrierless reaction between a single carbon atom and a single dihydrogen molecule was detected. Reactions between dihydrogen clusters and carbon atoms have been studied by high-resolution mass spectrometry. The formation of hydrocarbon cations of the type C$_m$H$_n^+$, with $m$ = 1-4 and $n$ = 1-15 was observed. With enhanced concentration of dihydrogen, the mass spectra demonstrated the main "magic" peak assigned to the CH$_5^+$ cation. A simple formation pathway and the high stability of this cation suggest its high abundance in the interstellar medium.

  12. Effect of Trapping Agent and Polystyrene Chain End Functionality on Radical Trap-Assisted Atom Transfer Radical Coupling

    Directory of Open Access Journals (Sweden)

    Elizabeth M. Carnicom

    2014-10-01

    Full Text Available Coupling reactions were performed to gauge the effect of the inclusion of a radical trap on the success of coupling reactions of monohalogenated polystyrene (PSX chains in atom transfer radical coupling (ATRC type reactions. The effect of both the specific radical trap chosen and the structure of the polymer chain end were evaluated by the extent of dimerization observed in a series of analogous coupling reactions. The commonly used radical trap 2-methyl-2-nitrosopropane (MNP showed the highest amounts of dimerization for PSX (X = Br, Cl compared to coupling reactions performed in its absence or with a different radical trap. A dinitroxide coupling agent was also studied with the extent of coupling nearly matching the effectiveness of MNP in RTA (Radical trap-assisted-ATRC reactions, while N-nitroso and electron rich nitroso coupling agents were the least effective. (2,2,6,6-Tetramethyl-piperin-l-yloxyl-capped PS (PS-TEMPO, prepared by NMP, was subjected to a coupling sequence conceptually similar to RTA-ATRC, but dimerization was not observed regardless of the choice of radical trap. Kinetic experiments were performed to observe rate changes on the coupling reaction of PSBr as a result of the inclusion of MNP, with substantial rate enhancements found in the RTA-ATRC coupling sequence compared to traditional ATRC.

  13. 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

    2016-01-01

    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.

  14. Theoretical aspects of electron transfer reactions of complex molecules

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Ulstrup, Jens

    2001-01-01

    Features of electron transfer involving complex molecules are discussed. This notion presently refers to molecular reactants where charge transfer is accompanied by large molecular reorganization, and commonly used displaced harmonic oscillator models do not apply. It is shown that comprehensive ...

  15. AIM Study on the Reaction of CH2SH Radical with Fluorine Atom

    Institute of Scientific and Technical Information of China (English)

    Cui-hong Sun; Yan-li Zeng; Ling-peng Meng; Shi-jun Zheng

    2008-01-01

    The reaction of CH2SH radical with fluorine atom was studied at the levels of B3LYP/6-311G(d,p) and MP2(Full)/6-311G(d,p).The computational results show that the reaction has three channels and proceeds by the addition of fluorine atoms on carbon or sulfur sites of CH2SH,forming initial intermediates.The calculated results show that the channel,in which fluorine attaches to the carbon atom to form CH2S and HF,is the most likely reaction pathway.Topological analysis of electron density was carried out for the three channels.The change trends of the chemical bonds on the reaction paths were discussed.The energy transition states and the structure transition regions (states) of the three channels were found.The calculated results show that the structure transition regions axe broad in unobvions exothermic reactions or unobvions endothermic reactions,and are narrow in obvious exothermic reactions or obvious endothermic reactions.

  16. Population transfer by femtosecond laser pulses in a ladder-type atomic system

    Institute of Scientific and Technical Information of China (English)

    Fan Xi-Jun; Li Ai-Yun; Tong Dian-Min; Liu Cheng-Pu

    2008-01-01

    The population transfer in a ladder-type atomic system driven by linearly polarized sech-shape femtosecond laser pulses is investigated by numerically solving Schrodinger equation without including the rotating wave approximation (RWA). It is shown that population transfer is mainly determined by the Rabi frequency (strength) of the driving laser field and the chirp rate, and that the ratio of the dipole moments and the pulse width also have a prominent effect on the population transfer. By choosing appropriate values of the above parameters, complete population transfer can be realized.

  17. Revisiting Zeno's paradox: Flying arrows for atom-diatom reactions

    CERN Document Server

    Sanz-Sanz, C; Gonzalez-Lezana, T; Roncero, O; Miret-Artes, S

    2011-01-01

    The possibility to observe quantum Zeno and anti-Zeno scenarios for atom-diatom reactive collisions is investigated for two diferent processes (F+HD and H+O_2) by means of time-dependent wave packet propagations. A novel approach is proposed in which the survival probabilities investigated are those obtained when the initial state is redefined after time intervals tau at which measurements are performed on the system. The comparison with the actual probability for the unperturbed system reveals the existence of a regime in which the decay from the initial state appears to be inhibited (the quantum Zeno effect) or accelerated (the anti-Zeno effect). In contrast with preceding interpretations, given that the time-evolving wave packet is not affected at any time ("flying arrow"), the present procedure does not require to invoke to counterintuitive hindered evolutions ("stopping arrow") to explain the results. On the contrary the consecutive update of the reference state of the system solves the apparent modern v...

  18. A semiclassical theory of electron transfer reactions in Condon approximation and beyond

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Sokolov, V. V.; Ulstrup, Jens

    2001-01-01

    of adiabatic electron transfer reactions is elaborated. A new formula for the transition probability of non-adiabatic electron transfer reactions is obtained in an improved Condon approximation A regular method for the calculation of non-Condon corrections is suggested. The importance of these effects for some...

  19. Correlation Between Energy Transfer Rate and Atomization Energy of Some Trinitro Aromatic Explosive Molecules

    Institute of Scientific and Technical Information of China (English)

    Su-hong Ge; Xin-lu Cheng; Zheng-lai Liu; Xiang-dong Yang; Fang-fang Dong

    2008-01-01

    An assumptive theoretical relationship is suggested to describe the property of molecular atomization energy and energy transfer rate in the initiation of explosions. To investigate the relationship between atomization energy and energy transfer rate, the number of doorway modes of explosives is estimated by the theory of Dlott and Fayer in which the rate is proportional to the number of normal mode vibrations. It was evaluated frequencies of normal mode vibrations of eight molecules by means of density functional theory (DFT) at the b3p86/6-31G(d,p) level. It is found that the number of doorway modes shows a linear correlation to the atomization energies of the molecules, which were also calculated by means of the same method. A mechanism of this correlation is discussed. It is also noted that in those explosives with similar molecular structure and molecular weight, the correlation between the atomization energy and the number of doorway modes is higher.

  20. Effect of mass transfer on the oxygen reduction reaction catalyzed by platinum dendrimer encapsulated nanoparticles.

    Science.gov (United States)

    Dumitrescu, Ioana; Crooks, Richard M

    2012-07-17

    Here we report on the effect of the mass transfer rate (k(t)) on the oxygen reduction reaction (ORR) catalyzed by Pt dendrimer-encapsulated nanoparticles (DENs) comprised of 147 and 55 atoms (Pt(147) and Pt(55)). The experiments were carried out using a dual-electrode microelectrochemical device, which enables the study of the ORR under high k(t) conditions with simultaneous detection of H(2)O(2). At low k(t) (0.02 to 0.12 cm s(-1)) the effective number of electrons involved in ORR, n(eff), is 3.7 for Pt(147) and 3.4 for Pt(55). As k(t) is increased, the mass-transfer-limited current for the ORR becomes significantly lower than the value predicted by the Levich equation for a 4-electron process regardless of catalyst size. However, the percentage of H(2)O(2) detected remains constant, such that n(eff) barely changes over the entire k(t) range explored (0.02 cm s(-1)). This suggests that mass transfer does not affect n(eff), which has implications for the mechanism of the ORR on Pt nanoparticles. Interestingly, there is a significant difference in n(eff) for the two sizes of Pt DENs (n(eff) = 3.7 and 3.5 for Pt(147) and Pt(55), respectively) that cannot be assigned to mass transfer effects and that we therefore attribute to a particle size effect.

  1. Laser-induced reaction of Yb atoms with hydrogen chloride in the gas phase

    International Nuclear Information System (INIS)

    The results are presented of an investigation of the reaction of ytterbium atoms with hydrogen chloride initiated by laser radiation resonant with the 1S/sub O/-3P1 intercombination transition. The rate constant of extinction of the excited state of the ytterbium atom by a molecular reagent was measured: k/sub d/ = (6.4 +- 1.5) x 10-10 cm3sec

  2. High spin levels populated in multinucleon transfer reaction with 480 MeV 12C

    International Nuclear Information System (INIS)

    Two- and three-nucleon stripping reactions induced by 480 MeV 12C have been studied on 12C, 16O, 28Si, 40Ca and 54Fe target nuclei. Discrete levels are fed with cross sections up to 1 mb/sr for d-transfer reactions and one order and two orders of magnitude less for 2p- and 3He-transfer reactions, respectively. These reactions preferentially populate high spin states with stretched configurations. Several spin assignments were known from transfer reactions induced by lighter projectiles at incident energies well above the Coulomb barrier. In the case of two-nucleon transfer reactions, the energy of these states is well reproduced by crude shell model calculations. Such estimates are of use in proposing spins of newly observed states especially as the shapes of the measured angular distributions are independent of the final spin of the residual nucleus

  3. Coupled-channels description of the 40Ca+58,64Ni transfer and fusion reactions

    CERN Document Server

    Scamps, G; Hagino, K; Haas, F; Courtin, S

    2016-01-01

    Preliminary experimental data for nucleon transfer reactions of the 40Ca+58Ni and 40Ca+64Ni systems are analyzed with the coupled- channels approach. It is shown that a simple treatment for the transfer in the coupled-channels method cannot reproduce simultaneously the transfer probabilities and the sub-barrier enhancement of fusion cross sections.

  4. Role of transfer reactions in heavy-ion collisions at the Coulomb barrier

    Directory of Open Access Journals (Sweden)

    Pollarolo Giovanni

    2011-10-01

    Full Text Available One and two neutron transfer reactions are discussed in the semiclassical formalism. The twoneutrons transfer cross sections are calculated in the successive approximation. Comparisons with new experimental data below the Coulomb barrier are discussed in term of transfer probabilities as a function of the distance of closest approach for Coulomb scattering.

  5. Modulation Transfer Spectroscopy of Ytterbium Atoms in a Hollow Cathode Lamp

    Institute of Scientific and Technical Information of China (English)

    WANG Wen-Li; XU Xin-Ye

    2011-01-01

    We present the experimental study of modulation transfer spectroscopy of ytterbium atoms in a hollow cathode lamp.The dependences of its linewidth, slope and magnitude on the various experimental parameters are measured and fitted by the well-known theoretical expressions. The experimental results are in good agreement with the theoretical prediction. We have observed the Dicke narrowing effect by increasing the current of the hollow cathode lamp. It is also found that there are the optimal current and laser power to generate the better modulation transfer spectroscopy signal, which can be employed for locking the laser frequency to the atomic transition.

  6. Is H Atom Abstraction Important in the Reaction of Cl with 1-Alkenes?

    Science.gov (United States)

    Walavalkar, M P; Vijayakumar, S; Sharma, A; Rajakumar, B; Dhanya, S

    2016-06-23

    The relative yields of products of the reaction of Cl atoms with 1-alkenes (C4-C9) were determined to see whether H atom abstraction is an important channel and if it is to identify the preferred position of abstraction. The presence of all the possible positional isomers of long chain alkenones and alkenols among the products, along with chloroketones and chloroalcohols, confirms the occurrence of H atom abstraction. A consistent pattern of distribution of abstraction products is observed with oxidation at C4 (next to allyl) being the lowest and that at CH2 groups away from the double bond being the highest. This contradicts with the higher stability of allyl (C3) radical. For a better understanding of the relative reactivity, ab initio calculations at MP2/6-311+G (d,p) level of theory are carried out in the case of 1-heptene. The total rate coefficient, calculated using conventional transition state theory, was found to be in good agreement with the experimental value at room temperature. The preferred position of Cl atom addition is predicted to be the terminal carbon atom, which matches with the experimental observation, whereas the rate coefficients calculated for individual channels of H atom abstraction do not explain the observed pattern of products. The distribution of abstraction products except at C4 is found to be better explained by reported structure activity relationship, developed from experimental rate coefficient data. This implies the reactions to be kinetically dictated and emphasizes the importance of secondary reactions.

  7. 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.

    1985-12-01

    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.).

  8. Ultracold Chemical Reactions of a Single Rydberg Atom in a Dense Gas

    Science.gov (United States)

    Schlagmüller, Michael; Liebisch, Tara Cubel; Engel, Felix; Kleinbach, Kathrin S.; Böttcher, Fabian; Hermann, Udo; Westphal, Karl M.; Gaj, Anita; Löw, Robert; Hofferberth, Sebastian; Pfau, Tilman; Pérez-Ríos, Jesús; Greene, Chris H.

    2016-07-01

    Within a dense environment (ρ ≈1014 atoms /cm3 ) at ultracold temperatures (T collision time leading to increased lifetimes of the Rydberg state independent of the densities investigated. Even at very high densities (ρ ≈4.8 ×1014 cm-3 ), the lifetime of a Rydberg atom exceeds 10 μ s at n >140 compared to 1 μ s at n =90 . In addition, a second observed reaction mechanism, namely, Rb2+ molecule formation, was studied. Both reaction products are equally probable for n =40 , but the fraction of Rb2+ created drops to below 10% for n ≥90 .

  9. Studies of high-spin cluster states induced by multiparticle transfer reactions

    International Nuclear Information System (INIS)

    The characteristic selectivity due to the reaction dynamics and clustering structure among transferred nucleons is first described. Using such an advantageous selectivity, high-spin cluster states can be sorted out. Examples involving either one-, two-, three- or four-nucleon transfer reactions are mentioned with emphazing spectroscopic problems. It is clear that a lack in reaction mechanism theory hinders quantitative arguments at present time

  10. Investigation of Surface Reaction and Degradation Mechanism of Kapton during Atomic Oxygen Exposure

    Institute of Scientific and Technical Information of China (English)

    Shuwang DUO; Meishuan LI; Yanchun ZHOU; Jingyu TONG; Gang SUN

    2003-01-01

    The erosion behavior of Kapton when exposed to atomic oxygen (AO) environment in the ground-based simulation facility was studied. The chemical and physical changes of sample surfaces after exposed to AO fluxes were investigated by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results indicated that Kapton underwent dramatically degradation, including much mass loss and change of surface morphologies; vacuum outgassing effect of Kapton was the key factor for initial mass loss in the course of atomic oxygen beam exposures. XPS analysis showed that the carbonyl group in Kapton reacted with oxygen atoms to generate CO2, then CO2 desorbed from Kapton surface. In addition, PMDA in the polyimide structure degraded due to the reaction with atomic oxygen of 5 eV.

  11. Excited atomic bromine energy transfer and quenching mechanisms

    Science.gov (United States)

    Johnson, Ray O.

    1993-08-01

    Pulsed and steady-state photolysis experiments have been conducted to determine the rate coefficients for collisional deactivation of the spin-orbit excited state of atomic bromine, Br((sup 2)P(sub 1/2)). Pulsed lifetime studies for quenching by Br2 and CO2 established absolute rate coefficients at room temperature of k(sub Br2) = 1.2 +/- 0.1 x 10(exp-12) and k(sub CO2) = 1.5 +/0.2 x 10(exp-11) cu cm/molecule-s. Steady-state photolysis methods were used to determine the quenching rates for the rare gases, N2, 02, H2, D2, NO, NO2, N2O, SF6, CF4, CH4, CO, CO2, COS, SO2, H2S, HBr, HC1, and HI relative to that for Br2. Quenching rate temperature dependence was examined for Br2, CO2, N2O, HCl, COS, NO, and NO2 for temperatures from 300 to 420 K. Diffusion and three body effects were examined in order to determine the slowest relative quenching rate measurable by this experimental technique.

  12. Generation of a cold pulsed beam of Rb atoms by transfer from a 3D magneto-optic trap

    CERN Document Server

    Chanu, Sapam Ranjita; Natarajan, Vasant

    2016-01-01

    We demonstrate a technique for producing a cold pulsed beam of atoms by transferring a cloud of atoms trapped in a three dimensional magneto-optic trap (MOT). The MOT is loaded by heating a getter source of Rb atoms. We show that it is advantageous to transfer with two beams (with a small angle between them) compared to a single beam, because the atoms stop interacting with the beams in the two-beam technique, which results in a Gaussian velocity distribution. The atoms are further cooled in optical molasses by turning off the MOT magnetic field before the transfer beams are turned on.

  13. Generation of a cold pulsed beam of Rb atoms by transfer from a 3D magneto-optic trap

    Science.gov (United States)

    Chanu, Sapam Ranjita; Rathod, Ketan D.; Natarajan, Vasant

    2016-08-01

    We demonstrate a technique for producing a cold pulsed beam of atoms by transferring a cloud of atoms trapped in a three dimensional magneto-optic trap (MOT). The MOT is loaded by heating a getter source of Rb atoms. We show that it is advantageous to transfer with two beams (with a small angle between them) compared to a single beam, because the atoms stop interacting with the beams in the two-beam technique, which results in a Gaussian velocity distribution. The atoms are further cooled in optical molasses by turning off the MOT magnetic field before the transfer beams are turned on.

  14. A silver bullet: elemental silver as an efficient reducing agent for atom transfer radical polymerization of acrylates.

    Science.gov (United States)

    Williams, Valerie A; Ribelli, Thomas G; Chmielarz, Pawel; Park, Sangwoo; Matyjaszewski, Krzysztof

    2015-02-01

    Elemental silver was used as a reducing agent in the atom transfer radical polymerization (ATRP) of acrylates. Silver wire, in conjunction with a CuBr(2)/TPMA catalyst, enabled the controlled, rapid preparation of polyacrylates with dispersity values down to Đ = 1.03. The silver wire in these reactions was reused several times in sequential reactions without a decline in performance, and the amount of copper catalyst used was reduced to 10 ppm without a large decrease in control. A poly(n-butyl acrylate)-block-poly(tert-butyl acrylate) diblock copolymer was synthesized with a molecular weight of 91 400 and Đ = 1.04, demonstrating good retention of chain-end functionality and a high degree of livingness in this ATRP system. PMID:25599253

  15. The reaction of nitromethane with hydrogen and deuterium atoms in the gas phase. A mechanistic study

    DEFF Research Database (Denmark)

    Lund Thomsen, E.; Nielsen, O.J.; Egsgaard, H.

    1993-01-01

    The mechanism of the reaction between H and CH3NO2, has been studied in a discharge flow system using electron paramagnetic resonance and modulated molecular beam mass spectrometry for the detection of reactants and products. Deuterium atoms have, in addition to CD3NO2, been used to support...... the proposed reaction mechanism. The reaction was studied with the atomic reactant in slight excess at 298 K and a total pressure of 2 Torr. Two concurrent reaction channels: (1a) H+CH3NO2-->HONO+.CH3 and (1b) H+CH3NO2-->CH3NO+.OH were observed. The branching ratio, k1a/(k1a+k1b), is 0.7+/-0.2....

  16. Kinetic Studies of Atom Transfer Radical Polymerisations of Styrene and Chloromethylstyrene with Poly(3-hexyl thiophene Macroinitiator

    Directory of Open Access Journals (Sweden)

    Nattawoot Rattanathamwat

    2015-01-01

    Full Text Available Poly(3-hexyl thiophene-b-poly(styrene-co-chloromethylstyrene copolymers, to be used as a prepolymer for preparing donor-acceptor block copolymers for organic solar cells, have been synthesised by reacting P3HT macroinitiators with styrene and chloromethylstyrene via three types of atom transfer radical polymerisation (ATRP systems, which are (1 a normal ATRP, (2 activators generated by electron transfer (AGET, and (3 a simultaneous reverse and normal initiation (SR&NI. The kinetics of these ATRP systems were studied as a function of monomers to the macroinitiator molar ratio. It was found that all of the three types of ATRP systems led to first order kinetics with respect to monomers. The highest rate constant (k of 3.4 × 10−3 s−1 was obtained from the SR&NI ATRP system. The molecular weights of the product determined by the GPC were lower than were the theoretical values. The result was discussed in light of the chain transfer reaction to the poly(chloromethylstyrene repeating units. Morphology of the synthesized block copolymers, examined by an atomic force microscopy (AFM, were also compared and discussed.

  17. Ultracold chemical reactions of a single Rydberg atom in a dense gas

    CERN Document Server

    Schlagmüller, Michael; Engel, Felix; Kleinbach, Kathrin S; Böttcher, Fabian; Westphal, Karl M; Gaj, Anita; Löw, Robert; Hofferberth, Sebastian; Pfau, Tilman; Pérez-Ríos, Jesús; Greene, Chris H

    2016-01-01

    Within a dense environment ($\\rho \\approx 10^{14}\\,$atoms/cm$^3$) at ultracold temperatures ($T 140$ compared to $1\\,\\mu\\text{s}$ at $n=90$. In addition, a second observed reaction mechanism, namely Rb$_2^+$ molecule formation, was studied. Both reaction products are equally probable for $n=40$ but the fraction of Rb$_2^+$ created drops to below 10$\\,$% for $n\\ge90$.

  18. Observation of the one- to six-neutron transfer reactions at sub-barrier energies

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, C.L.; Rehm, K.E.; Gehring, J. [and others

    1995-08-01

    It was suggested many years ago that when two heavy nuclei are in contact during a grazing collision, the transfer of several correlated neutron-pairs could occur. Despite considerable experimental effort, however, so far only cross sections for up to four-neutron transfers have been uniquely identified. The main difficulties in the study of multi-neutron transfer reactions are the small cross sections encountered at incident energies close to the barrier, and various experimental uncertainties which can complicate the analysis of these reactions. We have for the first time found evidence for multi-neutron transfer reactions covering the full sequence from one- to six-neutron transfer reactions at sub-barrier energies in the system {sup 58}Ni + {sup 100}Mo.

  19. Palladium-atom catalyzed formic acid decomposition and the switch of reaction mechanism with temperature.

    Science.gov (United States)

    He, Nan; Li, Zhen Hua

    2016-04-21

    Formic acid decomposition (FAD) reaction has been an innovative way for hydrogen energy. Noble metal catalysts, especially palladium-containing nanoparticles, supported or unsupported, perform well in this reaction. Herein, we considered the simplest model, wherein one Pd atom is used as the FAD catalyst. With high-level theoretical calculations of CCSD(T)/CBS quality, we investigated all possible FAD pathways. The results show that FAD catalyzed by one Pd atom follows a different mechanism compared with that catalyzed by surfaces or larger clusters. At the initial stage of the reaction, FAD follows a dehydration route and is quickly poisoned by CO due to the formation of very stable PdCO. PdCO then becomes the actual catalyst for FAD at temperatures approximately below 1050 K. Beyond 1050 K, there is a switch of catalyst from PdCO to Pd atom. The results also show that dehydration is always favoured over dehydrogenation on either the Pd-atom or PdCO catalyst. On the Pd-atom catalyst, neither dehydrogenation nor dehydration follows the formate mechanism. In contrast, on the PdCO catalyst, dehydrogenation follows the formate mechanism, whereas dehydration does not. We also systematically investigated the performance of 24 density functional theory methods. We found that the performance of the double hybrid mPW2PLYP functional is the best, followed by the B3LYP, B3PW91, N12SX, M11, and B2PLYP functionals.

  20. Novel Polymers Based on Atom Transfer Radical Polymerization of 2-Methoxyethyl Acrylate

    DEFF Research Database (Denmark)

    Bednarek, Melania; Jankova Atanasova, Katja; Hvilsted, Søren

    2007-01-01

    Atom transfer radical polymerization (ATRP) has been employed in the polymerization of 2-methoxyethyl acrylate (MEA) initiated by ethyl 2-bromoisobutyrate in bulk or in toluene solution at 90– 95 C with the catalytic systems Cu(I)Br/PMDETA or HMTETA. Kinetics investigations revealed that ATRP of...

  1. Bibliography on electron transfer processes in ion-ion/atom/molecule collisions (updated 1993)

    International Nuclear Information System (INIS)

    Following our previous compilations [IPPJ-AM-45 (1986), NIFS-DATA-7 (1990)], bibliographic information on experimental and theoretical studies on electron transfer processes in ion-ion/atom/molecule collisions is up-dated. The references published through 1980-1992 are included. For easy finding references for particular combination of collision partners, a simple list is also provided. (author) 1542 refs

  2. Polymer coating comprising 2-methoxyethyl acrylate units synthesized by surface-initiated atom transfer radical polymerization

    DEFF Research Database (Denmark)

    2011-01-01

    Source: US2012184029A The present invention relates to preparation of a polymer coating comprising or consisting of polymer chains comprising or consisting of units of 2-methoxyethyl acrylate synthesized by Surface-Initiated Atom Transfer Radical Polymerization (SI ATRP) such as ARGET SI ATRP or...

  3. Acrylamide Homopolymers and Acrylamide-N-Isopropylacrylamide Block Copolymers by Atomic Transfer Radical Polymerization in Water

    NARCIS (Netherlands)

    Wever, D. A. Z.; Raffa, P.; Picchioni, F.; Broekhuis, A. A.

    2012-01-01

    Atomic transfer radical polymerization (ATRP) of acrylamide has been accomplished in aqueous media at room temperature. By using methyl 2-chloropropionate (MeClPr) as the initiator and tris[2-(dimethylamino)ethyl]-amine (Me6TREN)/copper halogenide (CuX) as the catalyst system, different linear polya

  4. Surface-initiated Atom Transfer Radical Polymerization - a Technique to Develop Biofunctional Coatings

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Hvilsted, Søren

    2009-01-01

    The initial formation of initiating sites for atom transfer radical polymerization (ATRP) on various polymer surfaces and numerous inorganic and metallic surfaces is elaborated. The subsequent ATRP grafting of a multitude of monomers from such surfaces to generate thin covalently linked polymer...

  5. Effect of atomic transfer on the decay of a Bose-Einstein condensate

    CERN Document Server

    Zin, P; Charzynski, S; Herschbach, N; Tol, P; Hogervorst, W; Vassen, W; Zin, Pawel; Dragan, Andrzej; Charzynski, Szymon; Herschbach, Norbert; Tol, Paul; Hogervorst, Wim; Vassen, Wim

    2003-01-01

    We present a model describing the decay of a Bose-Einstein condensate, which assumes the system to remain in thermal equilibrium during the decay. We show that under this assumption transfer of atoms occurs from the condensate to the thermal cloud enhancing the condensate decay rate.

  6. Surface Modification of Nanoporous 1,2-Polybutadiene by Atom Transfer Radical Polymerization or Click Chemistry

    DEFF Research Database (Denmark)

    Guo, Fengxiao; Jankova Atanasova, Katja; Schulte, Lars;

    2010-01-01

    Surface-initiated atom transfer radical polymerization (ATRP) and click chemistry were used to obtain functional nanoporous polymers based oil nanoporous 1,2-polybutadiene (PB) with gyroid morphology. The ATRP monolith initiator was prepared by immobilizing bromoester initiators onto the pore walls...

  7. Learning about Regiochemistry from a Hydrogen-Atom Abstraction Reaction in Water

    Science.gov (United States)

    Sears-Dundes, Christopher; Huon, Yoeup; Hotz, Richard P.; Pinhas, Allan R.

    2011-01-01

    An experiment has been developed in which the hydrogen-atom abstraction and the coupling of propionitrile, using Fenton's reagent, are investigated. Students learn about the regiochemistry of radical formation, the stereochemistry of product formation, and the interpretation of GC-MS data, in a safe reaction that can be easily completed in one…

  8. A new class of rhodium complexes containing free donor atoms and their intramolecular substitution reaction

    Institute of Scientific and Technical Information of China (English)

    JIANG, Hua; YUAN, Guo-Qing; ZHANG, Shu-Feng; PAN, Ping-Lai; DIAO, Kai-Sheng

    2000-01-01

    A new class of rhodium complexes with high catalytic activity as well as excellent stability, which was used as catalyst for carlbonylation of methanol to acetic acid, is reported. It con tains free donor (namely un-coordinated donor) atoms which enable to improve its stability by intramolecular substitution rearction. Its synthesis, characteristic and catalytic reaction were discussed here.

  9. Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition.

    Science.gov (United States)

    Elliott, Simon D; Dey, Gangotri; Maimaiti, Yasheng; Ablat, Hayrensa; Filatova, Ekaterina A; Fomengia, Glen N

    2016-07-01

    Recent progress in the simulation of the chemistry of atomic layer deposition (ALD) is presented for technologically important materials such as alumina, silica, and copper metal. Self-limiting chemisorption of precursors onto substrates is studied using density functional theory so as to determine reaction pathways and aid process development. The main challenges for the future of ALD modeling are outlined.

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

    Energy Technology Data Exchange (ETDEWEB)

    Dupays, A

    2004-06-01

    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. Anticoagulant surface of 316 L stainless steel modified by surface-initiated atom transfer radical polymerization.

    Science.gov (United States)

    Guo, Weihua; Zhu, Jian; Cheng, Zhenping; Zhang, Zhengbiao; Zhu, Xiulin

    2011-05-01

    Polished 316 L stainless steel (SS) was first treated with air plasma to enhance surface hydrophilicity and was subsequently allowed to react with 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane to introduce an atom transfer radical polymerization (ATRP) initiator. Accordingly, the surface-initiated atom transfer radical polymerization of polyethylene glycol methacrylate (PEGMA) was carried out on the surface of the modified SS. The grafting progress was monitored by water contact angle measurements, X-ray photoelectron spectroscopy and atomic force microscopy. The polymer thickness as a function different polymerization times was characterized using a step profiler. The anticoagulative properties of the PEGMA modified SS surface were investigated. The results showed enhanced anticoagulative to acid-citrate-dextrose (ACD) blood after grafting PEGMA on the SS surface. PMID:21528878

  12. Examining the effect of nonlocality in (d ,n ) transfer reactions

    Science.gov (United States)

    Ross, A.; Titus, L. J.; Nunes, F. M.

    2016-07-01

    Background: In the past year we have been exploring the effect of the explicit inclusion of nonlocality in (d ,p ) reactions. Purpose: The goal of this paper is to extend previous studies to (d ,n ) reactions, which, although similar to (d ,p ) reactions, have specific properties that merit inspection. Method: We apply our methods (both the distorted-wave Born approximation and the adiabatic wave approximation) to (d ,n ) reactions on 16O,40Ca,48Ca,126Sn,132Sn , and 208Pb at 20 and 50 MeV. Results: We look separately at the modifications introduced by nonlocality in the final bound and scattering states as well as the consequences reflected on the differential angular distributions. The cross sections obtained when using nonlocality explicitly are significantly different than those using the local approximation, just as in (d ,p ) reactions. Due to the particular role of the Coulomb force in the bound state, often we found the effects of nonlocality to be larger in (d ,n ) than in (d ,p ) reactions. Conclusions: Our results confirm the importance of including nonlocality explicitly in deuteron-induced reactions.

  13. The electronic behavior of a photosynthetic reaction center monitored by conductive atomic force microscopy.

    Science.gov (United States)

    Mikayama, Takeshi; Iida, Kouji; Suemori, Yoshiharu; Dewa, Takehisa; Miyashita, Tokuji; Nango, Mamoru; Gardiner, Alastair T; Cogdell, Richard J

    2009-01-01

    The conductivity of a photosynthetic reaction center (RC) from Rhodobacter sphaeroides was measured with conductive atomic force microscopy (CAFM) on SAM-modified Au(111) substrates. 2-mercaptoethanol (2ME), 2-mercaptoacetic acid (MAC), 2-mercaptopyridine (2MP) and 4-mercaptopyridine (4MP) were prepared as SAM materials to investigate the stability and morphology of RCs on the substrate by using near-IR absorption spectroscopy and AFM, respectively. The clear presence of the three well known RC near-IR absorption peaks indicates that the RCs were native on the SAM-modified Au(111). Dense grains with various diameters of 5-20 nm, which corresponded to mixtures of single RCs up to aggregates of 10, were observed in topographs of RCs adsorbed on all the different SAM-modified Au(111) substrates. The size of currents obtained from the RC using a bare conductive cantilever were produced in the following order for SAM molecules: 2MP > 2ME > 4MP > MAC. A clear rectification of this current was observed for the modification of the Au(111) substrate with the pi-conjugated thiol, 2MP, indicating that 2MP was effective in both promoting the specific orientation of the RCs on the electrode and electron injection into the RC. Cyclic voltammetry measurements indicate that the 2MP is better mediator for the electron transfer between a quinone and substrate. The current with 2MP-modified cantilever was twice as high as that obtained with the Au-coated one alone, indicating that 2MP has an important role in lowering the electron injection barrier between special pair side of RC and gold electrode.

  14. Photoinduced Charge Transfer at Metal Oxide/Oxide Interfaces Prepared with Plasma Enhanced Atomic Layer Deposition

    Science.gov (United States)

    Kaur, Manpuneet

    LiNbO3 and ZnO have shown great potential for photochemical surface reactions and specific photocatalytic processes. However, the efficiency of LiNbO3 is limited due to recombination or back reactions and ZnO exhibits a chemical instability in a liquid cell. In this dissertation, both materials were coated with precise thickness of metal oxide layers to passivate the surfaces and to enhance their photocatalytic efficiency. LiNbO 3 was coated with plasma enhanced atomic layer deposited (PEALD) ZnO and Al2O3, and molecular beam deposited TiO2 and VO2. On the other hand, PEALD ZnO and single crystal ZnO were passivated with PEALD SiO2 and Al2O3. Metal oxide/LiNbO3 heterostructures were immersed in aqueous AgNO3 solutions and illuminated with ultraviolet (UV) light to form Ag nanoparticle patterns. Alternatively, Al2O3 and SiO2/ZnO heterostructures were immersed in K3PO 4 buffer solutions and studied for photoelectrochemical reactions. A fundamental aspect of the heterostructures is the band alignment and band bending, which was deduced from in situ photoemission measurements. This research has provided insight to three aspects of the heterostructures. First, the band alignment at the interface of metal oxides/LiNbO 3, and Al2O3 or SiO2/ZnO were used to explain the possible charge transfer processes and the direction of carrier flow in the heterostructures. Second, the effect of metal oxide coatings on the LiNbO3 with different internal carrier concentrations was related to the surface photochemical reactions. Third is the surface passivation and degradation mechanism of Al2O 3 and SiO2 on ZnO was established. The heterostructures were characterized after stability tests using atomic force microscopy (AFM), scanning electron microscopy (SEM), and cross-section transmission electron microscopy (TEM). The results indicate that limited thicknesses of ZnO or TiO2 on polarity patterned LiNbO3 (PPLN) enhances the Ag+ photoinduced reduction process. ZnO seems more efficient

  15. Reactions between cold methyl halide molecules and alkali-metal atoms

    CERN Document Server

    Lutz, Jesse J

    2013-01-01

    We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH$_{3}X$ ($X$ = F, Cl, Br, I) and alkali-metal atoms $A$ ($A$ = Li, Na, K, Rb) using high-level {\\it ab initio} calculations. We examine the anisotropy of each intermolecular potential energy surface (PES) and the mechanism and energetics of the only available exothermic reaction pathway, ${\\rm CH}_{3}X+A\\rightarrow{\\rm CH}_{3}+AX$. The region of the transition state is explored using two-dimensional PES cuts and estimates of the activation energies are inferred. Nearly all combinations of methyl halide and alkali-metal atom have positive barrier heights, indicating that reactions at low temperatures will be slow.

  16. Reactions between cold methyl halide molecules and alkali-metal atoms

    International Nuclear Information System (INIS)

    We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH3X (X = F, Cl, Br, I) and alkali-metal atoms A (A = Li, Na, K, Rb) using high-level ab initio calculations. We examine the anisotropy of each intermolecular potential energy surface (PES) and the mechanism and energetics of the only available exothermic reaction pathway, CH3X + A → CH3 + AX. The region of the transition state is explored using two-dimensional PES cuts and estimates of the activation energies are inferred. Nearly all combinations of methyl halide and alkali-metal atom have positive barrier heights, indicating that reactions at low temperatures will be slow

  17. Matrix reactions of copper atoms and ozone molecules. Infrared spectrum of CuO

    Science.gov (United States)

    Tevault, D. E.; Mowery, R. L.; De Marco, R. A.; Smardzewski, R. R.

    1981-04-01

    The matrix reactions of copper atoms with ozone have been studied by infrared spectroscopy. Two products were found in the initial deposit: CuO3, which has a strong absorption at 802.3 cm-1, and CuO, which has its main feature, corresponding to the 63Cu16O isotopic species, at 628.0 cm-1 in solid argon. Copper atom reactions with oxygen-18-enriched ozone samples were used to obtain species identifications. The CuO3 absorption was very similar in frequency and isotopic splitting behavior to alkali and alkaline earth metal ozonide species previously studied in matrices. The CuO frequency is in good agreement with gas phase measurements which put the ground state CuO vibrational fundamental at 631.3 cm-1. Temperature cycling of the Cu-O3 matrices leads to CuO4 formation by the secondary reaction of CuO with unreacted ozone.

  18. Hydrogen bonding tunes the early stage of hydrogen-atom abstracting reaction.

    Science.gov (United States)

    Yang, Yang; Liu, Lei; Chen, Junsheng; Han, Keli

    2014-09-01

    The spontaneous and collision-assisted hydrogen-atom abstracting reaction (HA) dynamics of triplet benzil are investigated through the combination of transient absorption spectroscopy with TD-DFT calculations. HA dynamics exhibit a remarkable dependence on the hydrogen donor properties. The effects of the triplet-state hydrogen bonding on the reaction dynamics are illustrated. In particular, it is experimentally observed that strengthened triplet-state hydrogen bonding could accelerate the HA, whereas weakened triplet-state hydrogen bonding would postpone the HA. The triplet-state hydrogen bonding has great influences on the early stage of the HA reaction, while the bond dissociation energy of the hydrogen donors determines the subsequent reaction pathways. Protic solvents could sustain longer lifetimes of the excited-state intermediate formed after HA than non-protic solvents by 10 μs. This investigation provides insights into the HA dynamics and guidance to improve the product efficiency of photochemical reactions. PMID:25036436

  19. Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

    OpenAIRE

    Syed Shahabuddin; Fatem Hamime Ismail; Sharifah Mohamad; Norazilawati Muhamad Sarih

    2015-01-01

    Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydro...

  20. Role of core excitation in (d,p) transfer reactions

    CERN Document Server

    Deltuva, A; Norvaišas, E; Nunes, F M

    2016-01-01

    [Background:] Recent work found that core excitation can be important in extracting structure information from (d,p) reactions. [Purpose:] Our objective is to systematically explore the role of core excitation in (d,p) reactions, and understand the origin of the dynamical effects. [Method:] Based on the particle-rotor model of $n+^{10}$Be, we generate a number of models with a range of separation energies ($S_n=0.1-5.0$ MeV), while maintaining a significant core excited component. We then apply the latest extension of the momentum-space based Faddeev method, including dynamical core excitation in the reaction mechanism to all orders, to the $^{10}$Be(d,p)$^{11}$Be like reactions, and study the excitation effects for beam energies from $E_d=15-90$ MeV. [Results:] We study the resulting angular distributions and the differences between the spectroscopic factor that would be extracted from the cross sections, when including dynamical core excitation in the reaction, to that of the original structure model. We al...

  1. Cross sections for deeply inelastic transfer reactions induced by heavy ions in rare-earth targets

    Science.gov (United States)

    Rivet, M. F.; Bimbot, R.; Gardès, D.; Fleury, A.; Hubert, F.; Llabador, Y.

    1982-04-01

    Cross sections have been measured for deeply inelastic transfer reactions leading to the production of several radio-nuclides. Rare-earth targets were used and the projectiles were Ar, Cr, Fe and Cu ions. The reactions studied corresponded to transfers of two to nine protons and variable numbers of neutrons. The results obtained were used to study the evolution of some characteristics of these reactions, such as integrated cross sections and widths of the isotopic distributions, versus incident mass and transferred mass. These results confirm that mass transfer is driven by the potential energy of the composite system. The decrease of cross sections for increasing charge transfer may be quantitatively explained by assuming thermodynamical equilibrium of the mass asymmetry degree of freedom.

  2. Recyclable Polystyrene-Supported Siloxane-Transfer Agent for Palladium-Catalyzed Cross-Coupling Reactions

    Science.gov (United States)

    2015-01-01

    The rational design, synthesis, and validation of a significantly improved insoluble polymer-supported siloxane-transfer agent has been achieved that permits efficient palladium-catalyzed cross-coupling reactions. The cross-linked polystyrene support facilitates product purification with excellent siloxane recycling. Drawbacks of a previous polymer-supported siloxane-transfer agent, relating to reaction efficiency and polymer stability after repeated cycles, have been addressed. PMID:24661113

  3. Velocity map imaging the dynamics of the reactions of Cl atoms with neopentane and tetramethylsilane

    Science.gov (United States)

    Rose, Rebecca A.; Greaves, Stuart J.; Orr-Ewing, Andrew J.

    2010-06-01

    The reactions of ground state Cl(P23/2) atoms with neopentane and tetramethylsilane have been studied at collision energies of 7.9±2.0 and 8.2±2.0 kcal mol-1, respectively. The nascent HCl(v=0,J) products were probed using resonance enhanced multiphoton ionization spectroscopy combined with velocity map imaging (VMI) to determine the rotational level population distributions, differential cross sections (DCSs), and product translational energy distributions. The outcomes from PHOTOLOC and dual beam methods are compared and are discussed in light of previous studies of the reactions of Cl atoms with other saturated hydrocarbons, including a recent crossed molecular beam and VMI investigation of the reaction of Cl atoms with neopentane [Estillore et al., J. Chem. Phys. 132, 164313 (2010)]. Rotational distributions were observed to be cold, consistent with the reactions proceeding via a transition state with a collinear Cl-H-C moiety. The DCSs for both reactions are forward peaked but show scatter across a broad angular range. Interpretation using a model based on linear dependence of scattering angle on impact parameter indicates that the probability of reaction is approximately constant across all allowed impact parameters. Product translational energy distributions from dual beam experiments have mean values, expressed as fractions of the total available energy, of 0.67 (Cl+neopentane) and 0.64 (Cl+tetramethylsilane) that are consistent with a kinematic model for the reaction in which the translational energy of the reactants is conserved into product translational energy.

  4. Direct determination of atom and radical concentrations in thermal reactions of hydrocarbons and other gases

    International Nuclear Information System (INIS)

    This is the sixth annual progress report on this project. During the period covered by the first five reports (June 1976 through December 1980) a shock tube and optical systems to measure H, D and O atom concentrations were built and fully characterized. The performance of our microwave discharge lamps was defined by numerous high-resolution spectroscopic profiles, while empirical calibrations were also made for all three of the above species. H, D and O atom concentrations were measured in gas mixtures containing H2, D2, O2, CD4, C2H6, C2D6, C3H8 and C3D8 in various proportions, and rate constants of several elementary reactions were deduced from the data. During the period covered by this report (January 1 to November 30, 1981) we have made an extensive series of measurements of O concentrations in shock-heated mixtures of C2H6-O2-AR, C2D6-O2-Ar, C3H8-O2-Ar and C3D8-O2-Ar. We have made kinetic modelling calculations for these mixtures to correlate these observed O concentrations, and also our earlier measurements of H and D atom concentrations in similar mixtures, with elementary reaction rate constants. From these calculations we expect to deduce rate constants for a number of reactions. We have also completed a series of O atom measurements in H2-N2O-Ar and D2-N2O-Ar mixtures, from which we have obtained good rate constant data for the reactions O + H2 → OH + H and O + D2 → OD + D. Our immediate future plans involve meaurements of H and D atoms in the dissociation of benzene, toluene, neopentane and their deuterium analogs leading to direct evaluation of rate constants for the unimolecular dissociation of these substances

  5. Synthesis and Reactions of Five-Membered Heterocycles Using Phase Transfer Catalyst (PTC Techniques

    Directory of Open Access Journals (Sweden)

    Ahmed M. El-Sayed

    2014-01-01

    Full Text Available Phase transfer catalysts (PTCs have been widely used for the synthesis of organic compounds particularly in both liquid-liquid and solid-liquid heterogeneous reaction mixtures. They are known to accelerate reaction rates by facilitating formation of interphase transfer of species and making reactions between reagents in two immiscible phases possible. Application of PTC instead of traditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment. On the basis of numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many active intermediates. In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compounds and their multifused rings.

  6. Studies on electron transfer reactions of Keggin-type mixed addenda heteropolytungstovanadophosphates with NADH

    Indian Academy of Sciences (India)

    Ponnusamy Sami; Kasi Rajasekaran

    2009-03-01

    The coenzyme nicotinamide adenine dinucleotide (NADH) undergoes facile electron transfer reaction with vanadium (V) substituted Keggin-type heteropolyanions (HPA) [PVVW11O40]4- (PV1) and [PV$^{V}_{2}$W10O40]5- (PV2) in aqueous phosphate buffer of pH 6 at ambient temperature. Electrochemical and optical studies show that the stoichiometry of the reaction is 1 : 2 (NADH : HPA). EPR and optical studies show that HPA act as one electron acceptor and the products of electron transfer reactions are one electron reduced heteropoly blues (HPB), viz. [PVIVW11O40]5- and [PVIVVVW10O40]6-. Oxygraph measurements show that there is no uptake of molecular oxygen during the course of reaction. The reaction proceeds through multi-step electron-proton-electron transfer mechanism, with rate limiting initial one electron transfer from NADH to HPA by outer sphere electron transfer process. Bimolecular rate constant for electron transfer reaction between NADH and PV2 in phosphate buffer of pH = 6 has been determined spectrophotometrically.

  7. Definition and determination of the triplet-triplet energy transfer reaction coordinate

    Energy Technology Data Exchange (ETDEWEB)

    Zapata, Felipe; Marazzi, Marco; Castaño, Obis; Frutos, Luis Manuel, E-mail: luisma.frutos@uah.es [Departamento de Química Física, Universidad de Alcalá, 28871 Alcalá de Henares, Madrid (Spain); Acuña, A. Ulises [Instituto de Química Física “Rocasolano”, C.S.I.C., Serrano 119, 28006 Madrid (Spain)

    2014-01-21

    A definition of the triplet-triplet energy transfer reaction coordinate within the very weak electronic coupling limit is proposed, and a novel theoretical formalism is developed for its quantitative determination in terms of internal coordinates The present formalism permits (i) the separation of donor and acceptor contributions to the reaction coordinate, (ii) the identification of the intrinsic role of donor and acceptor in the triplet energy transfer process, and (iii) the quantification of the effect of every internal coordinate on the transfer process. This formalism is general and can be applied to classical as well as to nonvertical triplet energy transfer processes. The utility of the novel formalism is demonstrated here by its application to the paradigm of nonvertical triplet-triplet energy transfer involving cis-stilbene as acceptor molecule. In this way the effect of each internal molecular coordinate in promoting the transfer rate, from triplet donors in the low and high-energy limit, could be analyzed in detail.

  8. Lewis acid-water/alcohol complexes as hydrogen atom donors in radical reactions.

    Science.gov (United States)

    Povie, Guillaume; Renaud, Philippe

    2013-01-01

    Water or low molecular weight alcohols are, due to their availability, low price and low toxicity ideal reagents for organic synthesis. Recently, it was reported that, despite the very strong BDE of the O-H bond, they can be used as hydrogen atom donors in place of expensive and/or toxic group 14 metal hydrides when boron and titanium(III) Lewis acids are present. This finding represents a considerable innovation and uncovers a new perspective on the paradigm of hydrogen atom transfers to radicals. We discuss here the influence of complex formation and other association processes on the efficacy of the hydrogen transfer step. A delicate balance between activation by complex formation and deactivation by further hydrogen bonding is operative.

  9. Neutron transfer reactions with neutron-rich radioactive ion beams

    Energy Technology Data Exchange (ETDEWEB)

    Cizewski, J.A. [Department of Physics and Astronomy, Rutgers University, New Brunswick, NJ 08903 (United States)]. E-mail: cizewski@physics.rutgers.edu; Jones, K.L. [Department of Physics and Astronomy, Rutgers University, New Brunswick, NJ 08903 (United States); Pain, S.D. [Department of Physics and Astronomy, Rutgers University, New Brunswick, NJ 08903 (United States); Thomas, J.S. [Department of Physics and Astronomy, Rutgers University, New Brunswick, NJ 08903 (United States); Baktash, C. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Bardayan, D.W. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Blackmon, J.C. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Gross, C. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Liang, J.F. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Shapira, D. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Smith, M.S. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Kozub, R.L.; Moazen, B.H.; Nesaraja, C.D. [Department of Physics, Tennessee Technological University, Cookeville, TN 38505 (United States); Carter, H.K. [Oak Ridge Associated Universities, Oak Ridge, TN 37831 (United States); Johnson, M.S. [Oak Ridge Associated Universities, Oak Ridge, TN 37831 (United States); Fitzgerald, R.P.; Visser, D.W. [Department of Physics and Astronomy, University of North Carolina, Chapel Hill, NC 27599 (United States); Greife, U.; Livesay, R.J. [Department of Physics, Colorado School of Mines, Golden, CO 80401 (United States); Catford, W. [Department of Physics, University of Surrey, Guildford, Surrey GU27XH, UK (United Kingdom); Ma, Z. [Department of Physics, University of Tennessee, Knoxville, TN 37996 (United States)

    2005-12-15

    Initial measurements are presented of the (d,p) reactions on neutron-rich N = 50 isotones along the r-process path of nucleosynthesis with radioactive ion beams of {sup 82}Ge and {sup 84}Se. Prospects for measurements with unstable {sup 130,132}Sn beams are discussed.

  10. Mass transfer with complex reversible chemical reactions—II. parallel reversible chemical reactions

    NARCIS (Netherlands)

    Versteeg, G.F.; Kuipers, J.A.M.; Beckum, F.P.H. van; Swaaij, W.P.M. van

    1990-01-01

    An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and co

  11. The diffusion transfer of sputtered atoms in plasma spraying on the internal cylindrical surface

    International Nuclear Information System (INIS)

    The sputtering of the surface of the solid by the glow discharge plasma is used widely in the electronics for the deposition of thin films. The sputtered atoms (SA), leaving the surface, clash with the gas atoms and the granules the energy. It is interesting to examine the effect of the condensation coefficient of the SA on the concentration of the SA in the cylindrical discharge volume and the fluxes of the SA to different areas of the wall. The solution of this problem for the case of the diffusion transfer of the SA is the subject of this work

  12. Negative ion-uranium hexafluoride charge transfer reactions

    Science.gov (United States)

    Streit, Gerald E.; Newton, T. W.

    1980-10-01

    The flowing afterglow technique has been used to study the process of charge transfer from selected negative ions (F-, Cl-, Br-, I-, SF6-) to UF6. The sole ionic product in all cases was observed to be UF6-. Data analysis was complicated by an unexpected coupling of chemical and diffusive ion loss processes when UF6- product ions were present. The rate coefficients for the charge transfer processes are (k in 10-9 cm3 molecule-1 s-1) F-, 1.3; Cl-, 1.1; Br-, 0.93; I-, 0.77; and SF6-, 0.69. The rate constants agree quite well with the classical Langevin predictions.

  13. Activators generated by electron transfer for atom transfer radical polymerization of styrene in the presence of mesoporous silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Khezri, Khezrollah, E-mail: kh.khezri@ut.ac.ir [School of Chemistry, University College of Science, University of Tehran, PO Box 14155-6455, Tehran (Iran, Islamic Republic of); Roghani-Mamaqani, Hossein [Department of Polymer Engineering, Sahand University of Technology, PO Box 51335-1996, Tabriz (Iran, Islamic Republic of)

    2014-11-15

    Graphical abstract: Effect of mesoporous silica nanoparticles (MCM-41) on the activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is investigated. Decrement of conversion and number average molecular weight and also increment of polydispersity index (PDI) values are three main results of addition of MCM-41 nanoparticles. Incorporation of MCM-41 nanoparticles in the polystyrene matrix can clearly increase thermal stability and decrease glass transition temperature of the nanocomposites. - Highlights: • Spherical morphology, hexagonal structure, and high surface area with regular pore diameters of the synthesized MCM-41 nanoparticles are examined. • AGET ATRP of styrene in the presence of MCM-41 nanoparticles is performed. • Effect of MCM-41 nanoparticles addition on the polymerization rate, conversion and molecular weights of the products are discussed. • Improvement in thermal stability of the nanocomposites and decreasing T{sub g} values was also observed by incorporation of MCM-41 nanoparticles. - Abstract: Activator generated by electron transfer for atom transfer radical polymerization was employed to synthesize well-defined mesoporous silica nanoparticles/polystyrene composites. Inherent features of spherical mesoporous silica nanoparticles were evaluated by nitrogen adsorption/desorption isotherm, X-ray diffraction and scanning electron microscopy analysis techniques. Conversion and molecular weight evaluations were carried out using gas and size exclusion chromatography respectively. By the addition of only 3 wt% mesoporous silica nanoparticles, conversion decreases from 81 to 58%. Similarly, number average molecular weight decreases from 17,116 to 12,798 g mol{sup −1}. However, polydispersity index (PDI) values increases from 1.24 to 1.58. A peak around 4.1–4.2 ppm at proton nuclear magnetic resonance spectroscopy results clearly confirms the living nature of the polymerization. Thermogravimetric

  14. Role of axial base coordination in isonitrile binding and chalcogen atom transfer to vanadium(III) complexes.

    Science.gov (United States)

    Majumdar, Subhojit; Stauber, Julia M; Palluccio, Taryn D; Cai, Xiaochen; Velian, Alexandra; Rybak-Akimova, Elena V; Temprado, Manuel; Captain, Burjor; Cummins, Christopher C; Hoff, Carl D

    2014-10-20

    The enthalpy of oxygen atom transfer (OAT) to V[(Me3SiNCH2CH2)3N], 1, forming OV[(Me3SiNCH2CH2)3N], 1-O, and the enthalpies of sulfur atom transfer (SAT) to 1 and V(N[t-Bu]Ar)3, 2 (Ar = 3,5-C6H3Me2), forming the corresponding sulfides SV[(Me3SiNCH2CH2)3N], 1-S, and SV(N[t-Bu]Ar)3, 2-S, have been measured by solution calorimetry in toluene solution using dbabhNO (dbabhNO = 7-nitroso-2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-diene) and Ph3SbS as chalcogen atom transfer reagents. The V-O BDE in 1-O is 6.3 ± 3.2 kcal·mol(-1) lower than the previously reported value for 2-O and the V-S BDE in 1-S is 3.3 ± 3.1 kcal·mol(-1) lower than that in 2-S. These differences are attributed primarily to a weakening of the V-Naxial bond present in complexes of 1 upon oxidation. The rate of reaction of 1 with dbabhNO has been studied by low temperature stopped-flow kinetics. Rate constants for OAT are over 20 times greater than those reported for 2. Adamantyl isonitrile (AdNC) binds rapidly and quantitatively to both 1 and 2 forming high spin adducts of V(III). The enthalpies of ligand addition to 1 and 2 in toluene solution are -19.9 ± 0.6 and -17.1 ± 0.7 kcal·mol(-1), respectively. The more exothermic ligand addition to 1 as compared to 2 is opposite to what was observed for OAT and SAT. This is attributed to less weakening of the V-Naxial bond in ligand binding as opposed to chalcogen atom transfer and is in keeping with structural data and computations. The structures of 1, 1-O, 1-S, 1-CNAd, and 2-CNAd have been determined by X-ray crystallography and are reported. PMID:25280113

  15. Kinetics and mechanism of the reaction of fluorine atoms with pentafluoropropionic acid.

    Science.gov (United States)

    Vasiliev, E S; Knyazev, V D; Karpov, G V; Morozov, I I

    2014-06-12

    The kinetics of the reaction between fluorine atoms and pentafluoropropionic acid has been studied experimentally at T = 262-343 K. The overall reaction rate constant decreases with temperature: k1(T) = 6.1 × 10(-13) exp(+1166 K)/T) cm(3) molecule(-1) s(-1). The potential energy surface of the reaction has been studied using quantum chemistry. The results were used in transition state theory calculations of the temperature dependences of the rate constants of the two channels of the reaction. The abstraction channel ultimately producing HF, C2F5, and CO2 is dominant at the experimental temperatures; the addition-elimination channel producing C2F5 and CF(O)OH becomes important above 1000 K. PMID:24819330

  16. The effect of intramolecular quantum modes on free energy relationships for electron transfer reactions

    DEFF Research Database (Denmark)

    Ulstrup, Jens; Jortner, Joshua

    1975-01-01

    A general quantum mechanical description of exothermic electron transfer reactions is formulated by treating such reactions as the nonradiative decay of a ''supermolecule'' consisting of the electron donor, the electron acceptor, and the polar solvent. In particular, the role of the high-frequenc...

  17. Highly dispersed ruthenium hydroxide supported on titanium oxide effective for liquid-phase hydrogen-transfer reactions.

    Science.gov (United States)

    Yamaguchi, Kazuya; Koike, Takeshi; Kim, Jung Won; Ogasawara, Yoshiyuki; Mizuno, Noritaka

    2008-01-01

    Supported ruthenium hydroxide catalysts (Ru(OH)(x)/support) were prepared with three different TiO(2) supports (anatase TiO(2) (TiO(2)(A), BET surface area: 316 m(2) g(-1)), anatase TiO(2) (TiO(2)(B), 73 m(2) g(-1)), and rutile TiO(2) (TiO(2)(C), 3.2 m(2) g(-1))), as well as an Al(2)O(3) support (160 m(2) g(-1)). Characterizations with X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), and X-ray absorption fine structure (XAFS) showed the presence of monomeric ruthenium(III) hydroxide and polymeric ruthenium(III) hydroxide species. Judging from the coordination numbers of the nearest-neighbor Ru atoms and the intensities of the ESR signals, the amount of monomeric hydroxide species increased in the order of Ru(OH)(x)ruthenium hydroxide catalysts, especially Ru(OH)(x)/TiO(2)(A), showed high catalytic activities and selectivities for liquid-phase hydrogen-transfer reactions, such as racemization of chiral secondary alcohols and the reduction of carbonyl compounds and allylic alcohols. The catalytic activities of Ru(OH)(x)/TiO(2)(A) for these hydrogen-transfer reactions were at least one order of magnitude higher than those of previously reported heterogeneous catalysts, such as Ru(OH)(x)/Al(2)O(3). These catalyses were truly heterogeneous, and the catalysts recovered after the reactions could be reused several times without loss of catalytic performance. The reaction rates monotonically increased with an increase in the amount of monomeric ruthenium hydroxide species, which suggests that the monomeric species are effective for these hydrogen-transfer reactions. PMID:19021181

  18. A cobalt(ii) iminoiodane complex and its scandium adduct: mechanistic promiscuity in hydrogen atom abstraction reactions.

    Science.gov (United States)

    Kundu, Subrata; Chernev, Petko; Engelmann, Xenia; Chung, Chan Siu; Dau, Holger; Bill, Eckhard; England, Jason; Nam, Wonwoo; Ray, Kallol

    2016-10-01

    In addition to oxometal [M(n+)[double bond, length as m-dash]O] and imidometal [M(n+)[double bond, length as m-dash]NR] units, transient metal-iodosylarene [M((n-2)+)-O[double bond, length as m-dash]IPh] and metal-iminoiodane [M((n-2)+)-N(R)[double bond, length as m-dash]IPh] adducts are often invoked as a possible "second oxidant" responsible for the oxo and imido group transfer reactivity. Although a few metal-iodosylarene adducts have been recently isolated and/or spectroscopically characterized, metal-iminoiodane adducts have remained elusive. Herein, we provide UV-Vis, EPR, NMR, XAS and DFT evidence supporting the formation of a metal-iminoiodane complex 2 and its scandium adduct 2-Sc. 2 and 2-Sc are reactive toward substrates in the hydrogen-atom and nitrene transfer reactions, which confirm their potential as active oxidants in metal-catalyzed oxidative transformations. Oxidation of para-substituted 2,6-di-tert-butylphenols by 2 and 2-Sc can occur by both coupled and uncoupled proton and electron transfer mechanisms; the exact mechanism depends on the nature of the para substituent. PMID:27465222

  19. Neutron Transfer Reactions: Surrogates for Neutron Capture for Basic and Applied Nuclear Science

    Science.gov (United States)

    Cizewski, J. A.; Jones, K. L.; Kozub, R. L.; Pain, S. D.; Peters, W. A.; Adekola, A.; Allen, J.; Bardayan, D. W.; Becker, J. A.; Blackmon, J. C.; Chae, K. Y.; Chipps, K. A.; Erikson, L.; Gaddis, A.; Harlin, C.; Hatarik, R.; Howard, J.; Jandel, M.; Johnson, M. S.; Kapler, R.; Krolas, W.; Liang, F.; Livesay, R. J.; Ma, Z.; Matei, C.; Matthews, C.; Moazen, B.; Nesaraja, C. D.; O'Malley, P.; Patterson, N.; Paulauskas, S. V.; Pelham, T.; Pittman, S. T.; Radford, D.; Rogers, J.; Schmitt, K.; Shapira, D.; Shriner, J. F.; Sissom, D. J.; Smith, M. S.; Swan, T.; Thomas, J. S.; Vieira, D. J.; Wilhelmy, J. B.; Wilson, G. L.

    2009-03-01

    Neutron capture reactions on unstable nuclei are important for both basic and applied nuclear science. A program has been developed at the Holifield Radioactive Ion Beam Facility at Oak Ridge National Laboratory to study single-neutron transfer (d,p) reactions with rare isotope beams to provide information on neutron-induced reactions on unstable nuclei. Results from (d,p) studies on 130,132Sn, 134Te and 75As are discussed.

  20. Neutron transfer reactions: Surrogates for neutron capture for basic and applied nuclear science

    Energy Technology Data Exchange (ETDEWEB)

    Cizewski, J. A. [Rutgers University; Jones, K. L. [University of Tennessee; Kozub, R. L. [Tennessee Technological University; Pain, Steven D [ORNL; Peters, W. A. [Rutgers University; Adekola, Aderemi S [ORNL; Allen, J. [Rutgers University; Bardayan, Daniel W [ORNL; Becker, J. [Lawrence Livermore National Laboratory (LLNL); Blackmon, Jeff C [ORNL; Chae, K. Y. [University of Tennessee; Chipps, K. [Colorado School of Mines, Golden; Erikson, Luke [Colorado School of Mines, Golden; Gaddis, A. L. [Furman University; Harlin, Christopher W [ORNL; Hatarik, Robert [Rutgers University; Howard, Joshua A [ORNL; Jandel, M. [Los Alamos National Laboratory (LANL); Johnson, Micah [ORNL; Kapler, R. [University of Tennessee; Krolas, W. [University of Warsaw; Liang, J Felix [ORNL; Livesay, Jake [ORNL; Ma, Zhanwen [ORNL; Matei, Catalin [Oak Ridge Associated Universities (ORAU); Matthews, C. [Rutgers University; Moazen, Brian [University of Tennessee; Nesaraja, Caroline D [ORNL; O' Malley, Patrick [Rutgers University; Patterson, N. P. [University of Surrey, UK; Paulauskas, Stanley [University of Tennessee; Pelham, T. [University of Surrey, UK; Pittman, S. T. [University of Tennessee, Knoxville (UTK); Radford, David C [ORNL; Rogers, J. [Tennessee Technological University; Schmitt, Kyle [University of Tennessee; Shapira, Dan [ORNL; ShrinerJr., J. F. [Tennessee Technological University; Sissom, D. J. [Tennessee Technological University; Smith, Michael Scott [ORNL; Swan, T. P. [University of Surrey, UK; Thomas, J. S. [Rutgers University; Vieira, D. J. [Los Alamos National Laboratory (LANL); Wilhelmy, J. B. [Los Alamos National Laboratory (LANL); Wilson, Gemma L [ORNL

    2009-04-01

    Neutron capture reactions on unstable nuclei are important for both basic and applied nuclear science. A program has been developed at the Holifield Radioactive Ion Beam Facility at Oak Ridge National Laboratory to study single-neutron transfer (d,p) reactions with rare isotope beams to provide information on neutron-induced reactions on unstable nuclei. Results from (d,p) studies on {sup 130,132}Sn, {sup 134}Te and {sup 75}As are discussed.

  1. Atomic alignment effect on reactivity and on product alignment in the energy-transfer reaction of oriented Ar (3P2, 4s [3/2]2, M(J) = 2) + Kr (4p6, 1S0) → Ar (3p6, 1S0) + Kr (5p [3/2]2).

    Science.gov (United States)

    Ohoyama, H

    2015-03-12

    Steric effect for the formation of Kr (5p [3/2]₂) in the energy transfer reaction of Ar (³P₂, 4s [3/2]₂) + Kr has been studied by using an oriented Ar (³P₂, 4s [3/2]₂, M(J) = 2) beam at a collision energy of ∼0.09 eV. The emission intensity of Kr (5p [3/2]₂) is ca. 2 times enhanced when the angular momentum (J(Ar)) of Ar (³P₂) is aligned perpendicular to the relative velocity vector (v(R)). In addition, the Kr (5p [3/2]₂) emission is highly polarized parallel to v(R) (I(∥)/I(⊥) ∼ 1.2) when JAr is aligned perpendicular to v(R). The observed polarization moments indicate that the alignment of the unpaired Ar (3p) orbital of Ar (³P₂) to v(R), (Σ (|L′| = 0), Π (|L′| = 1)), dominates the energy transfer probability (σ(Π)(∥): σ(Σ)(∥): σ(Π)(⊥): σ(Σ)(⊥) = 0.49:1.33:0.55:1.23) and also the alignment of the Kr (5p) orbital of Kr (5p [3/2]₂) to v(R): the Σ-configuration of the Ar (3p) orbital leads to the parallel alignment (Σ-configuration) of the Kr(5p) orbital to v(R), conversely, the Π-configuration of Ar (3p) orbital leads to the perpendicular alignment (Π-configuration) of the Kr(5p) orbital. In addition, the selectivity of the alignment of the Kr (5p) orbital turns out to vary from perpendicular to parallel as the collision energy increases after a threshold down to 0.03 eV.

  2. Surface reactions of molecular and atomic oxygen with carbon phosphide films.

    Science.gov (United States)

    Gorham, Justin; Torres, Jessica; Wolfe, Glenn; d'Agostino, Alfred; Fairbrother, D Howard

    2005-11-01

    The surface reactions of atomic and molecular oxygen with carbon phosphide films have been studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Carbon phosphide films were produced by ion implantation of trimethylphosphine into polyethylene. Atmospheric oxidation of carbon phosphide films was dominated by phosphorus oxidation and generated a carbon-containing phosphate surface film. This oxidized surface layer acted as an effective diffusion barrier, limiting the depth of phosphorus oxidation within the carbon phosphide film to phosphorus atoms as well as the degree of phosphorus oxidation. For more prolonged AO exposures, a highly oxidized phosphate surface layer formed that appeared to be inert toward further AO-mediated erosion. By utilizing phosphorus-containing hydrocarbon thin films, the phosphorus oxides produced during exposure to AO were found to desorb at temperatures >500 K under vacuum conditions. Results from this study suggest that carbon phosphide films can be used as AO-resistant surface coatings on polymers.

  3. Surface-Initiated Atom Transfer Radical Polymerization and Electrografting Technique as a Means For Attaining Tailor-Made Polymer Coatings

    DEFF Research Database (Denmark)

    Chernyy, Sergey

    2012-01-01

    Atom transfer radical polymerization initiated from a surface of various substrates (SI-ATRP) has become a progressively popular technique for obtaining thin polymer films with predetermined properties. The present work addresses the main features of SI-ATRP with respect to the controllability......, rates of polymerization, suitable monomers, reaction mixture compositions etc. An alternative potential-driven polymerization approach is discussed, although to a smaller extent. Chapter 1 provides an overview of controlled/living polymerization techniques with an accent made on ATRP. Different...... strategies for initiator grafting, physicochemical properties of polymer brushes and basic principles of quartz crystal microbalance technique (QCM) are discussed. In Chapter 2 various ATRP conditions are probed. The effects of solvent polarity, monomer concentration, initiator surface density, ligand nature...

  4. Some consequences from polylinearity of thermodynamic functions of atomization reactions of binary compounds

    International Nuclear Information System (INIS)

    Interrelation between thermodynamic functions of atomization reactions of binary halides E(Xi)n, values of the functions in an isoparametric point and interatomic distances l(E-Xi) has been revealed on the basis of literature data. An equation describing the interrelation is suggested. It has been identical to correlation ratios used in organic chemistry for characterizing electronic and steric effects of halides ions. 14 refs., 1 fig., 1 tab

  5. Atmospheric Chemistry of CF3CF=CH2: Reactions With Cl Atoms, OH Radicals and Ozone

    Science.gov (United States)

    Sulbaek Andersen, M. P.; Javadi, M. S.; Nielsen, O. J.; Hurley, M. D.; Wallington, T. J.; Singh, R.

    2006-12-01

    The detrimental effects of chlorine chemistry on stratospheric ozone levels are well established. Consequently, there has been a concerted international effort to find replacements for chlorofluorocarbons (CFCs) used previously as electronic equipment cleaners, heat transfer agents, refrigerants, and carrier fluids for lubricant deposition. The replacements for CFCs, hydrofluorocarbons (HFCs) and hydrofluorochlorocarbons (HCFCs), have found widespread industrial use over the past decade. Unsaturated fluorinated hydrocarbons are a new class of compounds which have been developed to replace CFCs and HFCs in air condition units. Prior to any large-scale industrial use an assessment of the atmospheric chemistry, and hence environmental impact, of these compounds is needed. To address this need the atmospheric chemistry of CF3CF=CH2 was investigated. Smog chamber/FTIR techniques were used to determine the following properties for this compound: (i) kinetics of reactions with chlorine atoms (ii) kinetics of reactions with hydroxyl radicals (iii) kinetics of reactions with ozone, (iv) atmospheric lifetimes, (v) atmospheric degradation mechanism, and (vi) global warming potentials. The results are discussed with regard to the environmental impact of CF3CF=CH2 and the atmospheric chemistry of unsaturated fluorinated hydrocarbons.

  6. 9,10-Diphenylanthracene as a matrix for MALDI-MS electron transfer secondary reactions.

    Science.gov (United States)

    Boutaghou, M Nazim; Cole, Richard B

    2012-08-01

    The most common secondary-ionization mechanism in positive ion matrix-assisted laser desorption/ionization (MALDI) involves a proton transfer reaction to ionize the analyte. Peptides and proteins are molecules that have basic (and acidic) sites that make them susceptible to proton transfer. However, non-polar, aprotic compounds that lack basic sites are more difficult to protonate, and creating charged forms of this type of analyte can pose a problem when conventional MALDI matrices are employed. In this case, forming a radical molecular ion through electron transfer is a viable alternative, and certain matrices may facilitate the process. In this work, we investigate the performance of a newly developed electron-transfer secondary reaction matrix: 9,10-diphenylanthracene (9,10-DPA). The use of 9,10-DPA as matrix for MALDI analysis has been tested using several model compounds. It appears to promote ionization through electron transfer in a highly efficient manner as compared to other potential matrices. Thermodynamic aspects of the observed electron transfers in secondary-ionization reactions were also considered, as was the possibility for kinetically controlled/endothermic, electron-transfer reactions in the MALDI plume.

  7. Functional Virus-Based Polymer-Protein Nanoparticles by Atom Transfer Radical Polymerization

    OpenAIRE

    Pokorski, Jonathan K.; Breitenkamp, Kurt; Finn, M. G.

    2011-01-01

    Viruses and virus-like particles (VLPs) are useful tools in biomedical research. Their defined structural attributes make them attractive platforms for engineered interactions over large molecular surface areas. In this report, we describe the use of VLPs as multivalent macroinitiators for atom transfer radical polymerization (ATRP). The introduction of chemically reactive monomers during polymerization provides a robust platform for post-synthetic modification via the copper-catalyzed azide-...

  8. On Surface-Initiated Atom Transfer Radical Polymerization Using Diazonium Chemistry To Introduce the Initiator Layer

    DEFF Research Database (Denmark)

    Chernyy, Sergey; Lillethorup, Mie; Ceccato, Marcel;

    2011-01-01

    This work features the controllability of surface-initiated atom transfer radical polymerization (SI-ATRP) of methyl methacrylate, initiated by a multilayered 2-bromoisobutyryl moiety formed via diazonium chemistry. The thickness as a function of polymerization time has been studied by varying...... Cu(II)/Cu(I) complexes (L = Me(6)TREN, PMDETA, and BIPY). It is also observed that the ability of polymer brushes to reinitiate depends on the initial thickness and the solvent used for generating it....

  9. Bibliography on electron transfer processes in ion-ion/atom/molecule collisions. Updated 1997

    International Nuclear Information System (INIS)

    Following our previous compilations (IPPJ-AM-45 (1986), NIFS-DATA-7 (1990), NIFS-DATA-20 (1993)), bibliographic information on experimental and theoretical studies on electron transfer processes in ion-ion/atom/molecule collisions is up-dated. The references published through 1954-1996 are listed in the order of the publication year. For easy finding of the references for a combination of collision partners, a simple list is provided. (author)

  10. Bibliography on electron transfer processes in ion-ion/atom/molecule collisions, updated 1990

    International Nuclear Information System (INIS)

    Following a previous compilation, new bibliographic information on experimental and theoretical studies on electron transfer processes in ion-ion/atom/molecule collisions is up-dated. The references published through 1989 are surveyed. For easy finding references for particular combination of collision partners, a simple list is also provided. Furthermore, for convenience, a copy of the previous compilation (IPPJ-AM-45 (1986)) is included. (author) 1363 refs

  11. Bibliography on electron transfer processes in ion-ion/atom/molecule collisions. Updated 1997

    Energy Technology Data Exchange (ETDEWEB)

    Tawara, H.

    1997-04-01

    Following our previous compilations (IPPJ-AM-45 (1986), NIFS-DATA-7 (1990), NIFS-DATA-20 (1993)), bibliographic information on experimental and theoretical studies on electron transfer processes in ion-ion/atom/molecule collisions is up-dated. The references published through 1954-1996 are listed in the order of the publication year. For easy finding of the references for a combination of collision partners, a simple list is provided. (author)

  12. Coherence preservation of a single neutral atom qubit transferred between magic-intensity optical traps

    CERN Document Server

    Yang, Jiaheng; Guo, Ruijun; Xu, Peng; Wang, Kunpeng; Sheng, Cheng; Liu, Min; Wang, Jin; Derevianko, Andrei; Zhan, Mingsheng

    2016-01-01

    We demonstrate that the coherence of a single mobile atomic qubit can be well preserved during a transfer process among different optical dipole traps (ODTs). This is a prerequisite step in realizing a large-scale neutral atom quantum information processing platform. A qubit encoded in the hyperfine manifold of $^{87}$Rb atom is dynamically extracted from the static quantum register by an auxiliary moving ODT and reinserted into the static ODT. Previous experiments were limited by decoherences induced by the differential light shifts of qubit states. Here we apply a magic-intensity trapping technique which mitigates the detrimental effects of light shifts and substantially enhances the coherence time to $225 \\pm 21\\,\\mathrm{ms}$. The experimentally demonstrated magic trapping technique relies on the previously neglected hyperpolarizability contribution to the light shifts, which makes the light shift dependence on the trapping laser intensity to be parabolic. Because of the parabolic dependence, at a certain ...

  13. H{sup .} atom and OH{sup .} radical reactions with 5-methyl-cytosine

    Energy Technology Data Exchange (ETDEWEB)

    Grand, A.; Morell, C.; Labet, V.; Cadet, J. [CEA Grenoble, Lab Les Acides Nucl, DRFMC/SCIB, UMR-E 3, CEA-UJF, F-38054 Grenoble, (France); Eriksson, L.A. [Univ Orebro, Dept Nat Sci and Orebro Life Sci Ctr, S-70182 Orebro, (Sweden)

    2007-07-01

    The reactions between either a hydrogen atom or a hydroxyl radical and 5-methyl-cytosine (5-MeCyt) are studied by using the hybrid kinetic energy meta-GGA functional MPW1B95. H{sup .} atom and OH{sup .} radical addition to positions C5 and C6 of 5-MeCyt, or OH{sup .} radical induced H-abstraction from the C5 methyl group, are explored. All systems are optimized in bulk solvent. The data presented show that the barriers to reaction are very low: ca. 7 kCal/mol for the H{sup .} atom additions and 1 kCal/mol for the reactions involving the OH{sup .} radical. Thermodynamically, the two C6 radical adducts and the H{sup .}- abstraction product are the most stable ones. The proton hyperfine coupling constants (HFCC), computed at the IEFPCM/MPW1B95/6-311++G(2d,2p) level, agree well with B3LYP results and available experimental and theoretical data on related thymine and cytosine radicals. (authors)

  14. H. atom and OH. radical reactions with 5-methyl-cytosine

    International Nuclear Information System (INIS)

    The reactions between either a hydrogen atom or a hydroxyl radical and 5-methyl-cytosine (5-MeCyt) are studied by using the hybrid kinetic energy meta-GGA functional MPW1B95. H. atom and OH. radical addition to positions C5 and C6 of 5-MeCyt, or OH. radical induced H-abstraction from the C5 methyl group, are explored. All systems are optimized in bulk solvent. The data presented show that the barriers to reaction are very low: ca. 7 kCal/mol for the H. atom additions and 1 kCal/mol for the reactions involving the OH. radical. Thermodynamically, the two C6 radical adducts and the H.- abstraction product are the most stable ones. The proton hyperfine coupling constants (HFCC), computed at the IEFPCM/MPW1B95/6-311++G(2d,2p) level, agree well with B3LYP results and available experimental and theoretical data on related thymine and cytosine radicals. (authors)

  15. Efficiency limitation for realizing an atom-molecule adiabatic transfer based on a chainwise system

    CERN Document Server

    Zhai, Jingjing; Zhang, Keye; Qian, Jing; Zhang, Weiping

    2015-01-01

    In a recent work we have developed a robust chainwise atom-molecule adiabatic passage scheme to produce ultracold ground-state molecules via photo-associating free atoms [J. Qian {\\it et.al.} Phys. Rev. A 81 013632 (2010)]. With the help of intermediate auxiliary levels, the pump laser intensity requested in the atomic photo-association process can be greatly reduced. In the present work, we extend the scheme to a more generalized (2$n$+1)-level system and investigate the efficiency limitation for it. As the increase of intermediate levels and auxiliary lasers, the atom-molecule adiabatic passage would be gradually closed, leading to a poor transfer efficiency. For the purpose of enhancing the efficiency, we present various optimization approaches to the laser parameters, involving order number $n$, relative strength ratio and absolute strength. We show there can remain a limit on the population transfer efficiency given by a three-level $\\Lambda$ system. In addition, we illustrate the importance of selecting...

  16. [Spectrophotometric determination of cinnarizine based on charge-transfer reaction].

    Science.gov (United States)

    Xu, B; Zhao, F; Tong, S

    1999-12-01

    The charge-transfer (CT) complex formed between cinnarizine as the donor and 7, 7, 8, 8-Tetracyanoquinodimethane (TCNQ) as the acceptor in acetone-methanol has been studied by spectrophotometric method. Beer's law is obeyed in the range of 0-18 microg x mL(-1) of cinnarizine. The apparent molar absorptivity of CT complex at 743 nm is 1.58 x 10(4) L x mol(-1) x cm(-1). The composition of CT complex is found to be 1 : 1 by Bent-French and Job's methods. The relative standard deviation is less than 3% (n = 10). The method has been applied to the determination of cinnarizine in tablets with satisfactory results. PMID:15822327

  17. Significance Of Deuteron Breakup In A Halo Transfer Reaction

    CERN Document Server

    Yilmaz, M; Yilmaz, Mustafa; Gonul, Bulent

    2000-01-01

    We discuss the quasi-adiabatic approximations to the three-body wavefunction in breakup processes, clarifying the assumptions underlying the model. This suggests alternative approximation schemes. Using different theoretical three-body models, calculated differential cross section angular distributions for the Be-11(p,d) reaction,for which new preliminary data have been reported at 35 MeV, are presented. We show that calculations are sensitive to the inclusion of deuteron breakup and to the breakup model used, particularly if used to deduce absolute spectroscopic information on the 0{+} and 2{+} Be-10 core state parentages. There is also considerable sensitivity to the model used in calculations of the relative cross sections to the two states.

  18. Tracer investigations of the fate of sulphur atoms in the course of high-temperature reactions

    International Nuclear Information System (INIS)

    The fact that sulphur occurs in many different chemical conditions suggests a number of interesting problems in connexion with the movement of the sulphur atoms in the course of reactions between different compounds of this element. Quite an amount of information is available concerning reactions between compounds of sulphur in solution and, in general, the different sulphur fractions do not mix under these conditions. An entirely different situation is found in reactions between gases and solid compounds. For these processes much higher temperatures are, in general, required and at these higher temperatures the sulphur atoms in the different fractions tend to mix to a very large extent. This behaviour is illustrated by means of data obtained on the exchange of radiosulphur between sulphur vapour and sulphur dioxide, between sulphur dioxide and solid sulphite and between sulphur dioxide and solid sulphate. The same behaviour has been observed in the chemical decomposition of thiosulphate, labelled in one of the two sulphur fractions and in the oxidation of this compound. Finally, it has been shown that mixing is also very strong in the reaction between sulphur vapour- and solid sulphate. (author)

  19. NI (II AND PB (II INHIBIT THE ENZYMATIC ACTIVITY OF DNA IN AN ELECTRON TRANSFER REACTION

    Directory of Open Access Journals (Sweden)

    B FARZAMI

    2002-03-01

    Full Text Available Introduction. Ni and Pb are metals with several suggested mechanisms for their toxicity on the biological systems. We have recently investigated involvement of DNA in an electron transfer reaction as an enzyme. In this reaction non- fluorescent dichlorofluorescin (LDCF is converted to the dichlorofluorescein (DCF in the presence of peroxides and hematin. Methods. The fluorometric technique was used in this study. The pH effect on the reaction rate was investigated. The results showed that DCF has the maximum emission on tris buffer 0.05 Mat pH 8.4. Results. DNA and carnosine catalyze the reaction, which proceeds by the electron transfer mechanism. The presence of carnosine is necessary for the catalytic action of DNA as a cofactor. Ni (II and Pb (11 are the potent inhibitors of the reaction. The kinetic parameters and determined in the presence and absence of the above ligands. Discussion. DNA, which has the electrical properties only in the double helical forms, acts as a catalyst in the conversion of LDCF to DCF. The existence of the carnosine, an endogenous dipeptide with antioxidant and free radical scavenging roles, is an important factor for the progress of the reaction. Both Ni (11 and Pb (II inhibit the reaction. These metals could act as the electron pool to cause inhibition in such electron transfer reaction. This phenomenon could be related to the carcinogenic effect of these metals.

  20. Atomic layer deposition by reaction of molecular oxygen with tetrakisdimethylamido-metal precursors

    Energy Technology Data Exchange (ETDEWEB)

    Provine, J, E-mail: jprovine@stanford.edu; Schindler, Peter; Torgersen, Jan; Kim, Hyo Jin [Department of Mechanical Engineering, Stanford University, Stanford, California 94305 (United States); Karnthaler, Hans-Peter [Physics of Nanostructured Materials, University of Vienna, 1090 Vienna (Austria); Prinz, Fritz B. [Department of Mechanical Engineering, Stanford University, Stanford, California 94305 and Department of Materials Science and Engineering, Stanford University, Stanford, California 94305 (United States)

    2016-01-15

    Tetrakisdimethylamido (TDMA) based precursors are commonly used to deposit metal oxides such as TiO{sub 2}, ZrO{sub 2}, and HfO{sub 2} by means of chemical vapor deposition and atomic layer deposition (ALD). Both thermal and plasma enhanced ALD (PEALD) have been demonstrated with TDMA-metal precursors. While the reactions of TDMA-type precursors with water and oxygen plasma have been studied in the past, their reactivity with pure O{sub 2} has been overlooked. This paper reports on experimental evaluation of the reaction of molecular oxygen (O{sub 2}) and several metal organic precursors based on TDMA ligands. The effect of O{sub 2} exposure duration and substrate temperature on deposition and film morphology is evaluated and compared to thermal reactions with H{sub 2}O and PEALD with O{sub 2} plasma.

  1. Atomic layer deposition by reaction of molecular oxygen with tetrakisdimethylamido-metal precursors

    International Nuclear Information System (INIS)

    Tetrakisdimethylamido (TDMA) based precursors are commonly used to deposit metal oxides such as TiO2, ZrO2, and HfO2 by means of chemical vapor deposition and atomic layer deposition (ALD). Both thermal and plasma enhanced ALD (PEALD) have been demonstrated with TDMA-metal precursors. While the reactions of TDMA-type precursors with water and oxygen plasma have been studied in the past, their reactivity with pure O2 has been overlooked. This paper reports on experimental evaluation of the reaction of molecular oxygen (O2) and several metal organic precursors based on TDMA ligands. The effect of O2 exposure duration and substrate temperature on deposition and film morphology is evaluated and compared to thermal reactions with H2O and PEALD with O2 plasma

  2. Incident angle dependence of reactions between graphene and hydrogen atom by molecular dynamics simulation

    CERN Document Server

    Saito, Seiki; Nakamura, Hiroaki

    2009-01-01

    Incident angle dependence of reactions between graphene and hydrogen atoms are obtained qualitatively by classical molecular dynamics simulation under the NVE condition with modified Brenner reactive empirical bond order (REBO) potential. Chemical reaction depends on two parameters, i.e., polar angle $\\theta$ and azimuthal angle $\\phi$ of the incident hydrogen. From the simulation results, it is found that the reaction rates strongly depend on polar angle $\\theta$. Reflection rate becomes larger with increasing $\\theta$, and the $\\theta$ dependence of adsorption rate is also found. The $\\theta$ dependence is caused by three dimensional structure of the small potential barrier which covers adsorption sites. $\\phi$ dependence of penetration rate is also found for large $\\theta$.

  3. Multiply Confined Nickel Nanocatalysts Produced by Atomic Layer Deposition for Hydrogenation Reactions.

    Science.gov (United States)

    Gao, Zhe; Dong, Mei; Wang, Guizhen; Sheng, Pei; Wu, Zhiwei; Yang, Huimin; Zhang, Bin; Wang, Guofu; Wang, Jianguo; Qin, Yong

    2015-07-27

    To design highly efficient catalysts, new concepts for optimizing the metal-support interactions are desirable. Here we introduce a facile and general template approach assisted by atomic layer deposition (ALD), to fabricate a multiply confined Ni-based nanocatalyst. The Ni nanoparticles are not only confined in Al2 O3 nanotubes, but also embedded in the cavities of Al2 O3 interior wall. The cavities create more Ni-Al2 O3 interfacial sites, which facilitate hydrogenation reactions. The nanotubes inhibit the leaching and detachment of Ni nanoparticles. Compared with the Ni-based catalyst supported on the outer surface of Al2 O3 nanotubes, the multiply confined catalyst shows a striking improvement of catalytic activity and stability in hydrogenation reactions. Our ALD-assisted template method is general and can be extended for other multiply confined nanoreactors, which may have potential applications in many heterogeneous reactions.

  4. Ultrafast Electron Transfer Kinetics in the LM Dimer of Bacterial Photosynthetic Reaction Center from Rhodobacter sphaeroides.

    Science.gov (United States)

    Sun, Chang; Carey, Anne-Marie; Gao, Bing-Rong; Wraight, Colin A; Woodbury, Neal W; Lin, Su

    2016-06-23

    It has become increasingly clear that dynamics plays a major role in the function of many protein systems. One system that has proven particularly facile for studying the effects of dynamics on protein-mediated chemistry is the bacterial photosynthetic reaction center from Rhodobacter sphaeroides. Previous experimental and computational analysis have suggested that the dynamics of the protein matrix surrounding the primary quinone acceptor, QA, may be particularly important in electron transfer involving this cofactor. One can substantially increase the flexibility of this region by removing one of the reaction center subunits, the H-subunit. Even with this large change in structure, photoinduced electron transfer to the quinone still takes place. To evaluate the effect of H-subunit removal on electron transfer to QA, we have compared the kinetics of electron transfer and associated spectral evolution for the LM dimer with that of the intact reaction center complex on picosecond to millisecond time scales. The transient absorption spectra associated with all measured electron transfer reactions are similar, with the exception of a broadening in the QX transition and a blue-shift in the QY transition bands of the special pair of bacteriochlorophylls (P) in the LM dimer. The kinetics of the electron transfer reactions not involving quinones are unaffected. There is, however, a 4-fold decrease in the electron transfer rate from the reduced bacteriopheophytin to QA in the LM dimer compared to the intact reaction center and a similar decrease in the recombination rate of the resulting charge-separated state (P(+)QA(-)). These results are consistent with the concept that the removal of the H-subunit results in increased flexibility in the region around the quinone and an associated shift in the reorganization energy associated with charge separation and recombination. PMID:27243380

  5. Back-Influence of Molecular Motion on Energy Transfer in the Landau-Teller Model of Atom Molecule Scattering.

    Science.gov (United States)

    Pollak, Eli

    2016-07-21

    This year we celebrate the 80th anniversary of the Landau-Teller model for energy exchange in a collinear collision of an atom with a harmonic diatomic molecule. Even after 80 years though, the analytic theory to date has not included in it the back-influence of the oscillator's motion on the energy transfer between the approaching particle and the molecule. This is the topic of the present paper. The back-influence can be obtained by employing classical second-order perturbation theory. The second-order theory is used in both a classical and semiclassical context. Classically, analytic expressions are derived for the final phase and action of the diatom, after the collision. The energy loss of the atom is shown to decrease linearly with the increasing energy of the oscillator. The magnitude of this decrease is a direct consequence of the back-reaction of the oscillator on the translational motion. The qualitative result is universal, in the sense that it is not dependent on the details of the interaction of the atom with the oscillator. A numerical application to a model collision of an Ar atom with a Br2 diatom demonstrates the importance and accuracy of the second-order perturbation theory. The same results are then used to derive a second-order perturbation theory semiclassical expression for the quantum transition probability from initial vibrational state ni to final vibrational state nf of the oscillator. A comparison of the theory with exact quantum data is presented for a model collision of Br2 with a hydrogen molecule, where the hydrogen molecule is considered as a single approaching particle.

  6. Back-Influence of Molecular Motion on Energy Transfer in the Landau-Teller Model of Atom Molecule Scattering.

    Science.gov (United States)

    Pollak, Eli

    2016-07-21

    This year we celebrate the 80th anniversary of the Landau-Teller model for energy exchange in a collinear collision of an atom with a harmonic diatomic molecule. Even after 80 years though, the analytic theory to date has not included in it the back-influence of the oscillator's motion on the energy transfer between the approaching particle and the molecule. This is the topic of the present paper. The back-influence can be obtained by employing classical second-order perturbation theory. The second-order theory is used in both a classical and semiclassical context. Classically, analytic expressions are derived for the final phase and action of the diatom, after the collision. The energy loss of the atom is shown to decrease linearly with the increasing energy of the oscillator. The magnitude of this decrease is a direct consequence of the back-reaction of the oscillator on the translational motion. The qualitative result is universal, in the sense that it is not dependent on the details of the interaction of the atom with the oscillator. A numerical application to a model collision of an Ar atom with a Br2 diatom demonstrates the importance and accuracy of the second-order perturbation theory. The same results are then used to derive a second-order perturbation theory semiclassical expression for the quantum transition probability from initial vibrational state ni to final vibrational state nf of the oscillator. A comparison of the theory with exact quantum data is presented for a model collision of Br2 with a hydrogen molecule, where the hydrogen molecule is considered as a single approaching particle. PMID:27309793

  7. Influence of Complex Stabilities on Electron-Transfer Reactions

    International Nuclear Information System (INIS)

    The rate of exchange in solutions containing sulphate ions was measured in the system FeII/FeIII at different temperatures with 5'9Fe as a tracer. At 25°C and an ionic strength of 1 the rate constants are: k1[FeSO+4/Fe2+] =295 litres mole-1 sec-1, k2[Fe(SO4)2-/Fe2+] =17 500 litres mole-1 sec-1. The activation energies are E1 =13.8 kcal/mole, E2 = 15kcal/mole. For the rate constants of the electron exchange between different complexes of FeIII and Fe2+ ions the following relation was found: log10k = 1.1 + 0. 5 |Δlog10K|, where Δ log10K is the difference between the logarithms of the stability constants of the FeIII and FeII complexes with the same ligands. All rate constants for electron exchange between FeIII complexes and Fe2+ ions follow this relation (as far as stability constants are known). In the system CeIII/ CeIV a first-order reaction with respect to CeIII contributes to the exchange reaction. This is explained by the formation of excited CeIII ions. The rate constant is k5 = 4.45 x 10-4 sec-1 (0°C). At 0°C the rate constants for the second-order reactions are: k1[CeSO+24/Ce3+] = 0.10 litres mole-1 sec-1, k2[Ce(SO4)2/Ce3+] = 0.11 litres mole-1 sec-1; k3[Ce(SO4)2-3/Ce3+] = 0.17 litres mole-1 sec-1, k4 [Ce4+/Ce3+] = 5.05 x 10-3 litres mole-1 sec-1. The electron exchange is accelerated by sulphate ions, but not to the same extent as in the system FeII/FeIII. The fact that the rate constants k, k2 and k3 are nearly equal shows that the charge of the complexes has no influence. The rate constants in the system CeIII/CeIV also follow a relation of the form log k = a + bΔlog K. The constants a and b were found to be: a = -2.3, b = 0.4. In the system UIV/UVI - in the absence of light - the rate of the electron exchange in solutions containing sulphate ions is proportional to the concentrations of UIV and UVI and inversely proportional to the third power of the H+ concentration. The rate determining step is the disproportionation of UV which is present in

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

    International Nuclear Information System (INIS)

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

  9. Excited state intramolecular charge transfer reaction in 4-(1-azetidinyl)benzonitrile: Solvent isotope effects

    Indian Academy of Sciences (India)

    Tuhin Pradhan; Piue Ghoshal; Ranjit Biswas

    2009-01-01

    Excited state intramolecular charge transfer reaction of 4-(1-azetidinyl) benzonitrile (P4C) in deuterated and normal methanol, ethanol and acetonitrile has been studied in order to investigate the solvent isotope effects on reaction rates and yields. These quantities (reaction rates and yields) along with several other properties such as quantum yield and radiative rates have been found to be insensitive to the solvent isotope substitution in all these solvents. The origin of the solvent isotope insensitivity of the reaction is discussed and correlated with the observed slowing down of the solvation dynamics upon isotope substitution.

  10. Sodium-water reaction test to confirm thermal influence on heat transfer tubes

    International Nuclear Information System (INIS)

    Sodium-water reaction tests are carried out using the Sodium Water Reaction Test Rig. (SWAT-1R). The objective of this study is to obtain the experimental knowledge of following items. 1) Thermal characteristics of sodium-water reaction jet. 2) Effects on heat transfer tubes by high temperature reaction jet. Those are necessary to establish a systematic evaluate method for the failure propagation of FBR steam generator heat transfer tubes. Then we performed parametric three HT tests (series of test to confirm thermal influence on tubes), and the parameter is water leak rate. Following items are clarified in this report. 1) No difference was observed about the maxim temperature of reaction jet in each test. HT-1:1161degC, HT-2:1013degC, HT-3:1164degC The reaction jet became stable within ten seconds, and the jet size depended on water leak rate. 2) The thermal data for calculating the heat transfer coefficient were obtained and it's evaluation method was established. The thermal influence of heat transfer tubes suffered by more than 1100degC high temperature jet in 20 seconds are almost equal to that of standardization test materials suffered by 900degC in 20 seconds. (author)

  11. Removal of Hg~0 with sodium chlorite solution and mass transfer reaction kinetics

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The absorption behavior of Hg0 was studied experimentally by using sodium chlorite solution(NaClO2) as the absorbent in a bubble reactor.Primary influencing factors on removal efficiency of Hg0 such as NaClO2 concentration,pH,reaction temperature and the concentration of Hg0 were investigated.The results indicated that 72.91% of Hg0 removal efficiency could be achieved in acidic NaClO2 solution.The removal mechanism of Hg0 was proposed by analyzing of Hg2+ concentration in ab-sorption solution after reaction and comparing the electrode potentials between NaClO2 species and Hg2+/Hg0.The experimental results of mass transfer-reaction kinetics on oxidation of Hg0 by NaClO2 solution showed that with the increase of NaClO2 concentration and the decrease of pH value,the enhancement factor(E) and ratio of KG(Hg0)/kG(Hg0) increased and the liquid phase mass transfer resistance decreased,which is benefit to the mass transfer adsorption reaction.Although the increase of reaction temperature could improve the enhancement factor(E),but the ratio of KG(Hg0)/kG(Hg0) decreased;as a result,the liquid phase mass transfer resistance increased,therefore,the reaction rate for removal of Hg0 decreased.

  12. Nobel Prize 1992: Rudolph A. Marcus: theory of electron transfer reactions in chemical systems

    International Nuclear Information System (INIS)

    A review of the theory developed by Rudolph A. Marcus is presented, who for his rating to the theory of electron transfer in chemical systems was awarded the Nobel Prize in Chemistry in 1992. Marcus theory has constituted not only a good extension of the use of a spectroscopic principle, but also has provided an energy balance and the application of energy conservation for electron transfer reactions. A better understanding of the reaction coordinate is exposed in terms energetic and establishing the principles that govern the transfer of electrons, protons and some labile small molecular groups as studied at present. Also, the postulates and equations described have established predictive models of reaction time, very useful for industrial environments, biological, metabolic, and others that involve redox processes. Marcus theory itself has also constituted a large contribution to the theory of complex transition

  13. Transfer reactions for the /sup 50/Ti + /sup 90/Zr system below the Coulomb barrier

    International Nuclear Information System (INIS)

    The analysis of quasielastic cross section data for the /sup 90/Zr projectile plus /sup 50/Ti target system shows that the probability for /sup 50/Ti(/sup 90/Zr, /sup 49/Ti)/sup 91/Zr, 1n-transfer reaction near the barrier is much larger than estimates based on semiclassical theory. The probability for /sup 50/Ti(/sup 90/Zr,/sup 51/V)/sup 89/Y, 1p-transfer reaction, on the other hand, agrees with the same theory. The internuclear distance where the 1n-transfer probability first deviates from tunneling predictions coincides with the threshold of the fusion barrier distribution deduced from the experimental fusion cross sections of the /sup 50/Ti+/sup 90/Zr system, suggesting a common mechanism for the large enhancement of 1n-transfer and fusion cross sections

  14. Quantum Coherence as a Witness of Vibronically Hot Energy Transfer in Bacterial Reaction Centre

    CERN Document Server

    Paleček, David; Westenhoff, Sebastian; Zigmantas, Donatas

    2016-01-01

    Photosynthetic proteins have evolved over billions of years so as to undergo optimal energy transfer to the sites of charge separation. Based on spectroscopically detected quantum coherences, it has been suggested that this energy transfer is partially wavelike. This conclusion critically depends on assignment of the coherences to the evolution of excitonic superpositions. Here we demonstrate for a bacterial reaction centre protein that long-lived coherent spectroscopic oscillations, which bear canonical signatures of excitonic superpositions, are essentially vibrational excited state coherences shifted to the ground state of the chromophores . We show that appearance of these coherences is brought about by release of electronic energy during the energy transfer. Our results establish how energy migrates on vibrationally hot chromophores in the reaction centre and they call for a re-examination of claims of quantum energy transfer in photosynthesis.

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

    CERN Document Server

    Gibbard, Jemma A

    2016-01-01

    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...

  16. Gas-Phase Reactions of Atomic Gold Cations with Linear Alkanes (C2-C9).

    Science.gov (United States)

    Zhang, Ting; Li, Zi-Yu; Zhang, Mei-Qi; He, Sheng-Gui

    2016-06-30

    To develop proper ionization methods for alkanes, the reactivity of bare or ligated transition metal ions toward alkanes has attracted increasing interests. In this study, the reactions of the gold cations with linear alkanes from ethane up to nonane (CnH2n+2, n = 2-9) under mild conditions have been characterized by mass spectrometry and density functional theory calculations. When reacting with Au(+), small alkanes (n = 2-6) were confirmed to follow specific reaction channels of dehydrogenation for ethane and hydride transfer for others to generate product ions characteristic of the original alkanes, which indicates that Au(+) can act as a reagent ion to ionize alkanes from ethane to n-hexane. Strong dependence of the chain length of alkanes was observed for the rate constants and reaction efficiencies. Extensive fragmentation took place for larger alkanes (n > 6). Theoretical results show that the fragmentation induced by the hydride transfer occurs after the release of AuH. Moreover, the fragmentation of n-heptane was successfully avoided when the reaction took place in a high-pressure reactor. This implies that Au(+) is a potential reagent ion to ionize linear and even the branched alkanes. PMID:27266670

  17. Dynamics of interfacial reactions between O(3 P) atoms and long-chain liquid hydrocarbons

    Science.gov (United States)

    Allan, Mhairi; Bagot, Paul A. J.; Köhler, Sven P. K.; Reed, Stewart K.; Westacott, Robin E.; Costen, Matthew L.; McKendrick, Kenneth G.

    2007-09-01

    Recent progress that has been made towards understanding the dynamics of collisions at the gas-liquid interface is summarized briefly. We describe in this context a promising new approach to the experimental study of gas-liquid interfacial reactions that we have introduced. This is based on laser-photolytic production of reactive gas-phase atoms above the liquid surface and laser-spectroscopic probing of the resulting nascent products. This technique is illustrated for reaction of O(3P) atoms at the surface of the long-chain liquid hydrocarbon squalane (2,6,10,15,19,23-hexamethyltetracosane). Laser-induced fluorescence detection of the nascent OH has revealed mechanistically diagnostic correlations between its internal and translational energy distributions. Vibrationally excited OH molecules are able to escape the surface. At least two contributions to the product rotational distributions are identified, confirming and extending previous hypotheses of the participation of both direct and trapping-desorption mechanisms. We speculate briefly on future experimental and theoretical developments that might be necessary to address the many currently unanswered mechanistic questions for this, and other, classes of gas-liquid interfacial reaction.

  18. 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

    2003-01-01

    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.

  19. The 2H(e, e' p)n reaction at large energy transfers

    NARCIS (Netherlands)

    Willering, Hendrik Willem

    2003-01-01

    At the ELSA accelerator facillity in Bonn, Germany, we have measured the deutron "breakup" reaction 2H(e,e' p)n at four-momentum transfers around Q2 = -0 .20(GeV/c)2 with an electron beam energy of E0 = 1.6 GeV. The cross section has been determined for energy transfers extending from the quasielast

  20. A Novel Micro-hole Electrode Used to Investigate Electron Transfer Reactions at ITIES

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A novel micro-hole electrode was fabricated to investigate the electron transfer reaction at the interface between two immiscible electrolyte solutions (ITIES). The electron transfer reaction between ferro/ferricyanide in aqueous phase (W) and ferrocene in 1, 2-dichloroethane (O) phase was studied as a test experiment. The results showed that the diffusion coefficient obtained from the micro-hole electrode was consistent with that obtained at macro-interface. Due to its simplicity and the very small IR drop it will be a useful tool for the study of ITIES systems.

  1. A Novel Micro—hole Electrode Used to Investigate Electron Transfer Reactions at ITIES

    Institute of Scientific and Technical Information of China (English)

    DongPingZHAN; BingLiangWU

    2002-01-01

    A novel micro-hole electrode was fabricated to investigate the electron transfer reaction at the interface between two immiscible electrolyte solutions (ITIES). The electron transfer reaction between feero/ferricyanide in aqueous phase(W) and ferrocene in 1,2-dichloroethane (O) phase was studied as a test experiment. The results showed that the diffusion coefficient obtained from the micro-hole electrode was consistent with that obtained at macro-interface. Due to its simplicity and the very small IR drop it will be a useful tool for the study of ITIES systems.

  2. Spin transfer coefficients for the (p suprho,n suprho) reaction in the plane wave approximation

    CERN Document Server

    Lee, H S; Kim, B T

    1998-01-01

    The spin transfer coefficients D sub n sub n (theta=0 .deg. ) for the intermediate energy charge exchange reaction (p suprho,n suprho) leading to the giant resonances in the continuum region are investigated. The dependence of the spin transfer coefficients on the nuclear wave function, the reaction Q-value, and the effective two-body interaction are studied using the plane wave approximation. It is shown that both the direct and the exchange parts of the tensor interaction play important roles in determining the D sub n sub n value.

  3. 2D momentum distribution of electron in transfer ionization of helium atom by fast proton

    International Nuclear Information System (INIS)

    2D distribution of momentum components of the ejected electron in the reaction H+ +He → H+He2++e at 630 keV proton is studied both theoretically and experimentally. This allows to unambiguously identify contributions from the shake-off and binary encounter mechanisms of transfer ionization. It is shown that the results are highly sensitive to the quality of the initial-state wave function.

  4. Theoretical Study on the NO2 + NO2- Electron Transfer Reaction

    Institute of Scientific and Technical Information of China (English)

    ZHOU,Zheng-Yu(周正宇); GAO,Hong-Wei(高洪伟); XING,Yu-Mei(邢玉梅); GUO,Li(郭丽); QU,Yu-Hui(曲玉辉)

    2002-01-01

    The NO2 + NO2- electron transfer reaction was studied with DFT-B3LYP method at 6-311 + G* basis set level for the eight selected structures: four species favor the strucure of "head to head". The geometry of transition state was obtained by the linear coordinate method. Three parameters, non-adiahatic activation energy (Ead), coupling matrix element (Hif) and reorganization energy (λ) for electron transfer reaction can be calculated. According to the reorganization energy of the ET reaction, the values obtained from George-Griffith-Marcus (GGM) method (the contribution only from diagonal elements of force constant matrix) are larger than those obtained from Hessian matrix method (including the contribution from both diagonal and off-diagonal elements), which suggests that the coupling interactions between different vibrational modes are important to the inner-sphere reogrganization energy for the ET reactions in gaseous phase. The value of rate constant was obtained by using above three activation parameters.

  5. Control and Transfer of Entanglement between Two Atoms Driven by Classical Fields under Dressed-State Representation

    Science.gov (United States)

    Liao, Qing-Hong; Zhang, Qi; Xu, Juan; Yan, Qiu-Rong; Liu, Ye; Chen, An

    2016-06-01

    We have studied the dynamics and transfer of the entanglement of the two identical atoms simultaneously interacting with vacuum field by employing the dressed-state representation. The two atoms are driven by classical fields. The influence of the initial entanglement degree of two atoms, the coupling strength between the atom and the classical field and the detuning between the atomic transition frequency and the frequency of classical field on the entanglement and atomic linear entropy is discussed. The initial entanglement of the two atoms can be transferred into the entanglement between the atom and cavity field when the dissipation is neglected. The maximally entangled state between the atoms and cavity field can be obtained under some certain conditions. The time of disentanglement of two atoms can be controlled and manipulated by adjusting the detuning and classical driving fields. Moreover, the larger the cavity decay rate is, the more quickly the entanglement of the two atoms decays. Supported by National Natural Science Foundation of China under Grant Nos. 11247213, 61368002, 11304010, 11264030, 61168001, China Postdoctoral Science Foundation under Grant No. 2013M531558, Jiangxi Postdoctoral Research Project under Grant No. 2013KY33, the Natural Science Foundation of Jiangxi Province under Grant No. 20142BAB217001, the Foundation for Young Scientists of Jiangxi Province (Jinggang Star) under Grant No. 20122BCB23002, the Research Foundation of the Education Department of Jiangxi Province under Grant Nos. GJJ13051, GJJ13057, and the Graduate Innovation Special Fund of Nanchang University under Grant No. cx2015137

  6. Atomic-Scale Modeling of Particle Size Effects for the Oxygen Reduction Reaction of Pt

    DEFF Research Database (Denmark)

    Tritsaris, Georgios; Greeley, Jeffrey Philip; Rossmeisl, Jan;

    2011-01-01

    both the specific and mass activities for particle sizes in the range between 2 and 30 nm. The mass activity is calculated to be maximized for particles of a diameter between 2 and 4 nm. Our study demonstrates how an atomic-scale description of the surface microstructure is a key component in...... understanding particle size effects on the activity of catalytic nanoparticles.......We estimate the activity of the oxygen reduction reaction on platinum nanoparticles of sizes of practical importance. The proposed model explicitly accounts for surface irregularities and their effect on the activity of neighboring sites. The model reproduces the experimentally observed trends in...

  7. Mechanistic Details of Surface Reactions in Atomic Layer Deposition (ALD) Processes

    Institute of Scientific and Technical Information of China (English)

    Menno; Bouman; Christopher; Clark; Hugo; Tiznado; Francisco; Zaera

    2007-01-01

    1 Results The reaction mechanisms of the atomic layer deposition (ALD) processes used for thin-film growth have been characterized by a combination of surface sensitive techniques. Our early studies focused on the deposition of TiN films from TiCl4 and ammonia,starting with the independent characterization of each of the two half steps comprising the ALD process. It was found that exposure of the substrate to TiCl4 leads to the initial deposition of titanium in the +3 oxidation state; only at a later st...

  8. Demystifying Introductory Chemistry. Part 4: An Approach to Reaction Thermodynamics through Enthalpies, Entropies, and Free Energies of Atomization.

    Science.gov (United States)

    Spencer, James N.; And Others

    1996-01-01

    Presents an alternative approach to teaching reaction thermodynamics in introductory chemistry courses using calculations of enthalpies, entropies, and free energies of atomization. Uses a consistent concept, that of decomposition of a compound to its gaseous atoms, to discuss not only thermodynamic parameters but also equilibrium and…

  9. Proton-Conducting Sulfonated Ionomers by Chemical Modification and Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Nielsen, Mads Møller

    The cornerstone in this dissertation is made up by three individual assessments of the diversity in the macromolecular landscape that can be obtained by applying relatively few efficient chemical tools. The intention is to gain deeper knowledge on the chemical tuning of proton exchange membranes...... of hydrocarbon macromolecular architectures, PSU with postsulfonated polystyrene (PS) grafts are investigated. Here, IEC is controlled through the degree of substitution, the graft length and DS. The grafting is performed with atom transfer radical polymerization (ATRP). The third assessment is dedicated...

  10. Reverse atom transfer radical polymerization of styrene in emulsion initiated by AIBN or V50

    Institute of Scientific and Technical Information of China (English)

    ZHANG Kai; ZHANG Hongwen; LI Hongtu; WANG Jingyuan

    2005-01-01

    Reverse atom transfer radical polymerization of styrene was conducted in emulsion by using Cu(II)/2,2′- bipydine or Cu(II)/phen complexes, AIBN or V50 as the initiator, Brij-98 or OP-10 as the surfactant. The results of GPC showed that both polymerization processes exhibit living characters when using AIBN as the initiator. However, when V50 was used, the monomer conversion was fairly low and the whole polymerization was not controlled well. The measurement of particle size and its distribution told us that the latex particles were mean and stable when using Brij-98 as the surfactant.

  11. Synthesis and characterization of carbon fibers functionalized with poly (glycidyl methacrylate) via atom transfer radical polymerization

    Science.gov (United States)

    Wu, Yongwei; Xiong, Lei; Qin, Xiaokang; Wang, Zhengyue; Ding, Bei; Ren, Huan; Pi, Xiaolong

    2015-07-01

    In this work, polyacrylonitrile (PAN)-based carbon fibers (CF) were chemically modified with poly (glycidyl methacrylate) (PGMA) via atom transfer radical polymerization (ATRP) to improve the interaction between the CF and polymer matrix. The FT-IR, TGA, and XPS were used to determine the chemical structure of the resulting products and the quantities of PGMA chains grafted from the CF surface. The experimental results confirm that the CF surface was functionalized and glycidyl methacrylate was graft-polymerized onto the CF, and the grafting content of polymer could reach 10.2%.

  12. Optimization of transfer of laser-cooled atom cloud to a quadrupole magnetic

    Indian Academy of Sciences (India)

    S P Ram; S K Tiwari; S R Mishra; H S Rawat

    2014-02-01

    We present here our experimental results on transfer of laser-cooled atom cloud to a quadrupole magnetic trap. We show that by choosing appropriately the ratio of potential energy in magnetic trap to kinetic energy of cloud in molasses, we can obtain the maximum phase-space density in the magnetic trap. These results guide us to choose the value of current to be switched in the quadrupole coils used for magnetic trapping for a given temperature of the cloud after molasses. This study is also useful to set the initial phase-space density of the cloud before evaporative cooling.

  13. Protein repellent hydrophilic grafts prepared by surface-initiated atom transfer radical polymerization from polypropylene

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Eskimergen, Rüya;

    2012-01-01

    Grafting of poly(ethylene glycol)methacrylate (PEGMA) and N,N-dimethylacrylamide (DMAAm) from UV-initiator modified polypropylene (PP) was performed by Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP). The modification and hydrophilization of the PP substrates were confirmed...... with Attenuated Total Reflectance (ATR) Fourier Transform Infrared (FTIR) spectroscopy and Water Contact Angle (WCA) measurements. Confocal fluorescence microscopy of modified and unmodified substrates immersed in labelled insulin aspart showed superior repulsion of this protein for the poly(PEGMA) grafts, due...

  14. Rate of reaction of the hydrogen atom with nitrous oxide in ambient water

    Science.gov (United States)

    Kazmierczak, Lukasz; Swiatla-Wojcik, Dorota; Szala-Bilnik, Joanna; Wolszczak, Marian

    2016-08-01

    The reaction of the hydrogen atom with nitrous oxide has been investigated by pulse radiolysis of N2O-saturated 0.1 M HCl solution at room temperature (24±1 °C). The value of (9±2)×104 M-1 s-1 obtained for the reaction rate constant is between the early estimates 1×104 M-1 s-1 by Czapski and Jortner (1960) and 4.3×105 M-1 s-1 by Thomas (1969), and is much lower than 2×106 M-1 s-1 used recently (Janik et al., 2007; Ismail et al., 2013; Liu et al., 2015; Meesungnoen et al., 2015).

  15. Importance of neutron transfer channels in sub-barrier fusion reaction mechanism

    International Nuclear Information System (INIS)

    Heavy ion fusion reaction has been extensively studied for the last two decades. Fusion cross-sections show large enhancement with respect to theoretical prediction in sub-barrier energy region. It is well known that the enhancement occurs due to nuclear vibration, deformation and nucleon transfer. The influence of nuclear vibration and deformation is well described within the framework of coupled channel (CC) calculations. However, the role of neutron transfer is not yet explained. Experimental investigations have shown that large enhancement in fusion cross-sections is due to neutron transfer channels with positive Q value. But, few systems did not show any enhancement in spite of having positive Q value neutron transfer channels. Hence, Q value is not the only criteria to infer the importance of neutron transfer on fusion. In a recent article, it was stated that enhancement is related to the increase in deformation of interacting nuclei after neutron transfer. In other words, fusion will be weakly influenced by positive Q value neutron transfer channel if deformation of nuclei do not change or decrease after transfer. Moreover, it was recently reported that only valence neutrons i.e. 1n and 2n transfer channel with positive Q value has significant impact on sub-barrier fusion

  16. A NOVEL PHOTO-INITIATING SYSTEM FOR ATOM TRANSFER RADICAL POLYMERIZATION OF STYRENE

    Institute of Scientific and Technical Information of China (English)

    Shu-hui Qin; Dong-qi Qin; Kun-yuan Qiu

    2001-01-01

    A novel photo-induced initiating system, 2,2-dimethoxy-2-phenylacetophenone (DMPA)/ferric tri(N,N-diethyldithiocarbamate) [Fe(DC)3], was developed and used for the atom transfer radical polymerization (ATRP) of styrene in toluene. The polymerization proceeds with DMPA as photo-initiator, Fe(DC)3 as catalyst and DC as a reversible transfer group, while the halogen and ligands are free. Well-defined PSt was prepared and the polymerization mechanism revealed by end group analysis belongs to a reverse ATRP. Block copolymer was prepared by using thus obtained PSt as macroinitiator and Fe(DC)2 as catalyst under UV light irradiation via a conventional ATRP process.``

  17. Correlation of Hydrogen-Atom Abstraction Reaction Efficiencies for Aryl Radicals with their Vertical Electron Affinities and the Vertical Ionization Energies of the Hydrogen Atom Donors

    OpenAIRE

    Jing, Linhong; Nash, John J.; Kenttämaa, Hilkka I.

    2008-01-01

    The factors that control the reactivities of aryl radicals toward hydrogen-atom donors were studied by using a dual-cell Fourier-transform ion cyclotron resonance mass spectrometer (FT – ICR). Hydrogen-atom abstraction reaction efficiencies for two substrates, cyclohexane and isopropanol, were measured for twenty-three structurally different, positively-charged aryl radicals, which included dehydrobenzenes, dehydronaphthalenes, dehydropyridines, and dehydro(iso)quinolines. A logarithmic corre...

  18. Theoretical study of the reaction kinetics of atomic bromine with tetrahydropyran

    KAUST Repository

    Giri, Binod

    2015-02-12

    A detailed theoretical analysis of the reaction of atomic bromine with tetrahydropyran (THP, C5H10O) was performed using several ab initio methods and statistical rate theory calculations. Initial geometries of all species involved in the potential energy surface of the title reaction were obtained at the B3LYP/cc-pVTZ level of theory. These molecular geometries were reoptimized using three different meta-generalized gradient approximation (meta-GGA) functionals. Single-point energies of the stationary points were obtained by employing the coupled-cluster with single and double excitations (CCSD) and fourth-order Møller-Plesset (MP4 SDQ) levels of theory. The computed CCSD and MP4(SDQ) energies for optimized structures at various DFT functionals were found to be consistent within 2 kJ mol-1. For a more accurate energetic description, single-point calculations at the CCSD(T)/CBS level of theory were performed for the minimum structures and transition states optimized at the B3LYP/cc-pVTZ level of theory. Similar to other ether + Br reactions, it was found that the tetrahydropyran + Br reaction proceeds in an overall endothermic addition-elimination mechanism via a number of intermediates. However, the reactivity of various ethers with atomic bromine was found to vary substantially. In contrast with the 1,4-dioxane + Br reaction, the chair form of the addition complex (c-C5H10O-Br) for THP + Br does not need to undergo ring inversion to form a boat conformer (b-C4H8O2-Br) before the intramolecular H-shift can occur to eventually release HBr. Instead, a direct, yet more favorable route was mapped out on the potential energy surface of the THP + Br reaction. The rate coefficients for all relevant steps involved in the reaction mechanism were computed using the energetics of coupled cluster calculations. On the basis of the results of the CCSD(T)/CBS//B3LYP/cc-pVTZ level of theory, the calculated overall rate coefficients can be expressed as kov.,calc.(T) = 4.60 × 10

  19. Atoms

    Institute of Scientific and Technical Information of China (English)

    刘洪毓

    2007-01-01

    Atoms(原子)are all around us.They are something like the bricks (砖块)of which everything is made. The size of an atom is very,very small.In just one grain of salt are held millions of atoms. Atoms are very important.The way one object acts depends on what

  20. Nucleus-nucleus potential, energy dissipation and mass dispersion in fusion and transfer reactions

    CERN Document Server

    Washiyama, Kouhei; Ayik, Sakir

    2009-01-01

    The nucleus-nucleus potential and energy dissipation in fusion reactions are obtained from microscopic mean-field dynamics. The deduced potentials nicely reproduce the one extracted from experimental data. Energy dissipation shows a universal behaviour between different reactions. Also, the dispersion of mass distribution in transfer reaction is investigated in a stochastic mean-field dynamics. By including initial fluctuations in collective space, the description of the dispersion is much improved compared to that of mean field only. The result is consistent with the macroscopic phenomenological analysis of the experimental data.

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

    KAUST Repository

    He, Lipeng

    2012-03-01

    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.

  2. Kinetic and mechanistic study of the atmospheric reaction of MBO331 with Cl atoms

    Science.gov (United States)

    Rodríguez, Diana; Rodríguez, Ana; Garzón, Andrés; Granadino-Roldán, José M.; Soto, Amparo; Aranda, Alfonso; Notario, Alberto

    2012-12-01

    The present work deals with the reaction of 3-methyl-3-buten-1-ol (MBO331) with Cl atoms, which has been investigated by gas chromatography with flame ionization detection (GC-FID) at atmospheric pressure in N2 or air, using the relative rate technique. The rate constant reaction at 298 ± 1 K was found to be (5.01 ± 0.70) × 10-10 cm3 molecule-1 s-1, using cyclohexane, octane and 1-butene as a reference compounds. The temperature dependence for the reaction was studied within the 298-333 K range. Additionally, a product identification under atmospheric conditions has been performed for the first time by GC-MS, with 3-methyl-3-butenal, methacrolein and chloroacetone being observed as degradation products. A theoretical study on the reaction at the QCISD(T)/6-311G**//MP2/6-311G** level was also carried out to obtain more information on the mechanism. From the theoretical study it can be predicted that Cl addition to the double bond proceeds through lower energy barriers than H-abstraction pathways and therefore is energetically favoured. Finally, atmospheric implications of the results obtained are discussed.

  3. Phthalimides as exceptionally efficient single electron transfer acceptors in reductive coupling reactions promoted by samarium diiodide.

    Science.gov (United States)

    Vacas, Tatiana; Alvarez, Eleuterio; Chiara, Jose Luis

    2007-12-20

    Experimental and theoretical evidence shows that phthalimides are highly efficient single electron transfer acceptors in reactions promoted by samarium diiodide, affording ketyl radical anion intermediates, which participate in high-yielding inter- and intramolecular reductive coupling processes with different radicophiles including imides, oxime ethers, nitrones, and Michael acceptors.

  4. Near-Barrier Neutron Transfer in Reactions 3,6He+197Au

    Science.gov (United States)

    Samarin, V. V.; Naumenko, M. A.; Penionzhkevich, Yu. E.; Skobelev, N. K.; Kroha, V.; Mrazek, J.

    2015-06-01

    Experimental excitation functions for near-barrier neutron transfer in 3,6He+197Au reactions have been measured and analyzed. Time-dependent Schrödinger equation and coupled channel equations for external neutrons of 3,6He and 197Au nuclei have been solved numerically taking into account spin-orbit interaction and Pauli exclusion principle.

  5. Atomic-Scale Observations of Catalyst Structures under Reaction Conditions and during Catalysis.

    Science.gov (United States)

    Tao, Franklin Feng; Crozier, Peter A

    2016-03-23

    Heterogeneous catalysis is a chemical process performed at a solid-gas or solid-liquid interface. Direct participation of catalyst atoms in this chemical process determines the significance of the surface structure of a catalyst in a fundamental understanding of such a chemical process at a molecular level. High-pressure scanning tunneling microscopy (HP-STM) and environmental transmission electron microscopy (ETEM) have been used to observe catalyst structure in the last few decades. In this review, instrumentation for the two in situ/operando techniques and scientific findings on catalyst structures under reaction conditions and during catalysis are discussed with the following objectives: (1) to present the fundamental aspects of in situ/operando studies of catalysts; (2) to interpret the observed restructurings of catalyst and evolution of catalyst structures; (3) to explore how HP-STM and ETEM can be synergistically used to reveal structural details under reaction conditions and during catalysis; and (4) to discuss the future challenges and prospects of atomic-scale observation of catalysts in understanding of heterogeneous catalysis. This Review focuses on the development of HP-STM and ETEM, the in situ/operando characterizations of catalyst structures with them, and the integration of the two structural analytical techniques for fundamentally understanding catalysis.

  6. Promotion of multi-electron transfer for enhanced photocatalysis: A review focused on oxygen reduction reaction

    Science.gov (United States)

    Wang, Changhua; Zhang, Xintong; Liu, Yichun

    2015-12-01

    Semiconductor photocatalysis has attracted significant interest for solar light induced environmental remediation and solar fuel generation. As is well known, photocatalytic performance is determined by three steps: photoexcitation, separation and transport of photogenerated charge carriers, and surface reactions. To achieve higher efficiency, significant efforts have been made on improvement of efficiency of above first two steps, which have been well documented in recent review articles. In contrast, this review intends to focus on strategies moving onto the third step of improvement for enhanced photocatalysis wherein active oxygen species including superoxide radical, hydrogen peroxide, hydroxyl radical are in situ detected. Particularly, surface electron-transfer reduction of oxygen over single component photocatalysts is reviewed and systems enabling multi-electron transfer induced oxygen reduction reaction (ORR) are highlighted. It is expected this review could provide a guideline for readers to better understand the critical role of ORR over photocatalyst in charge carrier separation and transfer and obtain reliable results for enhanced aerobic photocatalysis.

  7. Two-neutron transfer analysis of the 16O(18O,16O)18O reaction

    Science.gov (United States)

    Ermamatov, M. J.; Cappuzzello, F.; Lubian, J.; Cubero, M.; Agodi, C.; Carbone, D.; Cavallaro, M.; Ferreira, J. L.; Foti, A.; Garcia, V. N.; Gargano, A.; Lay, J. A.; Lenzi, S. M.; Linares, R.; Santagati, G.; Vitturi, A.

    2016-08-01

    Recently a quantitative description of the two-neutron transfer reaction 12C(18O,16O)14C was performed and the measured cross sections were successfully reproduced [M. Cavallaro et al., Phys. Rev. C 88, 054601 (2013), 10.1103/PhysRevC.88.054601]. This task was accomplished by combining nuclear structure calculations of spectroscopic amplitudes and a full quantum description of the reaction mechanism. Verification of such a theoretical approach to other heavy nuclear systems is mandatory in order to use (18O,16O ) reactions to assess pair configurations in nuclear states. In this work we apply this methodology to the 16O(18O,16O)18O reaction at 84 MeV. Experimental angular distributions for the two-neutron transfer to the ground state and 21+ state of 18O were obtained using the MAGNEX spectrometer at INFN-LNS. The roles of one- and two-step processes are analyzed under the exact finite range coupled reaction channel and the second order distorted wave Born approximation. We conclude that the one-step transfer mechanism is dominant in this system.

  8. Quantum Chemical Evaluation of the Astrochemical Significance of Reactions between S Atom and Acetylene or Ethylene

    Science.gov (United States)

    Woon, David E.

    2007-01-01

    Addition-elimination reactions of S atom in its P-3 ground state with acetylene (C2H2) and ethylene (C2H4) were characterized with both molecular orbital and density functional theory calculations employing correlation consistent basis sets in order to assess the likelihood either reaction might play a general role in astrochemistry or a specific role in the formation of S2 (X (sup 3 SIGMA (sub g) (sup -)) via a mechanism proposed by Saxena and Misra (Mon. Not. R. Astron. Soc. 1995, 272, 89). The acetylene and ethylene reactions proceed through C2H2S ((sup 3)A")) and C2H4S ((sup 3)A")) intermediates, respectively, to yield HCCS ((sup 2)II)) and C2H3S ((sup 2)A')). Substantial barriers were found in the exit channels for every combination of method and basis set considered in this work, which effectively precludes hydrogen elimination pathways for both S + C2H2 and S + C2H4 in the ultracold interstellar medium where only very modest barriers can be surmounted and processes without barriers tend to predominate. However, if one or both intermediates is formed and stabilized efficiently under cometary or dense interstellar cloud conditions, they could serve as temporary reservoirs for S atom and participate in reactions such as S + C2H2S (right arrow) S2 = C2H2 or S + C2H4S (right arrow) S2 + C2H4. For formation and stabilization to be efficient, the reaction must possess a barrier height small enough to be surmountable at low temperatures yet large enough to prevent redissociation to reactants. Barrier heights computed with B3LYP and large basis sets are very low, but more rigorous QCISD(T) and RCCSD(T) results indicate that the barrier heights are closer to 3-4 kcal/mol. The calculations therefore indicate that S + C2H2 or S + C2H4 could contribute to the formation of S2 in comets and may serve as a means to gauge coma temperature. The energetics of the ethylene reaction are more favorable.

  9. Electron-transfer reactions of fast Xe/sup n/+ ions with Xe in the energy range 15 keV to 1.6 MeV

    International Nuclear Information System (INIS)

    Electron-transfer cross sections for the reactions of Xe/sup n/+ (n = 1--4) with Xe atoms have been determined as a function of projectile-ion kinetic energy in the range 15 keV--1.6 MeV. For Xe/sup n/+ (n = 2, 3, 4), cross sections for sequential transfer of two or more electrons in single-ion--atom collisions have been obtained. These cross sections decrease with increasing number of electrons transferred. The observed insensitivity of cross sections to projectile kinetic energy in the range investigated follows the condition that the linear velocity of the ion is less than the orbital velocity of a valence electron in the slow-moving target atom. Attenuation cross sections for reactions of Xe/sup n/+ (n = 2, 3, 4) follow approximately a Z2/sub direct-sum/ charge dependence. A simple classical model based on Coulomb forces yields cross sections with a reasonable fit to the experimental data

  10. Functionalized polymer film surfaces via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    The ability to manipulate and control the surface properties of polymer films, without altering the substrate properties, is crucial to their wide-spread applications. In this work, a simple one-step method for the direct immobilization of benzyl chloride groups (as the effective atom transfer radical polymerization (ATRP) initiators) on the polymer films was developed via benzophenone-induced coupling of 4-vinylbenzyl chloride (VBC). Polyethylene (PE) and nylon films were selected as examples of polymer films to illustrate the functionalization of film surfaces via surface-initiated ATRP. Functional polymer brushes of (2-dimethylamino)ethyl methacrylate, sodium 4-styrenesulfonate, 2-hydroxyethyl methacrylate and glycidyl methacrylate, as well as their block copolymer brushes, have been prepared via surface-initiated ATRP from the VBC-coupled PE or nylon film surfaces. With the development of a simple approach to the covalent immobilization of ATRP initiators on polymer film surfaces and the inherent versatility of surface-initiated ATRP, the surface functionality of polymer films can be precisely tailored. - Highlights: ► Atom transfer radical polymerization initiators were simply immobilized. ► Different functional polymer brushes were readily prepared. ► Their block copolymer brushes were also readily prepared

  11. Hydrophilization of poly(ether ether ketone) films by surface-initiated atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Hvilsted, Søren

    2010-01-01

    Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) has been exploited to hydrophilize PEEK. The ketone groups on the PEEK surface were reduced to hydroxyl groups which were converted to bromoisobutyrate initiating sites for SI-ATRP. The modification steps were followed by contact an...... in the surface topography. Two possible applications arose from the hydrophilization of PEEK, metal deposition and protein repellency. The performed modification allowed for successful electroless deposition and good adhesion of nickel as well as copper.......Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) has been exploited to hydrophilize PEEK. The ketone groups on the PEEK surface were reduced to hydroxyl groups which were converted to bromoisobutyrate initiating sites for SI-ATRP. The modification steps were followed by contact...... angle measurements and XPS. Moreover, ATR FTIR has been used to confirm the formation of initiating groups. Grafting of PEGMA from PEEK was performed in aqueous solution. The presence of the PPEGMA grafts on PEEK was revealed by the thermograms from TGA whereas investigations with AFM rejected changes...

  12. Kinetics and mechanism of the gas-phase reaction of Cl atoms and OH radicals with fluorobenzene at 296 K

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Nielsen, Ole John; Hurley, MD;

    2002-01-01

    radical and adduct formation to give the C6H5F-Cl adduct. At 296 K the rate constant for the abstraction channel is k(5a)(Cl+C6H5F) = (1.1 +/- 0.1) x 10(-17) cm(3) molecule(-1) s(-1). The C6H5F-Cl adduct undergoes rapid (k similar to 10(8) s(-1)) decomposition to reform C6H5F and Cl atoms and reaction......Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms and OH radicals with fluorobenzene, C6H5F, in 700 Torr of N-2 or air diluent at 296 K. Reaction of Cl atoms with C6H5F proceeds via two pathways: H-atom abstraction to give HCl and the C6H4F...... with Cl atoms via a mechanism which, at least in part, leads neither to production of C6H5Cl nor to reformation of C6H5F. As the steady-state Cl atom concentration is increased, the fraction of the C6H5F-Cl adduct undergoing reaction with Cl atoms increases causing an increase in the effective rate...

  13. Characterizing Active Site Conformational Heterogeneity along the Trajectory of an Enzymatic Phosphoryl Transfer Reaction.

    Science.gov (United States)

    Zeymer, Cathleen; Werbeck, Nicolas D; Zimmermann, Sabine; Reinstein, Jochen; Hansen, D Flemming

    2016-09-12

    States along the phosphoryl transfer reaction catalyzed by the nucleoside monophosphate kinase UmpK were captured and changes in the conformational heterogeneity of conserved active site arginine side-chains were quantified by NMR spin-relaxation methods. In addition to apo and ligand-bound UmpK, a transition state analog (TSA) complex was utilized to evaluate the extent to which active site conformational entropy contributes to the transition state free energy. The catalytically essential arginine side-chain guanidino groups were found to be remarkably rigid in the TSA complex, indicating that the enzyme has evolved to restrict the conformational freedom along its reaction path over the energy landscape, which in turn allows the phosphoryl transfer to occur selectively by avoiding side reactions. PMID:27534930

  14. The improvement of the heat transfer model for sodium-water reaction jet code

    International Nuclear Information System (INIS)

    For confirming the reasonable DBL (Design Base Leak) on steam generator (SG), it is necessary to evaluate phenomena of sodium-water reaction (SWR) in an actual steam generator realistically. The improvement of a heat transfer model on sodium-water reaction (SWR) jet code (LEAP-JET ver.1.40) and application analysis to the water injection tests for confirmation of propriety for the code were performed. On the improvement of the code, the heat transfer model between a inside fluid and a tube wall was introduced instead of the prior model which was heat capacity model including both heat capacity of the tube wall and inside fluid. And it was considered that the fluid of inside the heat exchange tube was able to treat as water or sodium and typical heat transfer equations used in SG design were also introduced in the new heat transfer model. Further additional work was carried out in order to improve the stability of the calculation for long calculation time. The test calculation using the improved code (LEAP-JET ver.1.50) were carried out with conditions of the SWAT-IR·Run-HT-2 test. It was confirmed that the SWR jet behavior on the result and the influence to the result of the heat transfer model were reasonable. And also on the improved code (LEAP-JET ver.1.50), user's manual was revised with additional I/O manual and explanation of the heat transfer model and new variable name. (author)

  15. Definition and determination of the triplet-triplet energy transfer reaction coordinate.

    Science.gov (United States)

    Zapata, Felipe; Marazzi, Marco; Castaño, Obis; Acuña, A Ulises; Frutos, Luis Manuel

    2014-01-21

    A definition of the triplet-triplet energy transfer reaction coordinate within the very weak electronic coupling limit is proposed, and a novel theoretical formalism is developed for its quantitative determination in terms of internal coordinates The present formalism permits (i) the separation of donor and acceptor contributions to the reaction coordinate, (ii) the identification of the intrinsic role of donor and acceptor in the triplet energy transfer process, and (iii) the quantification of the effect of every internal coordinate on the transfer process. This formalism is general and can be applied to classical as well as to nonvertical triplet energy transfer processes. The utility of the novel formalism is demonstrated here by its application to the paradigm of nonvertical triplet-triplet energy transfer involving cis-stilbene as acceptor molecule. In this way the effect of each internal molecular coordinate in promoting the transfer rate, from triplet donors in the low and high-energy limit, could be analyzed in detail. PMID:25669358

  16. Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

    OpenAIRE

    Zong-Cheng Chen; Chia-Ling Chiu; Chih-Feng Huang

    2014-01-01

    In this paper, we propose a simple one-pot methodology for proceeding from atom transfer reaction-induced conventional free radical polymerization (AT-FRP) to atom transfer self-condensing vinyl polymerization (AT-SCVP) through manipulation of the catalyst phase homogeneity (i.e., CuBr/2,2'-bipyridine (CuBr/Bpy)) in a mixture of styrene (St), 4-vinyl benzyl chloride (VBC), and ethyl 2-bromoisobutyrate. Tests of the solubilities of CuBr/Bpy and CuBr2/Bpy under various conditions revealed that ...

  17. Chemical reaction of atomic oxygen with evaporated films of copper, part 4

    Science.gov (United States)

    Fromhold, A. T.; Williams, J. R.

    1990-01-01

    Evaporated copper films were exposed to an atomic oxygen flux of 1.4 x 10(exp 17) atoms/sq cm per sec at temperatures in the range 285 to 375 F (140 to 191 C) for time intervals between 2 and 50 minutes. Rutherford backscattering spectroscopy (RBS) was used to determine the thickness of the oxide layers formed and the ratio of the number of copper to oxygen atoms in the layers. Oxide film thicknesses ranged from 50 to 3000 A (0.005 to 0.3 microns, or equivalently, 5 x 10(exp -9) to 3 x 10(exp -7); it was determined that the primary oxide phase was Cu2O. The growth law was found to be parabolic (L(t) varies as t(exp 1/2)), in which the oxide thickness L(t) increases as the square root of the exposure time t. The analysis of the data is consistent with either of the two parabolic growth laws. (The thin-film parabolic growth law is based on the assumption that the process is diffusion controlled, with the space charge within the growing oxide layer being negligible. The thick-film parabolic growth law is also based on a diffusion controlled process, but space-charge neutrality prevails locally within very thick oxides.) In the absence of a voltage measurement across the growing oxide, a distinction between the two mechanisms cannot be made, nor can growth by the diffusion of neutral atomic oxygen be entirely ruled out. The activation energy for the reaction is on the order of 1.1 eV (1.76 x 10(exp -19) joule, or equivalently, 25.3 kcal/mole).

  18. Coupled sensitizer-catalyst dyads: electron-transfer reactions in a perylene-polyoxometalate conjugate.

    Science.gov (United States)

    Odobel, Fabrice; Séverac, Marjorie; Pellegrin, Yann; Blart, Errol; Fosse, Céline; Cannizzo, Caroline; Mayer, Cédric R; Elliott, Kristopher J; Harriman, Anthony

    2009-01-01

    Ultrafast discharge of a single-electron capacitor: A variety of intramolecular electron-transfer reactions are apparent for polyoxometalates functionalized with covalently attached perylene monoimide chromophores, but these are restricted to single-electron events. (et=electron transfer, cr=charge recombination, csr=charge-shift reaction, PER=perylene, POM=polyoxometalate).A new strategy is introduced that permits covalent attachment of an organic chromophore to a polyoxometalate (POM) cluster. Two examples are reported that differ according to the nature of the anchoring group and the flexibility of the linker. Both POMs are functionalized with perylene monoimide units, which function as photon collectors and form a relatively long-lived charge-transfer state under illumination. They are reduced to a stable pi-radical anion by electrolysis or to a protonated dianion under photolysis in the presence of aqueous triethanolamine. The presence of the POM opens up an intramolecular electron-transfer route by which the charge-transfer state reduces the POM. The rate of this process depends on the molecular conformation and appears to involve through-space interactions. Prior reduction of the POM leads to efficient fluorescence quenching, again due to intramolecular electron transfer. In most cases, it is difficult to resolve the electron-transfer products because of relatively fast reverse charge shift that occurs within a closed conformer. Although the POM can store multiple electrons, it has not proved possible to use these systems as molecular-scale capacitors because of efficient electron transfer from the one-electron-reduced POM to the excited singlet state of the perylene monoimide. PMID:19197929

  19. Quantum yield measurement in the chemical reactions of laser-excited Zn and Rb atoms with molecules

    International Nuclear Information System (INIS)

    Graphical abstract: A new method of determining the rate constants of chemical reactions proceeding with participant of Zn(4p 3P1) and Rb(11P3/2) atoms has been introduced. The method is based on the investigation of the spatial and temporary behavior of the atoms and their interaction with reagent-gas molecules in a carrier gas flow. For the excitation of the atom pulsed monochromatic resonance laser radiation was used. The interaction of electronically excited atoms with reagent-gas molecules causes a decrease in the concentration of atoms owing to chemical and physical quenching processes. Registering the change in the atom concentration at the end of the flow, one can evaluate the rate a constants of the reaction in which of stable chemical compounds forms. These investigations are necessary for the laser isotope separation. - Abstract: In the present paper, we introduce a method for measuring the apparent quantum yield θap and the rate-constant values of the physical kp and chemical kc quenching of electronically excited Zn and Rb atoms by gas molecules. The method is based on measuring the concentration of the atoms at the end of their flow in a mixture with a reagent-gas and a carrier gas, in the region where all quenching and secondary processes are already over. The concentration of the atoms was determined from measured absorbed energy of resonance laser radiation. The rate constants and the cross-sections of the chemical and physical quenching of Zn(3P10) and Rb(11P3/2) atoms with several molecules have been determined. For some collisions the quantum yield was found to be close to unity. The method may find applications in laser photochemical isotope separation and in measuring the rate constants of reactions proceeding with participation of ground state atoms.

  20. Curly arrows meet electron density transfers in chemical reaction mechanisms: from electron localization function (ELF) analysis to valence-shell electron-pair repulsion (VSEPR) inspired interpretation.

    Science.gov (United States)

    Andrés, Juan; Berski, Sławomir; Silvi, Bernard

    2016-07-01

    Probing the electron density transfers during a chemical reaction can provide important insights, making possible to understand and control chemical reactions. This aim has required extensions of the relationships between the traditional chemical concepts and the quantum mechanical ones. The present work examines the detailed chemical insights that have been generated through 100 years of work worldwide on G. N. Lewis's ground breaking paper on The Atom and the Molecule (Lewis, G. N. The Atom and the Molecule, J. Am. Chem. Soc. 1916, 38, 762-785), with a focus on how the determination of reaction mechanisms can be reached applying the bonding evolution theory (BET), emphasizing how curly arrows meet electron density transfers in chemical reaction mechanisms and how the Lewis structure can be recovered. BET that combines the topological analysis of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool providing insight into molecular mechanisms of chemical rearrangements. In agreement with physical laws and quantum theoretical insights, BET can be considered as an appropriate tool to tackle chemical reactivity with a wide range of possible applications. Likewise, the present approach retrieves the classical curly arrows used to describe the rearrangements of chemical bonds for a given reaction mechanism, providing detailed physical grounds for this type of representation. The ideas underlying the valence-shell-electron pair-repulsion (VSEPR) model applied to non-equilibrium geometries provide simple chemical explanations of density transfers. For a given geometry around a central atom, the arrangement of the electronic domain may comply or not with the VSEPR rules according with the valence shell population of the considered atom. A deformation yields arrangements which are either VSEPR defective (at least a domain is missing to match the VSEPR arrangement corresponding to the geometry of the ligands), VSEPR compliant

  1. Curly arrows meet electron density transfers in chemical reaction mechanisms: from electron localization function (ELF) analysis to valence-shell electron-pair repulsion (VSEPR) inspired interpretation.

    Science.gov (United States)

    Andrés, Juan; Berski, Sławomir; Silvi, Bernard

    2016-07-01

    Probing the electron density transfers during a chemical reaction can provide important insights, making possible to understand and control chemical reactions. This aim has required extensions of the relationships between the traditional chemical concepts and the quantum mechanical ones. The present work examines the detailed chemical insights that have been generated through 100 years of work worldwide on G. N. Lewis's ground breaking paper on The Atom and the Molecule (Lewis, G. N. The Atom and the Molecule, J. Am. Chem. Soc. 1916, 38, 762-785), with a focus on how the determination of reaction mechanisms can be reached applying the bonding evolution theory (BET), emphasizing how curly arrows meet electron density transfers in chemical reaction mechanisms and how the Lewis structure can be recovered. BET that combines the topological analysis of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool providing insight into molecular mechanisms of chemical rearrangements. In agreement with physical laws and quantum theoretical insights, BET can be considered as an appropriate tool to tackle chemical reactivity with a wide range of possible applications. Likewise, the present approach retrieves the classical curly arrows used to describe the rearrangements of chemical bonds for a given reaction mechanism, providing detailed physical grounds for this type of representation. The ideas underlying the valence-shell-electron pair-repulsion (VSEPR) model applied to non-equilibrium geometries provide simple chemical explanations of density transfers. For a given geometry around a central atom, the arrangement of the electronic domain may comply or not with the VSEPR rules according with the valence shell population of the considered atom. A deformation yields arrangements which are either VSEPR defective (at least a domain is missing to match the VSEPR arrangement corresponding to the geometry of the ligands), VSEPR compliant

  2. Study of transfer reactions in inverse kinematics with the TIARA array

    International Nuclear Information System (INIS)

    The newly commissioned TIARA array has been coupled for the first time to the VAMOS spectrometer and the EXOGAM germanium array to study nucleon transfer reactions in inverse kinematics and using beams of low intensity, which are typical of radioactive beam experiments. This set-up offers a high geometrical efficiency for the charged particle detection, a high efficiency for γ-ray detection and a final energy resolution only limited by the Doppler broadening. This report demonstrates the potential of such an apparatus to study single-nucleon transfer reactions with radioactive nuclear beams. A beam of 14N at 10.6 MeV/nucleon with an intensity of 105 s-1 was directed onto a CD2 target of 1 mg cm-2. Proton angular distributions have been measured for the population of 15N in the ground state and in excited states at 7.15 and 7.56 MeV. Transferred l-values deduced from comparison to DWBA calculations are in very good agreement with the well-known shell structure of 15N. We have therefore demonstrated the effectiveness of this set-up in studying nucleon transfer reactions in inverse kinematics and with low-intensity beams

  3. Probing the critical residues for intramolecular fructosyl transfer reaction of a levan fructotransferase.

    Science.gov (United States)

    Moon, Keum-Ok; Choi, Kyoung-Hwa; Kang, Ho-Young; Oh, Jeong-Il; Jang, Se Bok; Park, Cheon-Seok; Lee, Jong-Hoon; Cha, Jaeho

    2008-06-01

    Levan fructotransferase (LFTase) preferentially catalyzes the transfructosylation reaction in addition to levan hydrolysis, whereas other levan-degrading enzymes hydrolyze levan into a levan-oligosaccharide and fructose. Based on sequence comparisons and enzymatic properties, the fructosyl transfer activity of LFTase is proposed to have evolved from levanase. In order to probe the residues that are critical to the intramolecular fructosyl transfer reaction of the Microbacterium sp. AL-210 LFTase, an error-prone PCR mutagenesis process was carried out, and the mutants that led to a shift in activity from transfructosylation towards hydrolysis of levan were screened by the DNS method. After two rounds of mutagenesis, TLC and HPLC analyses of the reaction products by the selected mutants revealed two major products; one is a di-D-fructose- 2,6':6,2'-dianhydride (DFAIV) and the other is a levanbiose. The newly detected levanbiose corresponds to the reaction product from LFTase lacking transferring activity. Two mutants (2-F8 and 2-G9) showed a high yield of levanbiose (38-40%) compared with the wild-type enzyme, and thus behaved as levanases. Sequence analysis of the individual mutants responsible for the enhanced hydrolytic activity indicated that Asn-85 was highly involved in the transfructosylation activity of LFTase. PMID:18600048

  4. Probing surface distribution of $\\alpha$-cluster in $^{20}$Ne via $\\alpha$-transfer reaction

    CERN Document Server

    Fukui, Tokuro; Suhara, Tadahiro; Kanada-En'yo, Yoshiko; Ogata, Kazuyuki

    2015-01-01

    Direct evidence of the $\\alpha$-cluster development in bound states has not been obtained yet although a number of experimental studies were carried out to extract the information of the clustering. In particular in conventional analyses of $\\alpha$-transfer reactions, there exist a few significant problems on reaction models, which are insufficient to qualitatively discuss the cluster structure. We aim to verify the development of the $\\alpha$-cluster structure from observables. As the first application, it is argued to extract the spatial information of the cluster structure of the $^{20}$Ne nucleus in its ground state through the cross section of the $\\alpha$-transfer reaction $^{16}$O($^6$Li,~$d$)$^{20}$Ne. For the analysis of the transfer reaction, we work with the coupled-channels Born approximation (CCBA) approach, in which the breakup effect of $^6$Li is explicitly taken into account by means of the continuum-discretized coupled-channels method (CDCC) based on the three-body $\\alpha + d + {}^{16}$O mo...

  5. Studies on electron transfer reactions: Reduction of heteropoly 10-tungstodivanadophosphate by thioglycolic acid in aqueous medium

    Indian Academy of Sciences (India)

    Ponnusamy Sami; Natarajan Mariselvi; Kandasamy Venkateshwari; Arunachalam Sarathi; Kasi Rajasekaran

    2010-05-01

    Rates of electron transfer reaction of thioglycolic acid with vanadium(V) substituted Keggintype heteropolyanion, [PVVVVW10O40]5-, in acetate-acetic acid buffers have been measured spectrophotometrically at 25°C. The order of the reaction with respect to substrate and oxidant is unity. The reaction shows simple second order kinetics at constant pH. The rate of the reaction increases with increase of pH of the medium. The mono-anion HSCH2COO- and di-anion -SCH2COO- are found to be the reactive species. Rate constants for mono-anion and di-anion are evaluated from rate law derived from the mechanism. By applying Rehm-Weller relationship, self exchange rate constant for the -SCH2COO-/S$^{\\bullet}$ CH2COO- couple was evaluated as 3.3 × 103 dm3 mol-1 s-1 at 25°C.

  6. Squids, supercurrents, and slope anomalies: Nuclear structure from heavy-ion transfer reactions

    International Nuclear Information System (INIS)

    Within the past five years we have developed experimental techniques to study heavy-ion transfer reactions to high spin states in deformed nuclei. These methods have been turned into a quantitative tool to assess the influence of collective excitation on single-particle and pairing structure. I discuss some of the nuclear structure questions which are being answered in these experiments: How strong is ground state pairing? How does pairing change with angular momentum? Why is two-neutron transfer much stronger than expected at large radial separation? What is the evidence for a nuclear Josephson Effect? What is the evidence for a nuclear Berry phase effect (nuclear SQUID)? Why does one-neutron transfer populate much higher spins than would be naively expected? Conversely, why does two-neutron transfer populate much lower spins than anyone expected? The answer to each of these questions involves the influence of detailed nuclear structure on transfer reactions, and represents quantitative new information about the effect of angular momentum and excitation energy on many-body systems with a finite number of particles. 8 refs., 6 figs

  7. Minor actinide fission induced by multi-nucleon transfer reaction in inverse kinematics

    Directory of Open Access Journals (Sweden)

    Taieb J.

    2010-03-01

    Full Text Available In the framework of nuclear waste incineration and design of new generation nuclear reactors, experimental data on fission probabilities and on fission fragment yields of minor actinides are crucial to design prototypes. Transfer-induced fission has proven to be an efficient method to study fission probabilities of actinides which cannot be investigated with standard techniques due to their high radioactivity. We report on the preliminary results of an experiment performed at GANIL that investigates fission probabilities with multi-nucleon transfer reactions in inverse kinematics between a 238U beam on a 12C target. Actinides from U to Cm were produced with an excitation energy range from 0 to 30 MeV. In addition, inverse kinematics allowed to characterize the fission fragments in mass and charge. A key point of the analysis resides in the identification of the actinides produced in the different transfer channels. The new annular telescope SPIDER was used to tag the target-like recoil nucleus of the transfer reaction and to determine the excitation energy of the actinide. The fission probability for each transfer channel is accessible and the preliminary results for 238U are promising.

  8. Quantifying electron transfer reactions in biological systems: what interactions play the major role?

    Science.gov (United States)

    Sjulstok, Emil; Olsen, Jógvan Magnus Haugaard; Solov'Yov, Ilia A.

    2015-12-01

    Various biological processes involve the conversion of energy into forms that are usable for chemical transformations and are quantum mechanical in nature. Such processes involve light absorption, excited electronic states formation, excitation energy transfer, electrons and protons tunnelling which for example occur in photosynthesis, cellular respiration, DNA repair, and possibly magnetic field sensing. Quantum biology uses computation to model biological interactions in light of quantum mechanical effects and has primarily developed over the past decade as a result of convergence between quantum physics and biology. In this paper we consider electron transfer in biological processes, from a theoretical view-point; namely in terms of quantum mechanical and semi-classical models. We systematically characterize the interactions between the moving electron and its biological environment to deduce the driving force for the electron transfer reaction and to establish those interactions that play the major role in propelling the electron. The suggested approach is seen as a general recipe to treat electron transfer events in biological systems computationally, and we utilize it to describe specifically the electron transfer reactions in Arabidopsis thaliana cryptochrome-a signaling photoreceptor protein that became attractive recently due to its possible function as a biological magnetoreceptor.

  9. Reactions of substituted benzene anions with N and O atoms: Chemistry in Titan's upper atmosphere and the interstellar medium

    Science.gov (United States)

    Wang, Zhe-Chen; Bierbaum, Veronica M.

    2016-06-01

    The likely existence of aromatic anions in many important extraterrestrial environments, from the atmosphere of Titan to the interstellar medium (ISM), is attracting increasing attention. Nitrogen and oxygen atoms are also widely observed in the ISM and in the ionospheres of planets and moons. In the current work, we extend previous studies to explore the reactivity of prototypical aromatic anions (deprotonated toluene, aniline, and phenol) with N and O atoms both experimentally and computationally. The benzyl and anilinide anions both exhibit slow associative electron detachment (AED) processes with N atom, and moderate reactivity with O atom in which AED dominates but ionic products are also formed. The reactivity of phenoxide is dramatically different; there is no measurable reaction with N atom, and the moderate reactivity with O atom produces almost exclusively ionic products. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions and their relevance to ionospheric and interstellar chemistry.

  10. Heavy-ion transfer reactions at large internuclear distances using the PRISMA magnetic spectrometer

    Directory of Open Access Journals (Sweden)

    Montanari D. J.

    2013-12-01

    Full Text Available We measured excitation functions for the main transfer channels in the 116Sn+60Ni reaction at different bombarding energies from above to well below the Coulomb barrier. The experiment has been performed in inverse kinematics, detecting the lighter (target-like ions with the magnetic spectrometer PRISMA at very forward angles. Good mass, nuclear charge and kinetic energy resolutions have been achieved. The comparison between the data and microscopic calculations for the present case and for the previously measured 96Zr+40Ca system, namely superfluid and near closed shells nuclei, should significantly improve our understanding of nucleon-nucleon correlation properties in multinucleon transfer processes.

  11. Radiation, Chemical reaction, Double dispersion effects on Heat and mass transfer in Non-Newtonian fluids

    Directory of Open Access Journals (Sweden)

    Dr. A.S.N. Murti

    2010-03-01

    Full Text Available Radiation and chemical reaction effects on heat and mass transfer in non-Darcynon-Newtonian fluid over a vertical surface is considered. In this article we havemaintained the constant temperature. A mathematical model is developed takinginto the account the new elements introduced. Numerical solutions for thegoverning nonlinear momemtum, energy and concentration are obtained.Thegoverning boundary layer equations and boundary conditions are simplified byusing similarity transformations. The governing equations are solved numericallyby means of Fourth-order Runge-Kutta method coupled with double-shootingtechnique. The influence of viscosity index n , thermal and solute dispersion,velocity, temperature, concentration, Heat and mass transfer rates arediscussed.

  12. A water-soluble ruthenium glycosylated porphyrin catalyst for carbenoid transfer reactions in aqueous media with applications in bioconjugation reactions.

    Science.gov (United States)

    Ho, Chi-Ming; Zhang, Jun-Long; Zhou, Cong-Ying; Chan, On-Yee; Yan, Jessie Jing; Zhang, Fu-Yi; Huang, Jie-Sheng; Che, Chi-Ming

    2010-02-17

    Water-soluble [Ru(II)(4-Glc-TPP)(CO)] (1, 4-Glc-TPP = meso-tetrakis(4-(beta-D-glucosyl)phenyl)porphyrinato dianion) is an active catalyst for the following carbenoid transfer reactions in aqueous media with good selectivities and up to 100% conversions: intermolecular cyclopropanation of styrenes (up to 76% yield), intramolecular cyclopropanation of an allylic diazoacetate (68% yield), intramolecular ammonium/sulfonium ylide formation/[2,3]-sigmatroptic rearrangement reactions (up to 91% yield), and intermolecular carbenoid insertion into N-H bonds of primary arylamines (up to 83% yield). This ruthenium glycosylated porphyrin complex can selectively catalyze alkylation of the N-terminus of peptides (8 examples) and mediate N-terminal modification of proteins (four examples) using a fluorescent-tethered diazo compound (15). A fluorescent group was conjugated to ubiquitin via 1-catalyzed alkene cyclopropanation with 15 in aqueous solution in two steps: (1) incorporation of an alkenic group by the reaction of N-hydroxysuccinimide ester 19 with ubiquitin and (2) cyclopropanation of the alkene-tethered Lys(6) ubiquitin (23) with the fluorescent-labeled diazoacetate 15 in the presence of a catalytic amount of 1. The corresponding cyclopropanation product (24) was obtained with approximately 55% conversion based on MALDI-TOF mass spectrometry. The products 23, 24, and the N-terminal modified peptides and proteins were characterized by LC-MS/MS and/or SDS-PAGE analyses. PMID:20088517

  13. Proceedings of the 2nd joint seminar on atomic collisions and heavy ion induced nuclear reactions

    International Nuclear Information System (INIS)

    The meeting of the 2nd joint seminar on atomic collisions and heavy ion induced nuclear reactions was held at the University of Tokyo, May 13 and 14, 1982. The aim of this seminar has been not only to recognize the common problems lying between above two research fields, but also to obtain an overview of the theoretical and experimental approaches to clear the current problems. In the seminar, more than 50 participants gathered and presented 16 papers. These are two general reviews and fourteen comprehensive surveys on topical subjects which have been developed very intensively in recent years. The editors would like to thank all participants for their assistance and cooperation in making possible a publication of these proceedings. (author)

  14. Atomic-scale observation of lithiation reaction front in nanoscale SnO 2 materials

    KAUST Repository

    Nie, Anmin

    2013-07-23

    In the present work, taking advantage of aberration-corrected scanning transmission electron microscopy, we show that the dynamic lithiation process of anode materials can be revealed in an unprecedented resolution. Atomically resolved imaging of the lithiation process in SnO2 nanowires illustrated that the movement, reaction, and generation of b = [1Ì...1Ì...1] mixed dislocations leading the lithiated stripes effectively facilitated lithium-ion insertion into the crystalline interior. The geometric phase analysis and density functional theory simulations indicated that lithium ions initial preference to diffuse along the [001] direction in the {200} planes of SnO2 nanowires introduced the lattice expansion and such dislocation behaviors. At the later stages of lithiation, the Li-induced amorphization of rutile SnO2 and the formation of crystalline Sn and LixSn particles in the Li2O matrix were observed. © 2013 American Chemical Society.

  15. 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: sargsyan@theor.jinr.ru; Adamian, G. G.; Antonenko, N. V. [Joint Institute for Nuclear Research (Russian Federation); Scheid, W. [Institüt für Theoretische Physik der Justus-Liebig-Universität (Germany)

    2015-12-15

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

  16. Nucleophilic Substitution Reaction of p-Dinitrobenzene by a Carbanion: Evidence for Electron Transfer Mechanism

    Institute of Scientific and Technical Information of China (English)

    LIU,You-Cheng(刘有成); ZHANG,Kai-Dong(张凯东); L(U),Jian-Ming(吕建明); WU,Long-min(吴隆民); LIU,Zhong-Li(刘中立)

    2002-01-01

    On the basis of investigation of cyclic voltmmnetry, EPR spectroscopy and competition experunebts, the nucleophilic substitution reaction of p-dinitrobenzene with the sodium salt of ethyl α-cyanoacetate carbanion in dimethyl sulfoxide giving ethyl α-cyano- α- (p-nitrophenyl) acetate is shown to take place via the intermediacy of dinitrobenzene radical anion. The reaction rate goes faster than that between p-nitrohalobenzenes and the same sodium salt of ethyl α-cyanoacetate carbanion. There is an evidence for a single electron transfer mechanism.

  17. Preparation and characterization of optical-functional diblock copolymer brushes on hollow sphere surface via atom transfer radical polymerization

    International Nuclear Information System (INIS)

    The optical-functional poly(methyl methacrylate)-block-Tb complex diblock copolymer brushes grafted from hollow sphere surface via atom transfer radical polymerization were investigated in this work. A sufficient amount of azo initiator was introduced onto hollow sphere surface firstly. Then the monomer methyl methacrylate was polymerized via surface-initiated reverse atom transfer radical polymerization using azo group modified hollow sphere as initiator. Following, the poly(methyl methacrylate) modified hollow sphere was used as maroinitiator for surface-initiated atom transfer radical polymerization of Tb complex. The samples were characterized by Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance, gel permeation chromatographer and transmission electron microscopy, respectively. The results indicated that the poly(methyl methacrylate) had grafted from hollow sphere surface and the average diameter of hollow core was about 1 μm. The optical properties of the poly(methyl methacrylate)-block-Tb copolymer modified hollow sphere were also reported.

  18. Radiative charge transfer in cold and ultracold Sulfur atoms colliding with Protons

    CERN Document Server

    Shen, G; Wang, J G; McCann, J F; McLaughlin, B M

    2015-01-01

    Radiative decay processes at cold and ultra cold temperatures for Sulfur atoms colliding with protons are investigated. The MOLPRO quantum chemistry suite of codes was used to obtain accurate potential energies and transition dipole moments, as a function of internuclear distance, between low-lying states of the SH$^{+}$ molecular cation. A multi-reference configuration-interaction (MRCI) approximation together with the Davidson correction is used to determine the potential energy curves and transition dipole moments, between the states of interest, where the molecular orbitals (MO's) are obtained from state-averaged multi configuration-self-consistent field (MCSCF) calculations. The collision problem is solved approximately using an optical potential method to obtain radiative loss, and a fully two-channel quantum approach for radiative charge transfer. Cross sections and rate coefficients are determined for the first time for temperatures ranging from 10 $\\mu$ K up to 10,000 K. Results are obtained for all ...

  19. Robust entanglement between a movable mirror and atomic ensemble and entanglement transfer in coupled optomechanical system.

    Science.gov (United States)

    Bai, Cheng-Hua; Wang, Dong-Yang; Wang, Hong-Fu; Zhu, Ai-Dong; Zhang, Shou

    2016-01-01

    We propose a scheme for the creation of robust entanglement between a movable mirror and atomic ensemble at the macroscopic level in coupled optomechanical system. We numerically simulate the degree of entanglement of the bipartite macroscopic entanglement and show that it depends on the coupling strength between the cavities and is robust with respect to the certain environment temperature. Inspiringly and surprisingly, according to the reported relation between the mechanical damping rate and the mechanical frequency of the movable mirror, the numerical simulation result shows that such bipartite macroscopic entanglement persists for environment temperature up to 170 K, which breaks the liquid nitrogen cooling and liquid helium cooling and largely lowers down the experiment cost. We also investigate the entanglement transfer based on this coupled system. The scheme can be used for the realization of quantum memories for continuous variable quantum information processing and quantum-limited displacement measurements. PMID:27624534

  20. Modification of Jute Fibers with Polystyrene via Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Plackett, David; Jankova, Katja Atanassova; Egsgaard, Helge;

    2005-01-01

    Atom transfer radical polymerization (ATRP) was investigated as a method of covalently bonding polystyrene to jute (Corchorus capsularis) and as a possible approach to fiber composites with enhanced properties. Jute fibers were modified with a brominated initiator and subsequently ATRP modified...... to attach polystyrene and then examined using SEM, DSC, TGA, FTIR, XPS, elemental analysis, and Py-GC-MS. These techniques confirmed that polystyrene had been covalently bound to the fibers and consequently ATRP-modified jute fiber mats were used to prepare hot-pressed polystyrene composites. Composite...... applications, we conclude that further optimization of the ATRP method is required, possibly targeting higher and more uniform loading of polystyrene on the fibers....

  1. Distinguishing nonlinear processes in atomic media via orbital angular momentum transfer

    CERN Document Server

    Akulshin, Alexander M; Mikhailov, Eugeniy E; Novikova, Irina

    2014-01-01

    We suggest a technique based on the transfer of topological charge from applied laser radiation to directional and coherent optical fields generated in ladder-type excited atomic media to identify the major processes responsible for their appearance. As an illustration, in Rb vapours we analyse transverse intensity and phase profiles of the forward-directed collimated blue and near-IR light using self-interference and astigmatic transformation techniques when either or both of two resonant laser beams carry orbital angular momentum. Our observations unambiguously demonstrate that emission at 1.37 {\\mu}m is the result of a parametric four-wave mixing process involving only one of the two applied laser fields.

  2. Robust entanglement between a movable mirror and atomic ensemble and entanglement transfer in coupled optomechanical system

    Science.gov (United States)

    Bai, Cheng-Hua; Wang, Dong-Yang; Wang, Hong-Fu; Zhu, Ai-Dong; Zhang, Shou

    2016-09-01

    We propose a scheme for the creation of robust entanglement between a movable mirror and atomic ensemble at the macroscopic level in coupled optomechanical system. We numerically simulate the degree of entanglement of the bipartite macroscopic entanglement and show that it depends on the coupling strength between the cavities and is robust with respect to the certain environment temperature. Inspiringly and surprisingly, according to the reported relation between the mechanical damping rate and the mechanical frequency of the movable mirror, the numerical simulation result shows that such bipartite macroscopic entanglement persists for environment temperature up to 170 K, which breaks the liquid nitrogen cooling and liquid helium cooling and largely lowers down the experiment cost. We also investigate the entanglement transfer based on this coupled system. The scheme can be used for the realization of quantum memories for continuous variable quantum information processing and quantum-limited displacement measurements.

  3. Synthesis of End Functional Polymers via Atom Transfer Radical Polymerization in Immobilized Catalytic System

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Cross-linked polystyrene with azo-crown ether functional side chain (PSt-1, 10-dicarbonyl-3,6,9-trizaocylcodecane) was prepared under microwave irradiation and the structure was characterized through FT-IR and element analysis. The functionalized cross-linked polystyrene (cross-link degree, 3.5%) combining with immobilized catalyst system (CuBr and ethyl α-bromo-isobutyrate) can catalyze atom transfer radical polymerization of Styrene. Neat polymer products can be obtained then. Complex of La and the polymer end group (EBiB) was synthesized. The third order nonlinear optical property of the polymer-La complex was investigated and the structure was also characterized by FT-IR and XPS.

  4. Charge transfer in the interactions of partially stripped ions with atoms at intermediate and high energies

    International Nuclear Information System (INIS)

    The Coulomb-Born (CB) approximation has been employed to study charge transfer cross sections in collisions of Cq+, Nq+ and Oq+ (q = 1-5) with atomic hydrogen in ground state in the energy range of 30-200 keV/amu. The interaction of the active electron with the incoming projectile ion has been approximated by a model potential containing both a long-range part and a short-range part. Variations of total capture cross sections with impact energy compare favourable well with the available experimental observations and with other theoretical findings. In addition, sub-shell distributions of total capture cross sections are given in graphical form. However, we are unable to find any oscillation in the charge-state dependence of total capture cross sections. (author)

  5. Preparation of polystyrene-grafted titanate nanotubes by in situ atom transfer radical polymerization

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    This work successfully prepared nanohybrids by in situ atom transfer radical polymerization (ATRP) of styrene from titanate nanotubes (TNTs). Fourier-transform infrared (FT-IR), pronton nuclear magnetic resonance spectroscopy (1H NMR), and thermal gravimetric analysis (TGA) were used to verify the successful graft of polystyrene (PS) chains from TNTs. Transmission electron microscopy (TEM) dis-played that the obtained PS-g-TNTs nanohybrids had a core-shell structure of TNT core and PS shell. The grafted PS content was well controlled and increased with increasing of the monomer/initiator ratio. Further copolymerization of tert-butyl acrylate (tBA) from the surface of PS-g-TNTs was studied, illus-trating the "living" characteristics of the surface-induced ATRP method used in this work.

  6. Robust entanglement between a movable mirror and atomic ensemble and entanglement transfer in coupled optomechanical system.

    Science.gov (United States)

    Bai, Cheng-Hua; Wang, Dong-Yang; Wang, Hong-Fu; Zhu, Ai-Dong; Zhang, Shou

    2016-09-14

    We propose a scheme for the creation of robust entanglement between a movable mirror and atomic ensemble at the macroscopic level in coupled optomechanical system. We numerically simulate the degree of entanglement of the bipartite macroscopic entanglement and show that it depends on the coupling strength between the cavities and is robust with respect to the certain environment temperature. Inspiringly and surprisingly, according to the reported relation between the mechanical damping rate and the mechanical frequency of the movable mirror, the numerical simulation result shows that such bipartite macroscopic entanglement persists for environment temperature up to 170 K, which breaks the liquid nitrogen cooling and liquid helium cooling and largely lowers down the experiment cost. We also investigate the entanglement transfer based on this coupled system. The scheme can be used for the realization of quantum memories for continuous variable quantum information processing and quantum-limited displacement measurements.

  7. Prospects for Thermal Atomic Layer Etching Using Sequential, Self-Limiting Fluorination and Ligand-Exchange Reactions.

    Science.gov (United States)

    George, Steven M; Lee, Younghee

    2016-05-24

    Thermal atomic layer etching (ALE) of Al2O3 and HfO2 using sequential, self-limiting fluorination and ligand-exchange reactions was recently demonstrated using HF and tin acetylacetonate (Sn(acac)2) as the reactants. This new thermal pathway for ALE represents the reverse of atomic layer deposition (ALD) and should lead to isotropic etching. Atomic layer deposition and ALE can together define the atomic layer growth and removal steps required for advanced semiconductor fabrication. The thermal ALE of many materials should be possible using fluorination and ligand-exchange reactions. The chemical details of ligand-exchange can lead to selective ALE between various materials. Thermal ALE could produce conformal etching in high-aspect-ratio structures. Thermal ALE could also yield ultrasmooth thin films based on deposit/etch-back methods. Enhancement of ALE rates and possible anisotropic ALE could be achieved using radicals or ions together with thermal ALE. PMID:27216115

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

    CERN Document Server

    Derouich, Moncef

    2016-01-01

    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 ...

  9. Learned Cardiac Control with Heart Rate Biofeedback Transfers to Emotional Reactions

    OpenAIRE

    Nathalie Peira; Gilles Pourtois; Mats Fredrikson

    2013-01-01

    Emotions involve subjective feelings, action tendencies and physiological reactions. Earlier findings suggest that biofeedback might provide a way to regulate the physiological components of emotions. The present study investigates if learned heart rate regulation with biofeedback transfers to emotional situations without biofeedback. First, participants learned to decrease heart rate using biofeedback. Then, inter-individual differences in the acquired skill predicted how well they could dec...

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

    KAUST Repository

    Chen, Tao

    2012-08-01

    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.

  11. Hydrophilic modification of microporous polysulfone membrane via surface-initiated atom transfer radical polymerization of acrylamide

    International Nuclear Information System (INIS)

    Polyacrylamide (PAM) brushes were grafted from chloromethylated polysulfone (CMPSF) membrane surface by surface-initiated atom transfer radical polymerization (SI-ATRP) to improve the membrane's hydrophilic property. In order to anchor the initiator onto polysulfone (PSF) membrane surface, CMPSF was used to prepare the microporous membrane by phase-inversion process. Attachment of the PAM chains on membrane surface was confirmed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The grafted density of PAM was calculated to be 0.08 chains nm-2. Field emission scanning electron microscopy (FESEM) and atomic force microscope (AFM) were used to characterize the surface morphology of the CMPSF membrane and modified membrane. The number-average molecular weight (Mn) of PAM linearly increased with the polymerization time, while the static water contact angle (θ) of the membrane grafted with PAM linearly decreased. This indicated the hydrophilic property of the membrane was linearly correlated with the chain length of graft polymer. Therefore linear control of PSF membrane's hydrophilic property was realized through adjusting polymerization time.

  12. Effect of current and atomized grain size distribution on the solidification of Plasma Transferred Arc coatings

    Directory of Open Access Journals (Sweden)

    Danielle Bond

    2012-10-01

    Full Text Available Plasma Transferred Arc (PTA is the only thermal spray process that results in a metallurgical bond, being frequently described as a hardfacing process. The superior properties of coatings have been related to the fine microstructures obtained, which are finer than those processed under similar heat input with welding techniques using wire feedstock. This observation suggests that the atomized feedstock plays a role on the solidification of coatings. In this study a model for the role of the powders grains in the solidification of PTA coatings is put forward and discussed. An experiment was setup to discuss the model which involved the deposition of an atomized Co-based alloy with different grain size distributions and deposition currents. X ray diffraction showed that there were no phase changes due to the processing parameters. Microstructure analysis by Laser Confocal Microscopy, dilution with the substrate steel and Vickers microhardness were used the characterized coatings and enriched the discussion confirming the role of the powdered feedstock on the solidification of coatings.

  13. Reverse atom transfer radical polymerization (RATRP) for anti-clotting PU-LaCl3-g-P(MPC) films

    Science.gov (United States)

    Lu, Chunyan; Zhou, Ninglin; Xiao, Yinghong; Tang, Yida; Jin, Suxing; Wu, Yue; Shen, Jian

    2013-01-01

    Low grafting density is a disadvantage both in reverse atom transfer radical polymerization (RATRP) and ATRP. In this work, the surfaces of polyurethane (PU) were treated by LaCl3·6H2O to obtain modified surfaces with hydrated layers. The reaction of surface-initiated RATRP was carried out easily, which may be attributed to the enriched hydroxyl groups on the hydrated layers. An innovation found in this work is that some free lanthanum ions (La3+) reacted with the silane coupling agent (CPTM) and the product served as mixed ligand complex. The mixed ligand complex instead of conventional 2,2‧-bipyridine was adopted to serve as a ligand in the process of RATRP. As a result, PU surfaces grafted with well-defined polymer brushes (MPC) were obtained. PU substrates before and after modification were characterized by FTIR, XPS, AFM, SEM, SCA, respectively. The results showed that zwitterionic brushes were successfully fabricated on the PU surfaces (P(MPC)), and the content of the grafted layer increased gradually with polymerization time with the grafting density as high as 97.9%. The blood compatibility of the PU substrates was evaluated by plasma recalcification profiles test and platelet adhesion tests in vitro. It was found that all PU functionalized with zwitterionic brush showed improved resistance to nonspecific protein adsorption and platelet adhesion.

  14. Electron transfer reactions, cyanide and O2 binding of truncated hemoglobin from Bacillus subtilis

    DEFF Research Database (Denmark)

    Fernandez, Esther; Larsson, Jonas T.; McLean, Kirsty J.;

    2013-01-01

    The truncated hemoglobin from Bacillus subtilis (trHb-Bs) possesses a surprisingly high affinity for oxygen and resistance to (auto)oxidation; its physiological role in the bacterium is not understood and may be connected with its very special redox and ligand binding reactions. Electron transfer...... catalytic rate constant, kcat, of 56 ± 6 s−1. The results obtained are of particular interest for applications of trHb in environmental biosensing and toxicity screening....... in trHb-Bs shifted −59 mV per pH unit at pH higher than 7, consistently with a 1e−/1 H+ – transfer reaction. The heterogeneous rate constant ks for a quasi-reversible 1e− – 1H+ – transfer reaction between graphite and trHb-Bs was 10.1 ± 2.3 s−1. Upon reversible cyanide binding the ks doubled, while...... the redox potential of heme shifted 21 mV negatively, presumably reflecting changes in redox activity and in vivo signaling functions of trHb-Bs associated with ligand binding. Bioelectrocatalytic reduction of O2 catalyzed by trHb-Bs was one of the most efficient hitherto reported for Hbs, with an apparent...

  15. Spectroscopy of 46Ar by the (t,p) two-neutron transfer reaction

    CERN Document Server

    Nowak, K; Hellgartner, S; Mücher, D; Bildstein, V; Diriken, J; Elseviers, J; Gaffney, L P; Gernhäuser, R; Iwanicki, J; Johansen, J G; Huyse, M; Konki, J; Krücken, T Kröll R; Lutter, R; Orlandi, R; Pakarinen, J; Raabe, R; Reiter, P; Roger, T; Schrieder, G; Seidlitz, M; Sorlin, O; Van Duppen, P; Warr, N; De Witte, H; Zielinska, M

    2016-01-01

    States in the $N=28$ nucleus $^{46}$Ar have been studied by a two-neutron transfer reaction at REX-ISOLDE (CERN). A beam of radioactive $^{44}$ at an energy of 2.16~AMeV and a tritium loaded titanium target were used to populate $^{46}$ by the t($^{44}$,p) two-neutron transfer reaction. Protons emitted from the target were identified in the T-REX silicon detector array. The excitation energies of states in $^{46}$ have been reconstructed from the measured angles and energies of recoil protons. Angular distributions for three final states were measured and based on the shape of the differential cross section an excited state at 3695~keV has been identified as $J^\\pi = 0^+$. The angular differential cross section for the population of different states are compared to calculations using a reaction model employing both sequential and direct transfer of two neutrons. Results are compared to shell model calculations using state-of-the-art effective interactions.

  16. Dynamics of the gas-liquid interfacial reaction of O(3P) atoms with hydrocarbons

    Science.gov (United States)

    Kelso, Hailey; Köhler, Sven P. K.; Henderson, David A.; McKendrick, Kenneth G.

    2003-11-01

    We describe an experimental approach to the determination of the nascent internal state distribution of gas-phase products of a gas-liquid interfacial reaction. The system chosen for study is O(3P) atoms with the surface of liquid deuterated squalane, a partially branched long-chain saturated hydrocarbon, C30D62. The nascent OD products are detected by laser-induced fluorescence. Both OD (v'=0) and (v'=1) were observed in significant yield. The rotational distributions in both vibrational levels are essentially the same, and are characteristic of a Boltzmann distribution at a temperature close to that of the liquid surface. This contrasts with the distributions in the corresponding homogeneous gas-phase reactions. We propose a preliminary interpretation in terms of a dominant trapping-desorption mechanism, in which the OD molecules are retained at the surface sufficiently long to cause rotational equilibration but not complete vibrational relaxation. The significant yield of vibrationally excited OD also suggests that the surface is not composed entirely of -CD3 endgroups, but that secondary and/or tertiary units along the backbone are exposed.

  17. Product polarization distribution: Stereodynamics of the reaction of atom H and radical NH

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The product angular momentum polarization of the reaction of H+NH is calculated via the quasiclassical trajectory method(QCT)based on the extended London-Eyring-Polanyi-Sato(LEPS)potential energy surface(PES)at a collision energy of 5.1 kcal/mol.The calculated results of the vector correlations are denoted by using the angular distribution functions.The polarization-dependent differential cross sections(PDDCSs)demonstrate that the rotational angular momentum of the product H2 is aligned and oriented along the direction perpendicular to the scattering plane.Vector correlation shows that the angular momentum of the product H2 is aligned in the plane perpendicular to the velocity vector.It suggests that the reaction proceeds preferentially when the reactant velocity vector lies in a plane containing all three atoms.The orientation and alignment of the product angular momentum affects the scattering direction of the product molecules.The polarization-dependent differential cross sections(PDDCSs)reveal that scattering is predominantly in the backward hemisphere.

  18. Surface reaction mechanisms during ozone and oxygen plasma assisted atomic layer deposition of aluminum oxide.

    Science.gov (United States)

    Rai, Vikrant R; Vandalon, Vincent; Agarwal, Sumit

    2010-09-01

    We have elucidated the reaction mechanism and the role of the reactive intermediates in the atomic layer deposition (ALD) of aluminum oxide from trimethyl aluminum in conjunction with O(3) and an O(2) plasma. In situ attenuated total reflection Fourier transform infrared spectroscopy data show that both -OH groups and carbonates are formed on the surface during the oxidation cycle. These carbonates, once formed on the surface, are stable to prolonged O(3) exposure in the same cycle. However, in the case of plasma-assisted ALD, the carbonates decompose upon prolonged O(2) plasma exposure via a series reaction kinetics of the type, A (CH(3)) --> B (carbonates) --> C (Al(2)O(3)). The ratio of -OH groups to carbonates on the surface strongly depends on the oxidizing agent, and also the duration of the oxidation cycle in plasma-assisted ALD. However, in both O(3) and O(2) plasma cycles, carbonates are a small fraction of the total number of reactive sites compared to the hydroxyl groups.

  19. Mechanism of electron transfer reaction for xanthene dye-sensitized formation of methyl viologen radical

    Energy Technology Data Exchange (ETDEWEB)

    Usui, Y.; Misawa, H.; Sakuragi, H.; Tokumaru, K.

    1987-05-01

    Sensitized reduction of methyl viologen, MV/sup 2 +/, occurs efficiently through electron transfer from triplet xanthene dyes to MV/sup 2 +/ followed by electron transfer to the resulting semioxidized dyes from a reductant like triethanolamine. Unreactive ion pair complexes between these dyes and MV/sup 2 +/ are formed (formation constant: 1.2 x 10/sup 3/ M/sup -1/ for Eosine Y and MV/sup 2 +/ in 50% aqueous ethanol solution). The quantum yield for the reduced methyl viologen radical depends on the concentrations of MV/sup 2 +/ and the amine and on the ionic strength of solution. The efficiency of the electron transfer from triplet dyes to MV/sup 2 +/ is increased by addition of alcohol, and solvent effects on the reaction mechanism are discussed. 38 references, 5 figures, 2 tables.

  20. Electron transfer reaction in the Marcus inverted region: Role of high frequency vibrational modes

    International Nuclear Information System (INIS)

    A theoretical study of the dynamics of photo-electron transfer reactions in the Marcus inverted regime is presented. This study is motivated partly by the recent proposal of Barbara et al. (J. Phys. Chem. 96, 3728, 1991) that a minimal model of an electron transfer reaction should consist of a polar solvent mode (X), a low frequency vibrational mode (Q) and one high frequency mode (q). Interplay between these modes may be responsible for the crossover observed in the dynamics from a solvent controlled to a vibrational controlled electron transfer. The following results have been obtained. (i) In the case of slowly relaxing solvents, the proximity of the point of excitation to an effective sink on the excited surface is critical in determining the decay of the reactant population. This is because the Franck-Condon overlap between the reactant ground and the product excited states decreases rapidly with increase in the quantum number of the product vibrational state. (ii) Non-exponential solvation dynamics has an important effect in determining the rates of electron transfer. Especially, a biphasic solvation and a large coupling between the reactant and the product states both may be needed to explain the experimental results

  1. Antioxidant activities of [60]fullerene derivatives from chalcone, flavone and flavanone: A ONIOM approach via H-atom and electron transfer mechanism

    Science.gov (United States)

    Thong, Nguyen Minh; Dao, Duy Quang; Ngo, Thi Chinh; Huyen, Trinh Le; Nam, Pham Cam

    2016-05-01

    Antioxidant properties of C60 flavonoid conjugates were computationally examined via their O-H bond dissociation enthalpies (BDEs) and ionization energies (IEs) using two-layer ONIOM and PM6 methods, respectively. Eight ONIOM((RO)B3LYP/6-311++G(2df,2p):PM6) models were evaluated by computing BDE(O-H)s of a series of polyphenol. Synthetic mechanism of C60 flavonoid conjugates was also explored via the potential energy surfaces of reaction between C60 and malonate flavonoid derivatives (chalcone, flavone and flavanone) at the B3LYP/6-31G(d)//PM6. Antioxidant activities of C60 flavonoid conjugates were discussed via hydrogen atom transfer, single electron transfer mechanisms and the effect of C60 on the BDE(O-H)s and IEs of these compounds.

  2. Application of Magnetic Dicationic Ionic Liquid Phase Transfer Catalyst in Nuclophilic Substitution Reactions of Benzyl Halids in Water

    OpenAIRE

    Manouchehr Aghajeri; Ali Reza Kiasat; Bijan Mombeni Goodajdar

    2016-01-01

    magnetic dicationic ionic liquid (MDIL) was successfully prepared and evaluated as phase-transfer catalyst for nucleophilic substitution reactions. The reactions was occurred in water and furnished the corresponding benzyl derivatives in high yields. No evidence for the formation of by-product for example benzyl alcohol of the reaction was observed and the products were obtained in pure form without further purification.

  3. The improvement of the heat transfer model for sodium-water reaction jet code

    Energy Technology Data Exchange (ETDEWEB)

    Hashiguchi, Yoshirou; Yamamoto, Hajime; Kamoshida, Norio; Murata, Shuuichi [Hitachi Engineering Co., Ltd., Hitachi, Ibaraki (Japan)

    2001-02-01

    For confirming the reasonable DBL (Design Base Leak) on steam generator (SG), it is necessary to evaluate phenomena of sodium-water reaction (SWR) in an actual steam generator realistically. The improvement of a heat transfer model on sodium-water reaction (SWR) jet code (LEAP-JET ver.1.40) and application analysis to the water injection tests for confirmation of propriety for the code were performed. On the improvement of the code, the heat transfer model between a inside fluid and a tube wall was introduced instead of the prior model which was heat capacity model including both heat capacity of the tube wall and inside fluid. And it was considered that the fluid of inside the heat exchange tube was able to treat as water or sodium and typical heat transfer equations used in SG design were also introduced in the new heat transfer model. Further additional work was carried out in order to improve the stability of the calculation for long calculation time. The test calculation using the improved code (LEAP-JET ver.1.50) were carried out with conditions of the SWAT-IR{center_dot}Run-HT-2 test. It was confirmed that the SWR jet behavior on the result and the influence to the result of the heat transfer model were reasonable. And also on the improved code (LEAP-JET ver.1.50), user's manual was revised with additional I/O manual and explanation of the heat transfer model and new variable name. (author)

  4. Coke yield and heat transfer in reaction of liquid-solid agglomerates of Athabasca vacuum residue

    Energy Technology Data Exchange (ETDEWEB)

    Ali, M.; Courtney, M.; Boddez, L.; Gray, M. [Alberta Univ., Edmonton, AB (Canada). Dept. of Chemical and Materials Engineering

    2010-02-15

    Delayed coking and fluid-bed coking are the most common commercial processes used by the petroleum industry for the thermal conversion of vacuum residues into petroleum distillate products. This paper presented the results of an experimental study of coke yield at long reaction times from agglomerates of coke particles and Athabasca vacuum residue (AVR). The ultimate coke yield was determined for a range of agglomerate thicknesses, liquid concentrations and reaction temperatures. The agglomerates were heated on Curie-point alloy strips in an induction furnace at 503 and 530 degrees C until all toluene-soluble material was converted. A simple heat transfer model was used to describe the temperature profile within the agglomerates. Coke yield results from agglomerates were compared to the coke yield results from reacting thin films of vacuum residue. The average coke yield from the agglomerates was 23 per cent, while the coke yield from thin films of 20 {mu}m thickness was 11 per cent, which supports the role of mass transfer in coke formation reactions. The ultimate coke yield was insensitive to vacuum residue concentration, agglomerate size, and reaction temperature. According to control experiments on thin films of liquid at different heating rates, the temperature-time history has little effect on the ultimata coke yield. 13 refs., 2 tabs., 10 figs.

  5. Thermal proton transfer reactions in ultraviolet matrix-assisted laser desorption/ionization.

    Science.gov (United States)

    Chu, Kuan Yu; Lee, Sheng; Tsai, Ming-Tsang; Lu, I-Chung; Dyakov, Yuri A; Lai, Yin Hung; Lee, Yuan-Tseh; Ni, Chi-Kung

    2014-03-01

    One of the reasons that thermally induced reactions are not considered a crucial mechanism in ultraviolet matrix-assisted laser desorption ionization (UV-MALDI) is the low ion-to-neutral ratios. Large ion-to-neutral ratios (10(-4)) have been used to justify the unimportance of thermally induced reactions in UV-MALDI. Recent experimental measurements have shown that the upper limit of the total ion-to-neutral ratio is approximately 10(-7) at a high laser fluence and less than 10(-7) at a low laser fluence. Therefore, reexamining the possible contributions of thermally induced reactions in MALDI may be worthwhile. In this study, the concept of polar fluid was employed to explain the generation of primary ions in MALDI. A simple model, namely thermal proton transfer, was used to estimate the ion-to-neutral ratios in MALDI. We demonstrated that the theoretical calculations of ion-to-neutral ratios exhibit the same trend and similar orders of magnitude compared with those of experimental measurements. Although thermal proton transfer may not generate all of the ions observed in MALDI, the calculations demonstrated that thermally induced reactions play a crucial role in UV-MALDI.

  6. 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

    2011-01-01

    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.

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

    KAUST Repository

    Dehury, Niranjan

    2016-07-18

    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.

  8. Effects of acid concentration on intramolecular charge transfer reaction of 4-(azetidinyl) benzonitrile in solution

    Indian Academy of Sciences (India)

    Biswajit Guchhait; Tuhin Pradhan; Ranjit Biswas

    2014-01-01

    Effects of acid concentration on excited state intramolecular charge transfer reaction of 4-(azetidinyl) benzonitrile (P4C) in aprotic (acetonitrile and ethyl acetate) and protic (ethanol) solvents have been studied by means of steady state absorption and fluorescence, and time resolved fluorescence spectroscopic techniques. While absorption and fluorescence bands of P4C have been found to be shifted towards higher energy with increasing acid concentration in acetonitrile and ethyl acetate, no significant dependence has been observed in ethanolic solutions. Reaction rate becomes increasingly slower with acid concentration in acetonitrile and ethyl acetate. In contrast, acid in ethanolic solutions does not produce such an effect on reaction rate. Time-dependent density functional theory calculations have been performed to understand the observed spectroscopic results.

  9. Proton transfer reactions between nitric acid and acetone, hydroxyacetone, acetaldehyde and benzaldehyde in the solid phase.

    Science.gov (United States)

    Lasne, Jérôme; Laffon, Carine; Parent, Philippe

    2012-12-01

    The heterogeneous and homogeneous reactions of acetone, hydroxyacetone, acetaldehyde and benzaldehyde with solid nitric acid (HNO(3)) films have been studied with Reflection-Absorption Infrared Spectroscopy (RAIRS) under Ultra-High Vacuum (UHV) conditions in the 90-170 K temperature range. In the bulk or at the surface of the films, nitric acid transfers its proton to the carbonyl function of the organic molecules, producing protonated acetone-H(+), hydroxyacetone-H(+), acetaldehyde-H(+) and benzaldehyde-H(+), and nitrate anions NO(3)(-), a reaction not observed when nitric acid is previously hydrated [J. Lasne, C. Laffon and Ph. Parent, Phys. Chem. Chem. Phys., 2012, 14, 697]. This provides a molecular-scale description of the carbonyl protonation reaction in an acid medium, the first step of the acid-catalyzed condensation of carbonyl compounds, fuelling the growth of secondary organic aerosols (SOA) in the atmosphere.

  10. Ultra-low-temperature reactions of C(3P0) atoms with benzene molecules in helium droplets

    International Nuclear Information System (INIS)

    The reaction of carbon atoms with benzene has been investigated in liquid helium droplets at T = 0.37 K. We found an addition of the carbon atom to form an initial intermediate complex followed by a ring opening and the formation of a seven-membered ring. In contrast to a previous gas phase study, the reaction is frozen after these steps and the loss of hydrogen does not occur. A calorimetric technique was applied to monitor the energy balance of the reaction. It was found that more than 267 kJ mol−1 were released in this reaction. This estimation is in line with quantum chemical calculations of the formation energy of a seven-membered carbon ring. It is suggested that reactions of this kind could be responsible for the low abundance of small polycyclic aromatic hydrocarbon molecules in the interstellar medium. We also found the formation of weakly bonded water-carbon adducts, in which the carbon atom is linked to the oxygen atom of the water molecule with a binding energy of about 33.4 kJ mol−1

  11. pH-dependent electron transfer reaction and direct bioelectrocatalysis of the quinohemoprotein pyranose dehydrogenase.

    Science.gov (United States)

    Takeda, Kouta; Matsumura, Hirotoshi; Ishida, Takuya; Yoshida, Makoto; Igarashi, Kiyohiko; Samejima, Masahiro; Ohno, Hiroyuki; Nakamura, Nobuhumi

    2016-08-26

    A pyranose dehydrogenase from Coprinopsis cinerea (CcPDH) is an extracellular quinohemoeprotein, which consists a b-type cytochrome domain, a pyrroloquinoline-quinone (PQQ) domain, and a family 1-type carbohydrate-binding module. The electron transfer reaction of CcPDH was studied using some electron acceptors and a carbon electrode at various pH levels. Phenazine methosulfate (PMS) reacted directly at the PQQ domain, whereas cytochrome c (cyt c) reacted via the cytochrome domain of intact CcPDH. Thus, electrons are transferred from reduced PQQ in the catalytic domain of CcPDH to heme b in the N-terminal cytochrome domain, which acts as a built-in mediator and transfers electron to a heterogenous electron transfer protein. The optimal pH values of the PMS reduction (pH 6.5) and the cyt c reduction (pH 8.5) differ. The catalytic currents for the oxidation of l-fucose were observed within a range of pH 4.5 to 11. Bioelectrocatalysis of CcPDH based on direct electron transfer demonstrated that the pH profile of the biocatalytic current was similar to the reduction activity of cyt c characters. PMID:27338639

  12. The calibration of sub-Coulomb heavy ion proton transfer reactions

    International Nuclear Information System (INIS)

    Measurements were made of the cross sections for the 27Al(16O,15N)28Si, 89Y(15N,16O)88Sr and 89Y(27Al,28Si)88Sr reactions at energies near and below the Coulomb barrier. The first reaction required separate measurements of the transfer to elastic cross section ratio for particular charge states, the charge state distribution for 27Al and 28Si ions, and the absolute elastic scattering cross section for the 27Al + 16O system. The ratio measurement required the combined use of two relatively new scientific instruments: the momentum filter and the Bragg curve spectrometer. The latter two transfer measurements were performed using the same setup involving surface barrier detectors at backward angles. Additional elastic scattering data for the 15N + 28Si, 89Y + 15N, 89Sr + 27Al, and 88Sr + 28Si systems was collected to provide entrance and exit channel parameters needed for the theoretical calculations of the transfer reaction cross sections. The calculations were made using the DWBA code, LOLA, which assumes a one-step direct reaction mechanism. A correction was made to the code to properly include the effects of the spin-orbit force in the proton binding potentials. The original goal of these measurements was to combine the three normalization factors to determine the ground state proton spectroscopic factors for 16O, 28Si and 89Y. Such an analysis was found to yield a spectroscopic factor which significantly exceeded the shell model limit in the case of 16O. It is possible that the inclusion of multi-step processes may resolve this disagreement. 36 refs., 109 figs., 21 tabs

  13. Synthesis of Comblike Poly(methyl methacrylate) by Atom Transfer Radical Polymerization with Poly(ethyl 2-bromoacrylate) as Macroinitiator

    Institute of Scientific and Technical Information of China (English)

    Yan SHI; Zhi Feng FU; Yu Dong ZHANG; Shu Ke JIAO

    2003-01-01

    Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical polymerization of ethyl 2-bromoacrylate. The obtained comblike polymers were characterized by GPC and 1H NMR.

  14. Synthesis of triblock and random copolymers of 4- acetoxystyrene and styrene by living atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Gao, Bo; Chen, Xianyi; Ivan, Bela;

    1997-01-01

    Triblock copolymers containing polystyrene (PSt) and poly(4-acetoxystyrene) (PAcOSt) segments have been prepared by atom transfer radical polymerization (ATRP). In the first step one of the two monomers was polymerized in bulk using the initiating system alpha,alpha'-dibromo-p-xylene/CuBr/2...

  15. Ion conducting solid polymer electrolytes based on polypentafluorostyrene-b-polyether-b-polypentafluorostyrene prepared by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Jankova, Katja; Jannasch, P.; Hvilsted, Søren

    2004-01-01

    Novel triblock copolymers based on central poly( ethylene glycol) ( PEG) or poly( ethylene glycol-co-propylene glycol) (PEGPG) blocks with poly( pentafluorostyrene) (PFS) outer blocks were prepared by Atom Transfer Radical Polymerization (ATRP) with polydispersities on the order of 1.2 - 1...

  16. ANISOTROPY EFFECTS IN SINGLE-ELECTRON TRANSFER BETWEEN LASER-EXCITED ATOMS AND HIGHLY-CHARGED IONS

    NARCIS (Netherlands)

    1995-01-01

    Recent collision experiments are reviewed in which one-electron transfer between laser excited target atoms and (highly charged) keV-ions has been studied. Especially results showing a dependence of the charge exchange on the initial target orbital alignment are discussed. The question to what exten

  17. Metal ion-catalyzed cycloaddition vs hydride transfer reactions of NADH analogues with p-benzoquinones.

    Science.gov (United States)

    Fukuzumi, S; Fujii, Y; Suenobu, T

    2001-10-24

    1-Benzyl-4-tert-butyl-1,4-dihydronicotinamide (t-BuBNAH) reacts efficiently with p-benzoquinone (Q) to yield a [2+3] cycloadduct (1) in the presence of Sc(OTf)(3) (OTf = OSO(2)CF(3)) in deaerated acetonitrile (MeCN) at room temperature, while no reaction occurs in the absence of Sc(3+). The crystal structure of 1 has been determined by the X-ray crystal analysis. When t-BuBNAH is replaced by 1-benzyl-1,4-dihydronicotinamide (BNAH), the Sc(3+)-catalyzed cycloaddition reaction of BNAH with Q also occurs to yield the [2+3] cycloadduct. Sc(3+) forms 1:4 complexes with t-BuBNAH and BNAH in MeCN, whereas there is no interaction between Sc(3+) and Q. The observed second-order rate constant (k(obs)) shows a first-order dependence on [Sc(3+)] at low concentrations and a second-order dependence at higher concentrations. The first-order and the second-order dependence of the rate constant (k(et)) on [Sc(3+)] was also observed for the Sc(3+)-promoted electron transfer from CoTPP (TPP = tetraphenylporphyrin dianion) to Q. Such dependence of k(et) on [Sc(3+)] is ascribed to formation of 1:1 and 1:2 complexes between Q(*)(-) and Sc(3+) at the low and high concentrations of Sc(3+), respectively, which results in acceleration of the rate of electron transfer. The formation constants for the 1:2 complex (K(2)) between the radical anions of a series of p-benzoquinone derivatives (X-Q(*)(-)) and Sc(3+) are determined from the dependence of k(et) on [Sc(3+)]. The K(2) values agree well with those determined from the dependence of k(obs) on [Sc(3+)] for the Sc(3+)-catalyzed addition reaction of t-BuBNAH and BNAH with X-Q. Such an agreement together with the absence of the deuterium kinetic isotope effects indicates that the addition proceeds via the Sc(3+)-promoted electron transfer from t-BuBNAH and BNAH to Q. When Sc(OTf)(3) is replaced by weaker Lewis acids such as Lu(OTf)(3), Y(OTf)(3), and Mg(ClO(4))(2), the hydride transfer reaction from BNAH to Q also occurs besides the

  18. Investigations of electrochemical oxygen transfer reaction on boron-doped diamond electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Kapalka, Agnieszka; Foti, Gyoergy [Institute of Chemical Sciences and Engineering, Ecole Polytechnique Federale de Lausanne (EPFL), CH-1015 Lausanne (Switzerland); Comninellis, Christos [Institute of Chemical Sciences and Engineering, Ecole Polytechnique Federale de Lausanne (EPFL), CH-1015 Lausanne (Switzerland)], E-mail: christos.comninellis@epfl.ch

    2007-12-31

    In this paper, the electrochemical oxygen transfer reaction (EOTR) is studied on boron-doped diamond electrodes using simple C{sub 1} organic compounds (methanol and formic acid). The kinetics of both oxygen evolution (side reaction) and organics oxidation (main reaction) has been investigated using boron-doped diamond microelectrodes-array (BDD MEA). Oxygen evolution, in the high-potential region, takes place with a Tafel slope of 120 mV dec{sup -1} and zero reaction order with respect to H{sup +}. In the presence of organics, a shift of the polarization curves to lower potentials is observed while the Tafel slopes remain close to 120 mV dec{sup -1}. A simplified model of C{sub 1} organics oxidation is proposed. Both water discharge and organics oxidation are assumed to be fast reactions. The slowest step of the studied EOTR is the anodic discharge of hydroxyl radicals to oxygen. Further in this work, electrolysis of formic acid on boron-doped diamond macroelectrode is presented. In order to achieve 100% current efficiency, electrolysis was carried out under programmed current, in which the current density was adjusted to the limiting value.

  19. Transfer reaction cross sections from the interactions of 20Ne and 22Ne with 232Th

    International Nuclear Information System (INIS)

    A target of 232Th has been bombarded with 114 MeV 22Ne and with 114 MeV and 129 MeV 20Ne beams. Recoiling reaction products were chemically isolated and the cross sections for protactinium, uranium, and neptunium isotopes were determined. The width of the cross section distributions for a given Z and their neutron-richness are the same as those for similar transfers in Ne+ 248Cm reactions. Population of low spin isomeric states is favored in these reactions over population of high spin states. As was seen in reactions with heavier targets, an increase in reaction energy does little to shift the evaporation residues toward neutron deficiency. The implications are that only primary products with little or no excitation energy and angular momentum survive the fission process to become evaporation residues in these systems, and that the production of these nuclides is more controlled by the change in the identity of the projectile than by the corresponding change in the target

  20. Method of obtaining sulphur-labelled compounds by reaction of ''hot'' sulphur-35 atoms with cyclic hydrocarbons

    International Nuclear Information System (INIS)

    The authors discuss methods of obtaining sulphur-labelled compounds, such as aliphatic and cyclic mercaptans and sulphides, by direct synthesis employing recoil atoms from the reaction Cl35 (n, p) S35. Hot S35 atoms were obtained in the middle of the target substance by exposing mixtures of C Cl4 and a cyclic hydrocarbon (cyclopentane, cyelohexane) to neutrons in a reactor. A method is given for irradiating the mixtures and then separating the various sulphur-bearing compounds by specific chemical methods, rectification, and paper and gas-liquid chromatography. The purpose of the exchange is clarified. The relation of the yield of the separated sulphur-labelled products to the composition of the mixture and type of exposure was investigated, and an active-sulphur balance settled. New types of atomic sulphur reactions were established: the CH2-group is replaced and implanted on the C-C link. The cyclic molecule is destroyed in the interaction with the hot sulphur atoms. Hot sulphur atoms can initiate the formation of polymers containing sulphur. The yields of these reactions were established. Up to 98% of the active sulphur is linked in the form of organic sulphur compounds. It was shown that sulphur-labelled thiophene, tetrahydrothiopyrane, cyclopentyl-mercaptan, cyclohexylmercaptan, ethyl-propyl-butyl-mercaptans, dicyclopentyl-sulphide, polymeric mercaptans and sulphides could be synthesized by heat. I t is possible to regulate within broad limits the yield of various labelled compounds by changing the decelerating properties of the medium. (author)

  1. ({sup 18}O,{sup 16}O) Two-neutron transfer reactions for spectroscopic studies

    Energy Technology Data Exchange (ETDEWEB)

    Cavallaro, Manuela; Agodi, Clementina; Bondi, Mariangela; Cappuzzello, Francesco; Carbone, Diana; Cunsolo, Angelo; Foti, Antonino; Napoli, Marzio de; Nicolosi, Dario; Tropea, Stefania [University of Catania, INFN-LNS and INFN-Sez., Catania (Italy); Lubian, Jesus; Garcia, Vantelfo; Paes, Barbara [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Inst. de Fisica

    2012-07-01

    Full text: The {sup 12}C({sup 18}O,{sup 16}O){sup 14}C and {sup 13}C({sup 18}O,{sup 17}O){sup 14}C transfer reactions have been studied at 84 MeV incident energy at the INFN-LNS laboratory in Catania (Italy). The {sup 16}O and {sup 17}O ejectiles were detected at forward angles by the MAGNEX large acceptance magnetic spectrometer. Q-value spectra up to about 20 MeV and angular distributions were obtained with resolution of about 150 keV in energy and 0.2 deg in angle. In particular, excited states with relevant 1p-3h configuration with respect to the {sup 16}O core are mainly populated by the ({sup 18}O,{sup 17}O) reaction while states with known 2p-4h configuration are excited by the ({sup 18}O,{sup 16}O). This demonstrates the clear selectivity of such reactions. The shape of the measured angular distributions is found to be sensibly dependent on the transferred angular momentum. A theoretical description based on exact finite range coupled reaction channel calculations using the double folding Sao Paulo potential is used for the first time to analyze the data. The good agreement with the experimental cross section demonstrates that, despite the heavy ions involved, the one-step transfer of a two-neutron pair is dominant in the ({sup 18}O,{sup 16}O) reaction. A comparison with Distorted Wave Born Approximation calculations using the same potential shows that effects of channel couplings is visible but small. Supplementary two-neutron sequential transfer calculation are performed within the two-step DWBA formalism, introducing the intermediate partition {sup 13}C + {sup 17}O. This accounts only for a negligible contribution to the absolute cross section. As a consequence, the possibility to extract two-particle spectroscopic factor and, more in general, information on nuclear structure is demonstrated. (author)

  2. Femtosecond dynamics of fundamental reaction processes in liquids: Proton transfer, geminate recombination, isomerization and vibrational relaxation

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, B.J.

    1992-11-01

    The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured and effects of external hydrogen-bonding interactions on the proton transfer are studied. The proton transfer takes place in {approximately}240 fsec in nonpolar environments, but becomes faster than instrumental resolution of 110 fsec in methanol solution. The dynamics following photodissociation of CH{sub 2}I{sub 2} and other small molecules provide the first direct observations of geminate recombination. The recombination of many different photodissociating species occurs on a {approximately}350 fsec time scale. Results show that recombination yields but not rates depend on the solvent environment and suggest that recombination kinetics are dominated by a single collision with surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. Data show no simple correlation between hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes, implying that the isomerization does not provide a suitable for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial steps of the photochromic reaction process occur extremely rapidly. Laser system and computer codes for data analysis are discussed.

  3. Nafion®-catalyzed microwave-assisted Ritter reaction: An atom-economic solvent-free synthesis of amides

    Science.gov (United States)

    An atom-economic solvent-free synthesis of amides by the Ritter reaction of alcohols and nitriles under microwave irradiation is reported. This green protocol is catalyzed by solid supported Nafion®NR50 with improved efficiency and reduced waste production.

  4. Mechanism of electron transfer reaction of ternary dipicolinatochromium(III) complex involving oxalate as secondary ligand

    Indian Academy of Sciences (India)

    Hassan Amroun Ewais; Iqbal Mohamed Ibrhium Ismail

    2013-09-01

    Mechanism of electron transfer reaction of ternary Mechanism of the oxidation of [CrIII(DPA)(OX)(H2O)]− (DPA = dipicolinate and OX = oxalate) by periodate in aqueous acidic medium has been studied spectrophotometrically over the pH range of 4.45-5.57 at different temperatures. The reaction is first order with respect to both [IO$^{−}_{4}$] and the complex concentration, and it obeys the following rate law: $$d[{\\text Cr}^{\\text{VI}}]/dt = k_6K_4K_6[{\\text IO}^−_4][{\\text{Cr}}^{\\text{III}}]_{\\text{T}}/\\{([H^+] + K_4) + (K_5[H+] + K_6K_4)[{\\text{IO}}^{−}_{4}]\\}.$$ The rate of the reaction increases with increasing pH due to the deprotonation equilibria of the complex. The experimental rate law is consistent with a mechanism in which the deprotonated form [CrIII(DPA)(OX)(OH)]2− is more reactive than the conjugated acid. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO$^{−}_{4}$ to chromium(III). Thermodynamic activation parameters were calculated using the transition state theory equation.dipicolinatochromium(III) complex involving oxalate as secondary ligand

  5. Gamma ray spectroscopy of neutron-rich actinides after multi-nucleon transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Vogt, Andreas; Birkenbach, Benedikt; Reiter, Peter; Hess, Herbert; Lewandowski, Lars; Steinbach, Tim [Institut fuer Kernphysik, Universitaet zu Koeln (Germany); Collaboration: LNL 11.22-Collaboration

    2014-07-01

    Excited states in neutron-rich Th and U nuclei were investigated after multi-nucleon transfer reactions employing the AGATA demonstrator and PRISMA setup at LNL (INFN, Italy). A primary {sup 136}Xe beam of 1 GeV hitting a {sup 238}U target was used to produce the nuclei of interest in the actinide region. Beam-like reaction products in the Xe-Ba-region were identified and selected by the PRISMA spectrometer. Kinematic coincidences between the binary reaction products of beam-like and target-like nuclei are detected with an additional MCP detector. Those coincidences allow clean conditions for in-beam γ-ray spectroscopy. Background contributions from excited fission fragments are successfully discriminated. γ-rays from excited states in beam- and target-like particles were measured with the position sensitive AGATA HPGe detectors. Improved energy resolution after Doppler correction is based on the novel γ-ray tracking technique which was successfully exploited to increase the quality of the γ-spectra. γ-ray spectra of the produced beam-like isotopes in the one-proton and two-proton transfer channels will be presented. Corresponding results from the hard-to-reach neutron-rich isotopes beyond {sup 232}Th will focus on their collective properties and cross section limits for their production.

  6. In situ Regeneration of NADH via Lipoamide Dehydrogenase-catalyzed Electron Transfer Reaction Evidenced by Spectroelectrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Tam, Tsz Kin; Chen, Baowei; Lei, Chenghong; Liu, Jun

    2012-08-01

    NAD/NADH is a coenzyme found in all living cells, carrying electrons from one reaction to another. We report on characterizations of in situ regeneration of NADH via lipoamide dehydrogenase (LD)-catalyzed electron transfer reaction to regenerate NADH using UV-vis spectroelectrochemistry. The Michaelis-Menten constant (Km) and maximum velocity (Vmax) of NADH regeneration were measured as 0.80 {+-} 0.15 mM and 1.91 {+-} 0.09 {micro}M s-1 in a 1-mm thin-layer spectroelectrochemical cell using gold gauze as the working electrode at the applied potential -0.75 V (vs. Ag/AgCl). The electrocatalytic reduction of the NAD system was further coupled with the enzymatic conversion of pyruvate to lactate by lactate dehydrogenase to examine the coenzymatic activity of the regenerated NADH. Although the reproducible electrocatalytic reduction of NAD into NADH is known to be difficult compared to the electrocatalytic oxidation of NADH, our spectroelectrochemical results indicate that the in situ regeneration of NADH via LD-catalyzed electron transfer reaction is fast and sustainable and can be potentially applied to many NAD/NADH-dependent enzyme systems.

  7. Multi-step reaction mechanism for F atom interactions with organosilicate glass and SiO x films

    Science.gov (United States)

    Mankelevich, Yuri A.; Voronina, Ekaterina N.; Rakhimova, Tatyana V.; Palov, Alexander P.; Lopaev, Dmitry V.; Zyryanov, Sergey M.; Baklanov, Mikhail R.

    2016-09-01

    An ab initio approach with the density functional theory (DFT) method was used to study F atom interactions with organosilicate glass (OSG)-based low-k dielectric films. Because of the complexity and significant modifications of the OSG surface structure during the interaction with radicals and etching, a variety of reactions between the surface groups and thermal F atoms can happen. For OSG film etching and damage, we propose a multi-step mechanism based on DFT static and dynamic simulations, which is consistent with the previously reported experimental observations. The important part of the proposed mechanism is the formation of pentavalent Si atoms on the OSG surface due to a quasi-chemisorption of the incident F atoms. The revealed mechanism of F atom incorporation into the OSG matrix explains the experimentally observed phenomena of fast fluorination without significant modification of the chemical structure. We demonstrate that the pentavalent Si states induce the weakening of adjacent Si–O bonds and their breaking under F atom flux. The calculated results allow us to propose a set of elementary chemical reactions of successive removal of CH3 and CH2 groups and fluorinated SiO x matrix etching.

  8. Imaging Proton Transfer and Dihalide Formation Pathways in Reactions of F(-) + CH3I.

    Science.gov (United States)

    Carrascosa, Eduardo; Michaelsen, Tim; Stei, Martin; Bastian, Björn; Meyer, Jennifer; Mikosch, Jochen; Wester, Roland

    2016-07-14

    Ion-molecule reactions of the type X(-) + CH3Y are commonly assumed to produce Y(-) through bimolecular nucleophilic substitution (SN2). Beyond this reaction, additional reaction products have been observed throughout the last decades and have been ascribed to different entrance channel geometries differing from the commonly assumed collinear approach. We have performed a crossed beam velocity map imaging experiment on the F(-) + CH3I reaction at different relative collision energies between 0.4 and 2.9 eV. We find three additional channels competing with nucleophilic substitution at high energies. Experimental branching ratios and angle- and energy differential cross sections are presented for each product channel. The proton transfer product CH2I(-) is the main reaction channel, which competes with nucleophilic substitution up to 2.9 eV relative collision energy. At this level, the second additional channel, the formation of IF(-) via halogen abstraction, becomes more efficient. In addition, we present the first evidence for an [FHI](-) product ion. This [FHI](-) product ion is present only for a narrow range of collision energies, indicating possible dissociation at high energies. All three products show a similar trend with respect to their velocity- and scattering angle distributions, with isotropic scattering and forward scattering of the product ions occurring at low and high energies, respectively. Reactions leading to all three reaction channels present a considerable amount of energy partitioning in product internal excitation. The internally excited fraction shows a collision energy dependence only for CH2I(-). A similar trend is observed for the isoelectronic OH(-) + CH3I system. The comparison of our experimental data at 1.55 eV collision energy with a recent theoretical calculation for the same system shows a slightly higher fraction of internal excitation than predicted, which is, however, compatible within the experimental accuracy. PMID:26799548

  9. Theoretical and kinetic study of the hydrogen atom abstraction reactions of unsaturated C6 methyl esters with hydroxyl radical

    Science.gov (United States)

    Wang, Quan-De; Ni, Zhong-Hai

    2016-04-01

    This work reports a systematic ab initio and chemical kinetic study of the rate constants for hydrogen atom abstraction reactions by hydroxyl radical (OH) on typical isomers of unsaturated C6 methyl esters at the CBS/QB3 level of theory. The high-pressure limit rate constants at different reaction sites for all the methyl esters in the temperature range from 500 to 2000 K are calculated via transition-state theory with the Wigner method for quantum tunneling effect and fitted to the modified three parameters Arrhenius expression using least-squares regression. Further, a branching ratio analysis for each reaction site has been performed.

  10. Transferable aspherical atom model refinement of protein and DNA structures against ultrahigh-resolution X-ray data.

    Science.gov (United States)

    Malinska, Maura; Dauter, Zbigniew

    2016-06-01

    In contrast to the independent-atom model (IAM), in which all atoms are assumed to be spherical and neutral, the transferable aspherical atom model (TAAM) takes into account the deformed valence charge density resulting from chemical bond formation and the presence of lone electron pairs. Both models can be used to refine small and large molecules, e.g. proteins and nucleic acids, against ultrahigh-resolution X-ray diffraction data. The University at Buffalo theoretical databank of aspherical pseudo-atoms has been used in the refinement of an oligopeptide, of Z-DNA hexamer and dodecamer duplexes, and of bovine trypsin. The application of the TAAM to these data improves the quality of the electron-density maps and the visibility of H atoms. It also lowers the conventional R factors and improves the atomic displacement parameters and the results of the Hirshfeld rigid-bond test. An additional advantage is that the transferred charge density allows the estimation of Coulombic interaction energy and electrostatic potential.

  11. 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

    2015-01-01

    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) ...

  12. Methane formation from the reactions of hydroxyl radicals and hydrogen atoms with dimethyl sulfoxide (DMSO)

    International Nuclear Information System (INIS)

    Acidic, aqueous, deaerated solutions of pure DMSO, of DMSO-KBr and of DMSO-EtOH in completely filled glass ampoules were irradiated with a 60Co γ source. The gases formed were extracted under vacuum and analysed by gas chromatography. Argon and helium were used as carrier gases and the principal gaseous products were CH4, H2, C2H6: traces of CO2 and C2H4 were also detected. It was shown that both hydrogen atoms and hydroxyl radicals react with dimethylsulfoxide in aqueous acid solution to produce methane. In both cases however only a fraction of the radicals captured gives rise to this product. Thus methane formed in the reaction of DMSO with biological systems is not unequivocal proof of the presence of OH radicals; nor is the yield of methane a direct measure of an OH yield. The rate constants k(H+DMSO)=2.6x107M-1s-1 and k(OH+DMSO)=2.1x1010M-1s-1 were determined in the presence of 5x10-1M sulfuric acid

  13. Reaction Mechanism Underlying Atomic Layer Deposition of Antimony Telluride Thin Films.

    Science.gov (United States)

    Han, Byeol; Kim, Yu-Jin; Park, Jae-Min; Yusup, Luchana L; Ishii, Hana; Lansalot-Matras, Clement; Lee, Won-Jun

    2016-05-01

    The mechanism underlying the deposition of SbTe films by alternating exposures to Sb(NMe2)3 and Te(GeMe3)2 was investigated. Sb(NMe2)3 and Te(GeMe3)2 were selected because they have very high vapor pressure and are free of Si, Cl, and O atoms in the molecules. The mechanism of deposition was proposed by density functional theory (DFT) calculation and was verified by in-situ quartz crystal microbalance (QCM) analysis. DFT calculation expected the ligand-exchange reactions between the Sb and Te precursors to form Me2NGeMe3 as the byproduct. QCM analysis indicated that a single -NMe2 group in Sb(NMe2)3 reacts with -TeGeMe3 on the surface to form an Sb2Te3 film, and that a small fraction of Sb is incorporated into the film by the thermal decomposition of Sb(NMe2)3. The Te(GeMe3)2 molecules were thermally stable up to 120 degrees C, while the Sb(NMe2)3 molecules decomposed at temperatures of 60 degrees C and higher. Sb-rich SbTe films with different Sb contents were prepared by controlling the partial decomposition of Sb(NMe2)3 molecules, which was enhanced by increasing the pulse time of the precursor. PMID:27483847

  14. On the theory of electron transfer reactions at semiconductor electrode/liquid interfaces

    Science.gov (United States)

    Gao, Yi Qin; Georgievskii, Yuri; Marcus, R. A.

    2000-02-01

    Electron transfer reaction rate constants at semiconductor/liquid interfaces are calculated using the Fermi Golden Rule and a tight-binding model for the semiconductors. The slab method and a z-transform method are employed in obtaining the electronic structures of semiconductors with surfaces and are compared. The maximum electron transfer rate constants at Si/viologen2+/+ and InP/Me2Fc+/0 interfaces are computed using the tight-binding type calculations for the solid and the extended-Hückel for the coupling to the redox agent at the interface. These results for the bulk states are compared with the experimentally measured values of Lewis and co-workers, and are in reasonable agreement, without adjusting parameters. In the case of InP/liquid interface, the unusual current vs applied potential behavior is additionally interpreted, in part, by the presence of surface states.

  15. Electronic shift register memory based on molecular electron-transfer reactions

    International Nuclear Information System (INIS)

    The design of a shift register memory at the molecular level is described in detail. The memory elements are based on a chain of electron-transfer molecules incorporated on a very large scale integrated (VLSI) substrate, and the information is shifted by photoinduced electron-transfer reactions. The design requirements for such a system are discussed, and several realistic strategies for synthesizing these systems are presented. The immediate advantage of such a hybrid molecular/VLSI device would arise from the possible information storage density. The prospect of considerable savings of energy per bit processed also exists. This molecular shift register memory element design solves the conceptual problems associated with integrating molecular size components with larger (micron) size features on a chip

  16. Electron transfer reactions of osmium(II) complexes with phenols and phenolic acids

    Science.gov (United States)

    Rajeswari, Angusamy; Ramdass, Arumugam; Muthu Mareeswaran, Paulpandian; Velayudham, Murugesan; Rajagopal, Seenivasan

    2016-07-01

    Three [Os(NN)3]2+ complexes (NN = polypyridine) with ligands of varying hydrophobicity were synthesized and characterized by NMR spectral techniques. The geometry of the molecules are optimized by DFT calculations. The interaction between [Os(NN)3]2+ complexes and phenolate ion in ground state is confirmed by absorption spectral study and the binding constant values are in the range of 3-740 M-1. The photoinduced electron transfer reaction of these [Os(NN)3]2+ complexes with phenols and phenolic acids at pH 12.5 leads to the formation of phenoxyl radical confirmed through transient absorption spectral study. Binding constants and electron transfer rate constants within the [Os(NN)3]2+-phenolate ion adduct account for the change for the overall quenching constant with the change of structure of reactants.

  17. Learned cardiac control with heart rate biofeedback transfers to emotional reactions.

    Directory of Open Access Journals (Sweden)

    Nathalie Peira

    Full Text Available Emotions involve subjective feelings, action tendencies and physiological reactions. Earlier findings suggest that biofeedback might provide a way to regulate the physiological components of emotions. The present study investigates if learned heart rate regulation with biofeedback transfers to emotional situations without biofeedback. First, participants learned to decrease heart rate using biofeedback. Then, inter-individual differences in the acquired skill predicted how well they could decrease heart rate reactivity when later exposed to negative arousing pictures without biofeedback. These findings suggest that (i short lasting biofeedback training improves heart rate regulation and (ii the learned ability transfers to emotion challenging situations without biofeedback. Thus, heart rate biofeedback training may enable regulation of bodily aspects of emotion also when feedback is not available.

  18. On the ultrafast kinetics of the energy and electron transfer reactions in photosystem I

    Energy Technology Data Exchange (ETDEWEB)

    Slavov, Chavdar Lyubomirov

    2009-07-09

    The subject of the current work is one of the main participants in the light-dependent phase of oxygenic photosynthesis, Photosystem I (PS I). This complex carries an immense number of cofactors: chlorophylls (Chl), carotenoids, quinones, etc, which together with the protein entity exhibit several exceptional properties. First, PS I has an ultrafast light energy trapping kinetics with a nearly 100% quantum efficiency. Secondly, both of the electron transfer branches in the reaction center are suggested to be active. Thirdly, there are some so called 'red' Chls in the antenna system of PS I, absorbing light with longer wavelengths than the reaction center. These 'red' Chls significantly modify the trapping kinetics of PS I. The purpose of this thesis is to obtain better understanding of the above-mentioned, specific features of PS I. This will not merely cast more light on the mechanisms of energy and electron transfer in the complex, but also will contribute to the future developments of optimized artificial light-harvesting systems. In the current work, a number of PS I complexes isolated from different organisms (Thermosynechococcus elongatus, Chlamydomonas reinhardtii, Arabidopsis thaliana) and possessing distinctive features (different macroorganisation, monomers, trimers, monomers with a semibelt of peripheral antenna attached; presence of 'red' Chls) is investigated. The studies are primarily focused on the electron transfer kinetics in each of the cofactor branches in the PS I reaction center, as well as on the effect of the antenna size and the presence of 'red' Chls on the trapping kinetics of PS I. These aspects are explored with the help of several ultrafast optical spectroscopy methods: (i) time-resolved fluorescence ? single photon counting and synchroscan streak camera; and (ii) ultrafast transient absorption. Physically meaningful information about the molecular mechanisms of the energy trapping in PS I is

  19. Predicting the production of neutron rich heavy nuclei in multi-nucleon transfer reactions using GRAZING-F

    CERN Document Server

    Yanez, R

    2015-01-01

    Background: Multi-nucleon transfer reactions have recently attracted attention as a possible path to the synthesis of new neutron-rich heavy nuclei. Purpose: We study transfer reactions involving massive nuclei with the intention of understanding if the semi-classical model GRAZING coupled to an evaporation and fission competition model can satisfactory reproduce experimental data on transfer reactions in which fission plays a role. Methods: We have taken the computer code GRAZING and have added fission competition to it (GRAZING-F) using our current understanding of $\\Gamma_n/\\Gamma_f$, fission barriers and level densities. Results: The code GRAZING-F seems to satisfactory reproduce experimental data for $+1p$, $+2p$ and $+3p$ transfers, but has limitations in reproducing measurements of larger above-target and below-target transfers. Nonetheless, we use GRAZING-F to estimate production rates of neutron-rich $N=126$ nuclei, actinides and transactinides. Conclusions: The GRAZING code, with appropriate modific...

  20. Observation of Spontaneous C=C Bond Breaking in the Reaction between Atomic Boron and Ethylene in Solid Neon.

    Science.gov (United States)

    Jian, Jiwen; Lin, Hailu; Luo, Mingbiao; Chen, Mohua; Zhou, Mingfei

    2016-07-11

    A ground-state boron atom inserts into the C=C bond of ethylene to spontaneously form the allene-like compound H2 CBCH2 on annealing in solid neon. This compound can further isomerize to the propyne-like HCBCH3 isomer under UV light excitation. The observation of this unique spontaneous C=C bond insertion reaction is consistent with theoretical predictions that the reaction is thermodynamically exothermic and kinetically facile. This work demonstrates that the stronger C=C bond, rather than the less inert C-H bond, can be broken to form organoboron species from the reaction of a boron atom with ethylene even at cryogenic temperatures.

  1. Observation of Spontaneous C=C Bond Breaking in the Reaction between Atomic Boron and Ethylene in Solid Neon.

    Science.gov (United States)

    Jian, Jiwen; Lin, Hailu; Luo, Mingbiao; Chen, Mohua; Zhou, Mingfei

    2016-07-11

    A ground-state boron atom inserts into the C=C bond of ethylene to spontaneously form the allene-like compound H2 CBCH2 on annealing in solid neon. This compound can further isomerize to the propyne-like HCBCH3 isomer under UV light excitation. The observation of this unique spontaneous C=C bond insertion reaction is consistent with theoretical predictions that the reaction is thermodynamically exothermic and kinetically facile. This work demonstrates that the stronger C=C bond, rather than the less inert C-H bond, can be broken to form organoboron species from the reaction of a boron atom with ethylene even at cryogenic temperatures. PMID:27240114

  2. Stereodynamical Origin of Anti-Arrhenius Kinetics: Negative Activation Energy and Roaming for a Four-Atom Reaction.

    Science.gov (United States)

    Coutinho, Nayara D; Silva, Valter H C; de Oliveira, Heibbe C B; Camargo, Ademir J; Mundim, Kleber C; Aquilanti, Vincenzo

    2015-05-01

    The OH + HBr → H2O + Br reaction, prototypical of halogen-atom liberating processes relevant to mechanisms for atmospheric ozone destruction, attracted frequent attention of experimental chemical kinetics: the nature of the unusual reactivity drop from low to high temperatures eluded a variety of theoretical efforts, ranking this one among the most studied four-atom reactions. Here, inspired by oriented molecular-beams experiments, we develop a first-principles stereodynamical approach. Thermalized sets of trajectories, evolving on a multidimensional potential energy surface quantum mechanically generated on-the-fly, provide a map of most visited regions at each temperature. Visualizations of rearrangements of bonds along trajectories and of the role of specific angles of reactants' mutual approach elucidate the mechanistic change from the low kinetic energy regime (where incident reactants reorient to find the propitious alignment leading to reaction) to high temperature (where speed hinders adjustment of directionality and roaming delays reactivity). PMID:26263312

  3. Large-scale quantum mechanical scattering calculations for molecular energy transfer and chemical reactions

    International Nuclear Information System (INIS)

    The authors discuss two projects involving quantal collision theory calculations on supercomputers. In the first project the authors are considering HF-HF collisions and calculating rotational energy transfer for collisions of rigid molecules and vibrational-to-vibrational (V-V) energy transfer for collisions including all degrees of freedom. They examined several potential energy surfaces, and they parametrized a new one that should be more accurate for the cross correlation of the forces. For rotational energy transfer they also compared the results to classical trajectory calculations. The quantal calculations were carried out by integrating the close coupling equations with scattering boundary conditions using an extensively vectorized R matrix propagation code on the Control Data Corporation Cyber 205 computer. In the second project they are considering atom-diatom reactive collisions for low initial rotational states and both the ground and first excited vibrational state. The three arrangement channels (A =BC, AB+C, and AC+B) are coupled by the Fock scheme, and the reactive amplitude density (obtained by operating on the initial state with the reactance operator or the total wave function with the interaction potential) is expanded in a square-integrable basis set. This leads to a large system of coupled algebraic equations which are constructed and solved using a large-memory Cray-2 computer. Variational improvements have been tested successfully for nonreactive collisions and will soon be implemented for reactive collisions

  4. Surprisingly Long-Lived Ascorbyl Radicals in Acetonitrile: Concerted Proton-Electron Transfer Reactions and Thermochemistry

    OpenAIRE

    Warren, Jeffrey J.; Mayer, James M.

    2008-01-01

    Proton-coupled electron transfer (PCET) reactions and thermochemistry of 5,6-isopropylidene ascorbate (iAscH−) have been examined in acetonitrile solvent.iAscH− is oxidized by 2,4,6-tBu3C6H2O• and by excess TEMPO• to give the corresponding 5,6-isopropylidene ascorbyl radical anion (iAsc•−), which persists for hours at 298 K in dry MeCN solution. The stability of iAsc•− is surprising in light of the transience of the ascorbyl radical in aqueous solutions, and is due to the lack of the protons ...

  5. Heat and mass transfer in unsteady rotating fluid flow with binary chemical reaction and activation energy.

    Directory of Open Access Journals (Sweden)

    Faiz G Awad

    Full Text Available In this study, the Spectral Relaxation Method (SRM is used to solve the coupled highly nonlinear system of partial differential equations due to an unsteady flow over a stretching surface in an incompressible rotating viscous fluid in presence of binary chemical reaction and Arrhenius activation energy. The velocity, temperature and concentration distributions as well as the skin-friction, heat and mass transfer coefficients have been obtained and discussed for various physical parametric values. The numerical results obtained by (SRM are then presented graphically and discussed to highlight the physical implications of the simulations.

  6. Heat and mass transfer in unsteady rotating fluid flow with binary chemical reaction and activation energy.

    Science.gov (United States)

    Awad, Faiz G; Motsa, Sandile; Khumalo, Melusi

    2014-01-01

    In this study, the Spectral Relaxation Method (SRM) is used to solve the coupled highly nonlinear system of partial differential equations due to an unsteady flow over a stretching surface in an incompressible rotating viscous fluid in presence of binary chemical reaction and Arrhenius activation energy. The velocity, temperature and concentration distributions as well as the skin-friction, heat and mass transfer coefficients have been obtained and discussed for various physical parametric values. The numerical results obtained by (SRM) are then presented graphically and discussed to highlight the physical implications of the simulations. PMID:25250830

  7. Studies of Nuclei Close to 132Sn Using Single-Neutron Transfer Reactions

    International Nuclear Information System (INIS)

    Neutron transfer reactions were performed in inverse kinematics using radioactive ion beams of 132Sn, 130Sn, and 134Te and deuterated polyethylene targets. Preliminary results are presented. The Q-value spectra for 133Sn, 131Sn and 135Te reveal a number of previously unobserved peaks. The angular distributions are compatible with the expected lf7/2 nature of the ground state of 133Sn, and 2p3/2 for the 3.4 MeV state in 131Sn.

  8. Effects of mass transfer on MHD flow of casson fluid with chemical reaction and suction

    Directory of Open Access Journals (Sweden)

    S. A. Shehzad

    2013-03-01

    Full Text Available Effect of mass transfer in the magnetohydrodynamic flow of a Casson fluid over a porous stretching sheet is addressed in the presence of a chemical reaction. A series solution for the resulting nonlinear flow is computed. The skin friction coefficient and local Sherwood number are analyzed through numerical values for various parameters of interest. The velocity and concentration fields are illustrated for several pertinent flow parameters. We observed that the Casson parameter and Hartman number have similar effects on the velocity in a qualitative sense. We further analyzed that the concentration profile decreases rapidly in comparison to the fluid velocity when we increased the values of the suction parameter.

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

    DEFF Research Database (Denmark)

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

    .2 Metal complex of ligands possessing both H-donor and H-acceptor sites in the second coordination sphere should be interesting candidates for proton transfer reactions induced by photooxidation of the metal ion. We have prepared new oxime-containing ligands which coordinate to metal ions...... such that a pyridine group is sterically restricted so it does not coordinate. Instead it can act as proximal base for accepting the oxime proton. [1] M. H. V. Huynh, T. J. Meyer, Chem. Rev. 2007, 107, 5004-5064. [2] T. Irebo, O. Johansson, L. Hammarström, J. Am. Chem. Soc., 2008, 130, 9194-9195....

  10. Studies of Nuclei Close to 132Sn Using Single-Neutron Transfer Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Jones, K. L. [University of Tennessee, Knoxville (UTK); Pain, S. D. [Rutgers University; Kozub, R. L. [Tennessee Technological University; Adekola, Aderemi S [ORNL; Bardayan, Daniel W [ORNL; Blackmon, Jeff C [ORNL; Catford, Wilton N [ORNL; Chae, K. Y. [University of Tennessee, Knoxville (UTK); Chipps, K. [Colorado School of Mines, Golden; Cizewski, J. A. [Rutgers University; Erikson, Luke [Colorado School of Mines, Golden; Gaddis, A. L. [Furman University; Greife, U. [Colorado School of Mines, Golden; Grzywacz, R. K. [University of Tennessee, Knoxville (UTK); Harlin, Christopher W [ORNL; Hatarik, Robert [Rutgers University; Howard, Joshua A [ORNL; James, J. [Colorado School of Mines, Golden; Kapler, R. [University of Tennessee, Knoxville (UTK); Krolas, W. [University of Warsaw; Liang, J Felix [ORNL; Ma, Zhanwen [ORNL; Matei, Catalin [Oak Ridge Associated Universities (ORAU); Moazen, Brian [University of Tennessee, Knoxville (UTK); Nesaraja, Caroline D [ORNL; O' Malley, Patrick [Rutgers University; Patterson, N. P. [University of Surrey, UK; Paulauskas, Stanley [University of Tennessee, Knoxville (UTK); Shapira, Dan [ORNL; ShrinerJr., J. F. [Tennessee Technological University; Sikora, M. [Rutgers University; Sissom, D. J. [Tennessee Technological University; Smith, Michael Scott [ORNL; Swan, T. P. [University of Surrey, UK; Thomas, J. S. [Rutgers University; Wilson, Gemma L [ORNL

    2009-01-01

    Neutron transfer reactions were performed in inverse kinematics using radioactive ion beams of 132Sn, 130Sn, and 134Te and deuterated polyethylene targets. Preliminary results are presented. The Q-value spectra for 133Sn, 131Sn and 135Te reveal a number of previously unobserved peaks. The angular distributions are compatible with the expected lf7/2 nature of the ground state of 133Sn, and 2p3/2 for the 3.4 MeV state in 131Sn.

  11. A MATLAB-based finite-element visualization of quantum reactive scattering. I. Collinear atom-diatom reactions.

    Science.gov (United States)

    Warehime, Mick; Alexander, Millard H

    2014-07-14

    We restate the application of the finite element method to collinear triatomic reactive scattering dynamics with a novel treatment of the scattering boundary conditions. The method provides directly the reactive scattering wave function and, subsequently, the probability current density field. Visualizing these quantities provides additional insight into the quantum dynamics of simple chemical reactions beyond simplistic one-dimensional models. Application is made here to a symmetric reaction (H+H2), a heavy-light-light reaction (F+H2), and a heavy-light-heavy reaction (F+HCl). To accompany this article, we have written a MATLAB code which is fast, simple enough to be accessible to a wide audience, as well as generally applicable to any problem that can be mapped onto a collinear atom-diatom reaction. The code and user's manual are available for download from http://www2.chem.umd.edu/groups/alexander/FEM.

  12. A MATLAB-based finite-element visualization of quantum reactive scattering. I. Collinear atom-diatom reactions

    International Nuclear Information System (INIS)

    We restate the application of the finite element method to collinear triatomic reactive scattering dynamics with a novel treatment of the scattering boundary conditions. The method provides directly the reactive scattering wave function and, subsequently, the probability current density field. Visualizing these quantities provides additional insight into the quantum dynamics of simple chemical reactions beyond simplistic one-dimensional models. Application is made here to a symmetric reaction (H+H2), a heavy-light-light reaction (F+H2), and a heavy-light-heavy reaction (F+HCl). To accompany this article, we have written a MATLAB code which is fast, simple enough to be accessible to a wide audience, as well as generally applicable to any problem that can be mapped onto a collinear atom-diatom reaction. The code and user's manual are available for download from http://www2.chem.umd.edu/groups/alexander/FEM

  13. Operando NMR spectroscopic analysis of proton transfer in heterogeneous photocatalytic reactions.

    Science.gov (United States)

    Wang, Xue Lu; Liu, Wenqing; Yu, Yan-Yan; Song, Yanhong; Fang, Wen Qi; Wei, Daxiu; Gong, Xue-Qing; Yao, Ye-Feng; Yang, Hua Gui

    2016-01-01

    Proton transfer (PT) processes in solid-liquid phases play central roles throughout chemistry, biology and materials science. Identification of PT routes deep into the realistic catalytic process is experimentally challenging, thus leaving a gap in our understanding. Here we demonstrate an approach using operando nuclear magnetic resonance (NMR) spectroscopy that allows to quantitatively describe the complex species dynamics of generated H2/HD gases and liquid intermediates in pmol resolution during photocatalytic hydrogen evolution reaction (HER). In this system, the effective protons for HER are mainly from H2O, and CH3OH evidently serves as an outstanding sacrificial agent reacting with holes, further supported by our density functional theory calculations. This results rule out controversy about the complicated proton sources for HER. The operando NMR method provides a direct molecular-level insight with the methodology offering exciting possibilities for the quantitative studies of mechanisms of proton-involved catalytic reactions in solid-liquid phases. PMID:27311326

  14. Characterization of ferritin core on redox reactions as a nanocomposite for electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Kwang Min [Center for Bio-Artificial Muscle and Department of Biomedical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Watt, Richard K.; Watt, Gerald D. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Choi, Sang H. [Advanced Materials and Processing Branch, NASA Langley Research Center, Hampton, VA 23681 (United States); Kim, Hyug-Han [Department of Chemistry, School of Advanced Science, Dankook University, Chonan 330-180 (Korea, Republic of); Kim, Sun I. [Center for Bio-Artificial Muscle and Department of Biomedical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Kim, Seon Jeong, E-mail: sjk@hanyang.ac.k [Center for Bio-Artificial Muscle and Department of Biomedical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of)

    2010-04-01

    The kinetics of the change in mass related to the release from and deposition onto the cavities of a ferritin in the SWCNT nanocomposite by electrochemical redox reactions, and the effects of the SWCNT on the kinetics of the variation in mass of the ferritin nanocomposite were characterized using an electrochemical quartz crystal microbalance. The change in mass of reconstituted ferritin in the SWCNT nanocomposite shows reversible variation and stability of the ferritin/SWCNT nanocomposite on redox reactions was confirmed by using a coreless apoferritin and a Fe{sup 2+} chelating agent. The ferritin/SWCNT nanocomposite is a good candidate for applications based on electron transfer, such as biosensor, biobatteries and electrodes for biofuel cell.

  15. Angular momentum and linear momentum transfer in intermediate-energy heavy-ion reactions

    International Nuclear Information System (INIS)

    In order to explore the changing role of angular momentum transfer to the heavy target-like fragment in heavy-ion reactions, the gamma-ray multiplicities associated with projectile residues were measured in the reaction of 20Ne with 181Ta in the energy range of 7.5 to 42 MeV/nucleon. From the gamma-ray multiplicities, the intrinsic spin of the target-like nucleus was determined and corrected for the spin removed by evaporated particles. Comparisons of the measured intrinsic spin with that expected from the missing linear momentum were found to be good at low energies but failed around a bombarding energy of 17 MeV/nucleon. From the results of these studies we infer that angular momentum and therefore linear momentum is being carried away in significant amounts by particles which were not detected

  16. BALANCE : a computer program for calculating mass transfer for geochemical reactions in ground water

    Science.gov (United States)

    Parkhurst, David L.; Plummer, L. Niel; Thorstenson, Donald C.

    1982-01-01

    BALANCE is a Fortran computer designed to define and quantify chemical reactions between ground water and minerals. Using (1) the chemical compositions of two waters along a flow path and (2) a set of mineral phases hypothesized to be the reactive constituents in the system, the program calculates the mass transfer (amounts of the phases entering or leaving the aqueous phase) necessary to account for the observed changes in composition between the two waters. Additional constraints can be included in the problem formulation to account for mixing of two end-member waters, redox reactions, and, in a simplified form, isotopic composition. The computer code and a description of the input necessary to run the program are presented. Three examples typical of ground-water systems are described. (USGS)

  17. Modification of polysulfone membranes via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Hydrophilic poly((poly(ethylene glycol) methyl ether methacrylate) (P(PEGMA)) and poly(glycidylmethacrylate) (PGMA) brushes were grafted from chloromethylated polysulfone (CMPSF) membrane surfaces via surface-initiated atom transfer radical polymerization (ATRP). Prior to ATRP, chloromethylation of PSF was performed beforehand and the obtained CMPSF was prepared into porous membranes by phase inversion process. It was demonstrated that the benzyl chloride groups on the CMPSF membrane surface afforded effective macroinitiators to graft the well-defined polymer brushes. 1H NMR was employed to confirm the structure of CMPSF. The grafting yield of P(PEGMA) and PGMA was determined by weight gain measurement. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the grafting of P(PEGMA) and PGMA chains. Water contact angle measurements indicated that the introduction of P(PEGMA) and PGMA graft chains promoted remarkably the surface hydrophilicity of PSF membranes. The effects of P(PEGMA) and PGMA immobilization on membrane morphology, permeability and fouling resistance were investigated. It was found that P(PEGMA) and PGMA grafts brought higher pure water flux, improved hydrophilic surface and better anti-protein absorption ability to PSF membranes after modification. And evidently, macromonomer P(PEGMA) brought much better properties to the PSF membranes than PGMA macromonomer.

  18. Colorful Polyelectrolytes: An Atom Transfer Radical Polymerization Route to Fluorescent Polystyrene Sulfonate.

    Science.gov (United States)

    Huberty, Wayne; Tong, Xiaowei; Balamurugan, Sreelatha; Deville, Kyle; Russo, Paul S; Zhang, Donghui

    2016-03-01

    A labeled green fluorescent polystyrene sulfonate (LNaPSS) has been synthesized using atom transfer radical polymerization of a styrene sulfonate monomer with a fluorescent co-monomer, fluorescein thiocyanate-vinyl aniline. As a result this 100 % sulfonated polymer contains no hydrophobic patches along the chain backbone besides the fluorescent marker itself. The concentration of the fluorescent monomer was kept low to maintain the characteristic properties of the anionic polyelectrolyte, LNaPSS. ATRP conditions facilitated the production of polymers spanning a range of molecular weights from 35,000 to 175,000 in gram-scale batches with polydispersity indices of 1.01-1.24. Molecular weight increased with the monomer to initiator ratio. Gel permeation chromatography results show a unimodal distribution, and the polymer structure was also confirmed by (1)H NMR and FT-IR spectroscopy. Fluorescence spectroscopy confirmed covalent bonding of fluorescein isothiocyanate to the polymer, indicating that the polymer is suitable as a probe in fluorescence microscopy. To demonstrate this ability, the polymer was used to locate structural features in salt crystals formed during drying, as in the evaporation of sea mist. A second application to probe diffusion studies is also demonstrated. PMID:26745991

  19. The role of electronic symmetry in charge-transfer-to-solvent reactions: Quantum nonadiabatic computer simulation of photoexcited sodium anions

    OpenAIRE

    Smallwood, C J; Bosma, W B; Larsen, R E; Schwartz, Benjamin J.

    2003-01-01

    Since charge-transfer-to-solvent (CTTS) reactions represent the simplest class of solvent-driven electron transfer reactions, there has been considerable interest in understanding the solvent motions responsible for electron ejection. The major question that we explore in this paper is what role the symmetry of the electronic states plays in determining the solvent motions that account for CTTS. To this end, we have performed a series of one-electron mixed quantum/classical nonadiabatic molec...

  20. Study of quark flavor-dependence in exclusive reactions at large momentum transfers

    International Nuclear Information System (INIS)

    The measurement of exclusive reactions at large momentum transfers provides an important testing ground for models of hard quark-quark scattering. We have measured cross sections or set upper limits for 12 meson-bryon (π/sup +-/p → pπ/sup +-/, p/rho//sup +-/, π+Δ/sup +-/, K+Σ/sup +-/, π/sup /minus//p → Λ0/Σ0K0, K/sup +-/p → pK/sup +-/) and 2 baryon-baryon (p/sup +-/p → pp/sup /plus minus/) reactions near 90/degree/ C.M. by studying the flavor-dependence of these 2 exclusive reactions at t = -9(GeV/c)/sup 2/, we have been able to demonstrate in a perturbative QCD picture that the quark-interchange mechanism is dominant over gluon exchange and quark-antiquark annihilation. We will also present preliminary results on many of these reactions at t = -5(GeV/c)/sup 2/ with better resolution and statistical precision. 145 refs., 3 figs

  1. A Stefan model for mass transfer in a rotating disk reaction vessel

    KAUST Repository

    BOHUN, C. S.

    2015-05-04

    Copyright © Cambridge University Press 2015. In this paper, we focus on the process of mass transfer in the rotating disk apparatus formulated as a Stefan problem with consideration given to both the hydrodynamics of the process and the specific chemical reactions occurring in the bulk. The wide range in the reaction rates of the underlying chemistry allows for a natural decoupling of the problem into a simplified set of weakly coupled convective-reaction-diffusion equations for the slowly reacting chemical species and a set of algebraic relations for the species that react rapidly. An analysis of the chemical equilibrium conditions identifies an expansion parameter and a reduced model that remains valid for arbitrarily large times. Numerical solutions of the model are compared to an asymptotic analysis revealing three distinct time scales and chemical diffusion boundary layer that lies completely inside the hydrodynamic layer. Formulated as a Stefan problem, the model generalizes the work of Levich (Levich and Spalding (1962) Physicochemical hydrodynamics, vol. 689, Prentice-Hall Englewood Cliffs, NJ) and will help better understand the natural limitations of the rotating disk reaction vessel when consideration is made for the reacting chemical species.

  2. Synthesis and Properties of Fe3O4@SiO2-g-PDMAEMA Prepared via Combination of Atom Transfer Radical Polymerization and "Click" Reaction%原子转移自由基聚合与“Click”反应相结合制备Fe3O4@SiO2-g-PDMAEMA及其性质研究

    Institute of Scientific and Technical Information of China (English)

    张世华; 朱汇雯; 张明祖; 倪沛红

    2011-01-01

    Poly[2-(N,N-dimethylamino)ethyl methacrylate](PDMAEMA) was prepared and grafted onto Fe3O4 magnetic nanoparticles encapsulated with SiO2(Fe3O4@SiO2) via combination of ATRP and "Click" reaction.So the magnetic nanoparticles grafted with PDMAEMA(Fe3O4@SiO2-g-PDMAEMA) on the sur-face were obtained.1H NMR and GPC tests were carried out to study the structure,molecular weight and polydispersity index(PDI) of alkynyl-capped PDMAEMA.TEM,FT-IR,TGA,DLS and Zeta potential tests were used to study the structures,morphologies,particle diameters and surface properties of Fe3O4@SiO2 and Fe3O4@SiO2-g-PDMAEMA,respectively.%结合原子转移自由基聚合(ATRP)与点击反应("Click"reaction),在SiO2包裹的Fe3O4磁性纳米粒子(Fe3O4@SiO2)表面接枝聚[甲基丙烯酸-2-(N,N-二甲氨基)乙酯](PDMAEMA),得到了表面接枝PDMAEMA的磁性纳米粒子(Fe3O4@SiO2-g-PDMAEMA).通过1H NMR和GPC测试,研究炔基封端的PDMAEMA的结构、分子量及分子量分布.通过透射电镜(TEM)、红外光谱(FT-IR)、热重分析(TGA)、动态光散射(DLS)和Zeta电位测试,研究了Fe3O4@SiO2和Fe3O4@SiO2-g-PDMAEMA的结构、形貌、粒径及表面性质.

  3. Factors That Control the Reactivity of Cobalt(III)-Nitrosyl Complexes in Nitric Oxide Transfer and Dioxygenation Reactions: A Combined Experimental and Theoretical Investigation.

    Science.gov (United States)

    Kumar, Pankaj; Lee, Yong-Min; Hu, Lianrui; Chen, Jianwei; Park, Young Jun; Yao, Jiannian; Chen, Hui; Karlin, Kenneth D; Nam, Wonwoo

    2016-06-22

    Metal-nitrosyl complexes are key intermediates involved in many biological and physiological processes of nitric oxide (NO) activation by metalloproteins. In this study, we report the reactivities of mononuclear cobalt(III)-nitrosyl complexes bearing N-tetramethylated cyclam (TMC) ligands, [(14-TMC)Co(III)(NO)](2+) and [(12-TMC)Co(III)(NO)](2+), in NO-transfer and dioxygenation reactions. The Co(III)-nitrosyl complex bearing 14-TMC ligand, [(14-TMC)Co(III)(NO)](2+), transfers the bound nitrosyl ligand to [(12-TMC)Co(II)](2+) via a dissociative pathway, {[(14-TMC)Co(III)(NO)](2+) → {(14-TMC)Co···NO}(2+)}, thus affording [(12-TMC)Co(III)(NO)](2+) and [(14-TMC)Co(II)](2+) as products. The dissociation of NO from the [(14-TMC)Co(III)(NO)](2+) complex prior to NO-transfer is supported experimentally and theoretically. In contrast, the reverse reaction, which is the NO-transfer from [(12-TMC)Co(III)(NO)](2+) to [(14-TMC)Co(II)](2+), does not occur. In addition to the NO-transfer reaction, dioxygenation of [(14-TMC)Co(III)(NO)](2+) by O2 produces [(14-TMC)Co(II)(NO3)](+), which possesses an O,O-chelated nitrato ligand and where, based on an experiment using (18)O-labeled O2, two of the three O-atoms in the [(14-TMC)Co(II)(NO3)](+) product derive from O2. The dioxygenation reaction is proposed to occur via a dissociative pathway, as proposed in the NO-transfer reaction, and via the formation of a Co(II)-peroxynitrite intermediate, based on the observation of phenol ring nitration. In contrast, [(12-TMC)Co(III)(NO)](2+) does not react with O2. Thus, the present results demonstrate unambiguously that the NO-transfer/dioxygenation reactivity of the cobalt(III)-nitrosyl complexes bearing TMC ligands is significantly influenced by the ring size of the TMC ligands and/or the spin state of the cobalt ion. PMID:27221953

  4. Conformity between IBM and TQM (SU(6) quadrupole phonon model) in treating two-nucleon transfer reactions

    Science.gov (United States)

    Kyrchev, G.; Paar, V.

    1983-03-01

    It is shown that TQM is capable of treating two-nucleon transfer (TNT) reactions in an analogous manner to IBM. A proof that the IBM two-nucleon transfer amplitudes can be identically converted into standard matrix elements for TQM, is presented, using the relation between the Schwinger and Holstein-Primakoff representations of the SU(6) generators.

  5. Photoinduced C-C bond cleavage via electron-transfer reactions: visible-light-mediated scission of tertiary amines

    Energy Technology Data Exchange (ETDEWEB)

    Lee, L.Y.C.; Ci, X.; Giannotti, C.; Whitten, D.G.

    1986-01-08

    This paper reports the electron-transfer photochemistry of some substituted tertiary amines that contain potentially labile C-C bonds adjacent to the amine. Results are presented which indicate that photoinduced electron transfer can lead to reactions in which the net process involves use of visible light to mediate selective cleavage of C-C bonds to produce radicals. 34 references.

  6. On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants

    Science.gov (United States)

    Marcus, R. A.

    1962-01-01

    Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)

  7. Reverse atom transfer radical polymerization (RATRP) for anti-clotting PU-LaCl3-g-P(MPC) films

    International Nuclear Information System (INIS)

    Highlights: ► A facile and efficient approach for surface modification of PU was introduced. ► MPC was grafted onto the surface of PU film by RATRP. ► Some free La3+ ions reacted with CPTM and the product served as mixed ligand complex. ► The obtained PUs had good blood compatibility and a possible usage in biomedicine. - Abstract: Low grafting density is a disadvantage both in reverse atom transfer radical polymerization (RATRP) and ATRP. In this work, the surfaces of polyurethane (PU) were treated by LaCl3·6H2O to obtain modified surfaces with hydrated layers. The reaction of surface-initiated RATRP was carried out easily, which may be attributed to the enriched hydroxyl groups on the hydrated layers. An innovation found in this work is that some free lanthanum ions (La3+) reacted with the silane coupling agent (CPTM) and the product served as mixed ligand complex. The mixed ligand complex instead of conventional 2,2′-bipyridine was adopted to serve as a ligand in the process of RATRP. As a result, PU surfaces grafted with well-defined polymer brushes (MPC) were obtained. PU substrates before and after modification were characterized by FTIR, XPS, AFM, SEM, SCA, respectively. The results showed that zwitterionic brushes were successfully fabricated on the PU surfaces (P(MPC)), and the content of the grafted layer increased gradually with polymerization time with the grafting density as high as 97.9%. The blood compatibility of the PU substrates was evaluated by plasma recalcification profiles test and platelet adhesion tests in vitro. It was found that all PU functionalized with zwitterionic brush showed improved resistance to nonspecific protein adsorption and platelet adhesion.

  8. Reaction layer growth and reaction heat of U-Mo/Al dispersion fuels using centrifugally atomized powders

    Science.gov (United States)

    Ryu, Ho Jin; Han, Young Soo; Park, Jong Man; Park, Soon Dal; Kim, Chang Kyu

    2003-09-01

    The growth behavior of reaction layers and heat generation during the reaction between U-Mo powders and the Al matrix in U-Mo/Al dispersion fuels were investigated. Annealing of 10 vol.% U-10Mo/Al dispersion fuels at temperatures from 500 to 550 °C was carried out for 10 min to 36 h to measure the growth rate and the activation energy for the growth of reaction layers. The concentration profiles of reaction layers between the U-10Mo vs. Al diffusion couples were measured and the integrated interdiffusion coefficients were calculated for the U and Al in the reaction layers. Heat generation of U-Mo/Al dispersion fuels with 10-50 vol.% of U-Mo fuel during the thermal cycle from room temperature to 700 °C was measured employing the differential scanning calorimetry. Exothermic heat from the reaction between U-Mo and the Al matrix is the largest when the volume fraction of U-Mo fuel is about 30 vol.%. The unreacted fraction in the U-Mo powders increases as the volume fraction of U-Mo fuel increases from 30 to 50 vol.%.

  9. Cold heteronuclear atom-ion collisions

    CERN Document Server

    Zipkes, Christoph; Ratschbacher, Lothar; Sias, Carlo; Köhl, Michael

    2010-01-01

    We study cold heteronuclear atom ion collisions by immersing a trapped single ion into an ultracold atomic cloud. Using ultracold atoms as reaction targets, our measurement is sensitive to elastic collisions with extremely small energy transfer. The observed energy-dependent elastic atom-ion scattering rate deviates significantly from the prediction of Langevin but is in full agreement with the quantum mechanical cross section. Additionally, we characterize inelastic collisions leading to chemical reactions at the single particle level and measure the energy-dependent reaction rate constants. The reaction products are identified by in-trap mass spectrometry, revealing the branching ratio between radiative and non-radiative charge exchange processes.

  10. Peroxyl Radical Reactions in Water Solution: A Gym for Proton-Coupled Electron-Transfer Theories.

    Science.gov (United States)

    Amorati, Riccardo; Baschieri, Andrea; Morroni, Gloria; Gambino, Rossana; Valgimigli, Luca

    2016-06-01

    The reactions of alkylperoxyl radicals with phenols have remained difficult to investigate in water. We describe herein a simple and reliable method based on the inhibited autoxidation of water/THF mixtures, which we calibrated against pulse radiolysis. With this method we measured the rate constants kinh for the reactions of 2-tetrahydrofuranylperoxyl radicals with reference compounds: urate, ascorbate, ferrocenes, 2,2,5,7,8-pentamethyl-6-chromanol, Trolox, 6-hydroxy-2,5,7,8-tetramethylchroman-2-acetic acid, 2,6-di-tert-butyl-4-methoxyphenol, 4-methoxyphenol, catechol and 3,5-di-tert-butylcatechol. The role of pH was investigated: the value of kinh for Trolox and 4-methoxyphenol increased 11- and 50-fold from pH 2.1 to 12, respectively, which indicate the occurrence of a SPLET-like mechanism. H(D) kinetic isotope effects combined with pH and solvent effects suggest that different types of proton-coupled electron transfer (PCET) mechanisms are involved in water: less electron-rich phenols react at low pH by concerted electron-proton transfer (EPT) to the peroxyl radical, whereas more electron-rich phenols and phenoxide anions react by multi-site EPT in which water acts as proton relay.

  11. Pro duction of Exotic Nuclei in Low-Energy Multi-Nucleon Transfer Reactions

    Institute of Scientific and Technical Information of China (English)

    VI Zagrebaev; Walter Greiner

    2015-01-01

    Multinucleon transfer processes in low-energy heavy ion collisions open a new field of re-search in nuclear physics, namely, production and studying properties of heavy neutron rich nuclei. This not-yet-explored area of the nuclear map is extremely important for understanding the astrophysical nu-cleosynthesis and the origin of heavy elements. Beams of very heavy U-like ions are needed to produce new long-living isotopes of transfermium and superheavy elements located very close to the island of sta-bility. The calculated cross sections are high enough to perform the experiments at available accelerators. Beams of medium-mass ions (such as 136Xe, 192Os, 198Pt) can be used for the production of neutron rich nuclei located along the neutron closed shell N=126 (the last waiting point) having the largest impact on the astrophysical r-process. The Low-energy multinucleon transfer reactions is a very efficient tool also for the production and spectroscopic study of light exotic nuclei. The corresponding cross sections are 2 or 3 orders of magnitude larger as compared with high energy fragmentation reactions.

  12. Kinetic of the gas-phase reactions of OH radicals and Cl atoms with Diethyl Ethylphosphonate and Triethyl Phosphate

    KAUST Repository

    Laversin, H.

    2015-11-30

    In this paper, the relative-rate technique has been used to obtain rate coefficients for the reaction of two organophosphorus compounds: Triethyl phosphate (TEP) and Diethyl ethylphosphonate (DEEP) with OH radicals and Cl atoms at atmospheric pressure and at different temperatures. The calculated rate constants were fitted to the Arrhenius expression over the temperature range 298 – 352 K. The following expressions (in cm3molecule-1s-1) were obtained for the reactions of OH and CL with DEEP and TEP: kOH+DEEP= (7.84±0.65)x10-14exp((1866±824)/T), kOH+TEP = (6.54±0.42)x10-14exp((1897±626)/T), kCl+DEEP = (5.27± 0.80)x10−11exp(765±140/T) and kCl+TEP = (5.23± 0.80)x10−11exp(736± 110/T). These results show that the reaction of the studied compounds with Cl atoms proceeds more rapidly than that with OH radicals. The related tropospheric lifetimes suggest that once emitted into the atmosphere, TEP and DEEP can be removed within a few hours in areas close to their emission sources. TEP and DEEP are principally removed by OH radicals. However, in coastal areas where the Cl atoms’ concentration is higher, TEP and DEEP removal by reaction with Cl atoms could be a competitive process.

  13. Validated spectrophotometric methods for determination of sodium valproate based on charge transfer complexation reactions

    Science.gov (United States)

    Belal, Tarek S.; El-Kafrawy, Dina S.; Mahrous, Mohamed S.; Abdel-Khalek, Magdi M.; Abo-Gharam, Amira H.

    2016-02-01

    This work presents the development, validation and application of four simple and direct spectrophotometric methods for determination of sodium valproate (VP) through charge transfer complexation reactions. The first method is based on the reaction of the drug with p-chloranilic acid (p-CA) in acetone to give a purple colored product with maximum absorbance at 524 nm. The second method depends on the reaction of VP with dichlone (DC) in dimethylformamide forming a reddish orange product measured at 490 nm. The third method is based upon the interaction of VP and picric acid (PA) in chloroform resulting in the formation of a yellow complex measured at 415 nm. The fourth method involves the formation of a yellow complex peaking at 361 nm upon the reaction of the drug with iodine in chloroform. Experimental conditions affecting the color development were studied and optimized. Stoichiometry of the reactions was determined. The proposed spectrophotometric procedures were effectively validated with respect to linearity, ranges, precision, accuracy, specificity, robustness, detection and quantification limits. Calibration curves of the formed color products with p-CA, DC, PA and iodine showed good linear relationships over the concentration ranges 24-144, 40-200, 2-20 and 1-8 μg/mL respectively. The proposed methods were successfully applied to the assay of sodium valproate in tablets and oral solution dosage forms with good accuracy and precision. Assay results were statistically compared to a reference pharmacopoeial HPLC method where no significant differences were observed between the proposed methods and reference method.

  14. Application of Magnetic Dicationic Ionic Liquid Phase Transfer Catalyst in Nuclophilic Substitution Reactions of Benzyl Halids in Water

    Directory of Open Access Journals (Sweden)

    Manouchehr Aghajeri

    2016-06-01

    Full Text Available magnetic dicationic ionic liquid (MDIL was successfully prepared and evaluated as phase-transfer catalyst for nucleophilic substitution reactions. The reactions was occurred in water and furnished the corresponding benzyl derivatives in high yields. No evidence for the formation of by-product for example benzyl alcohol of the reaction was observed and the products were obtained in pure form without further purification.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Hongying; Huang, Guangming, E-mail: gmhuang@ustc.edu.cn

    2015-03-31

    Graphical abstract: Direct and humidity independent mass spectrometry analysis of gas phase chemicals could be achieved via ambient proton transfer ionization, ion intensity was found to be stable with humidity ranged from ∼10% to ∼100%. - Highlights: • A humidity independent mass spectrometric method for gas phase samples analysis. • A universal and good sensitivity method. • The method can real time identify plant released raw chemicals. - Abstract: In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m{sup −3}, ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages.

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

    International Nuclear Information System (INIS)

    Graphical abstract: Direct and humidity independent mass spectrometry analysis of gas phase chemicals could be achieved via ambient proton transfer ionization, ion intensity was found to be stable with humidity ranged from ∼10% to ∼100%. - Highlights: • A humidity independent mass spectrometric method for gas phase samples analysis. • A universal and good sensitivity method. • The method can real time identify plant released raw chemicals. - Abstract: In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m−3, ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages

  17. Protein microarrays based on polymer brushes prepared via surface-initiated atom transfer radical polymerization.

    Science.gov (United States)

    Barbey, Raphael; Kauffmann, Ekkehard; Ehrat, Markus; Klok, Harm-Anton

    2010-12-13

    Polymer brushes represent an interesting platform for the development of high-capacity protein binding surfaces. Whereas the protein binding properties of polymer brushes have been investigated before, this manuscript evaluates the feasibility of poly(glycidyl methacrylate) (PGMA) and PGMA-co-poly(2-(diethylamino)ethyl methacrylate) (PGMA-co-PDEAEMA) (co)polymer brushes grown via surface-initiated atom transfer radical polymerization (SI-ATRP) as protein reactive substrates in a commercially available microarray system using tantalum-pentoxide-coated optical waveguide-based chips. The performance of the polymer-brush-based protein microarray chips is assessed using commercially available dodecylphosphate (DDP)-modified chips as the benchmark. In contrast to the 2D planar, DDP-coated chips, the polymer-brush-covered chips represent a 3D sampling volume. This was reflected in the results of protein immobilization studies, which indicated that the polymer-brush-based coatings had a higher protein binding capacity as compared to the reference substrates. The protein binding capacity of the polymer-brush-based coatings was found to increase with increasing brush thickness and could also be enhanced by copolymerization of 2-(diethylamino)ethyl methacrylate (DEAEMA), which catalyzes epoxide ring-opening of the glycidyl methacrylate (GMA) units. The performance of the polymer-brush-based microarray chips was evaluated in two proof-of-concept microarray experiments, which involved the detection of biotin-streptavidin binding as well as a model TNFα reverse assay. These experiments revealed that the use of polymer-brush-modified microarray chips resulted not only in the highest absolute fluorescence readouts, reflecting the 3D nature and enhanced sampling volume provided by the brush coating, but also in significantly enhanced signal-to-noise ratios. These characteristics make the proposed polymer brushes an attractive alternative to commercially available, 2D microarray

  18. One nucleon transfer reactions around $^{68}$Ni at REX-ISOLDE

    CERN Multimedia

    Blazhev, A A; Kruecken, R; Mertzimekis, T; Darby, I G; Lagogiannis, A; Habs, D; Diriken, J V J; Patronis, N

    2008-01-01

    We intend to investigate the single particle properties of the neutron-rich Ni isotopes in the mass region around $^{68}$Ni and at a later stage towards the doubly-magic $^{78}$Ni. As a first experiment we propose to study the single particle character of the ground and first excited states of $^{67}$Ni. This nucleus will be the projectile-like reaction product for the one-neutron transfer reaction. A $^{66}$Ni beam at 3A MeV delivered from REX-ISOLDE will be directed on a CD$_{2}$ target. Protons produced from the (d,p) reaction will be detected either in singles or in coincidence with ${\\gamma}$-rays recorded by the MINIBALL array. The particles will be detected by the newly-built Si position-sensitive barrel configuration. The objectives of this work are the unambiguous determination of the spins and parities of the first excited states of $^{67}$Ni and measurement of the relative spectroscopic factors of those states as well as of the ground state. The experimental results will be compared with those from...

  19. Multinucleon transfer in O,1816,19F+208Pb reactions at energies near the fusion barrier

    Science.gov (United States)

    Rafferty, D. C.; Dasgupta, M.; Hinde, D. J.; Simenel, C.; Simpson, E. C.; Williams, E.; Carter, I. P.; Cook, K. J.; Luong, D. H.; McNeil, S. D.; Ramachandran, K.; Vo-Phuoc, K.; Wakhle, A.

    2016-08-01

    Background: Nuclear reactions are complex, involving collisions between composite systems where many-body dynamics determines outcomes. Successful models have been developed to explain particular reaction outcomes in distinct energy and mass regimes, but a unifying picture remains elusive. The irreversible transfer of kinetic energy from the relative motion of the collision partners to their internal states, as is known to occur in deep inelastic collisions, has yet to be successfully incorporated explicitly into fully quantal reaction models. The influence of these processes on fusion is not yet quantitatively understood. Purpose: To investigate the population of high excitation energies in transfer reactions at sub-barrier energies, which are precursors to deep inelastic processes, and their dependence on the internuclear separation. Methods: Transfer probabilities and excitation energy spectra have been measured in collisions of O,1816,19F+208Pb , at various energies below and around the fusion barrier, by detecting the backscattered projectile-like fragments in a Δ E -E telescope. Results: The relative yields of different transfer outcomes are strongly driven by Q values, but change with the internuclear separation. In 16O+208Pb , single nucleon transfer dominates, with a strong contribution from -2 p transfer close to the Coulomb barrier, though this channel becomes less significant in relation to the -2 p 2 n transfer channel at larger separations. For 18O+208Pb , the -2 p 2 n channel is the dominant charge transfer mode at all separations. In the reactions with 19F,-3 p 2 n transfer is significant close to the barrier, but falls off rapidly with energy. Multinucleon transfer processes are shown to lead to high excitation energies (up to ˜15 MeV), which is distinct from single nucleon transfer modes which predominantly populate states at low excitation energy. Conclusions: Kinetic energy is transferred into internal excitations following transfer, with this

  20. Coke Formation in a Zeolite Crystal During the Methanol-to-Hydrocarbons Reaction as Studied with Atom Probe Tomography.

    Science.gov (United States)

    Schmidt, Joel E; Poplawsky, Jonathan D; Mazumder, Baishakhi; Attila, Özgün; Fu, Donglong; de Winter, D A Matthijs; Meirer, Florian; Bare, Simon R; Weckhuysen, Bert M

    2016-09-01

    Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub-nm length scale in a single zeolite ZSM-5 crystal, which has been partially deactivated by the methanol-to-hydrocarbons reaction using (13) C-labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30-60 (13) C atoms. These clusters correlate with local increases in Brønsted acid site density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. This nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation.

  1. Coke Formation in a Zeolite Crystal During the Methanol-to-Hydrocarbons Reaction as Studied with Atom Probe Tomography.

    Science.gov (United States)

    Schmidt, Joel E; Poplawsky, Jonathan D; Mazumder, Baishakhi; Attila, Özgün; Fu, Donglong; de Winter, D A Matthijs; Meirer, Florian; Bare, Simon R; Weckhuysen, Bert M

    2016-09-01

    Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub-nm length scale in a single zeolite ZSM-5 crystal, which has been partially deactivated by the methanol-to-hydrocarbons reaction using (13) C-labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30-60 (13) C atoms. These clusters correlate with local increases in Brønsted acid site density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. This nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation. PMID:27485276

  2. Suppression of angular momentum transfer in cold collisions of transition metal atoms in ground States with nonzero orbital angular momentum.

    Science.gov (United States)

    Hancox, Cindy I; Doret, S Charles; Hummon, Matthew T; Krems, Roman V; Doyle, John M

    2005-01-14

    The Zeeman relaxation rate in cold collisions of Ti(3d(2)4s(2) 3F2) with He is measured. We find that collisional transfer of angular momentum is dramatically suppressed due to the presence of the filled 4s(2) shell. The degree of electronic interaction anisotropy, which is responsible for Zeeman relaxation, is estimated to be about 200 times smaller in the Ti-He complex than in He complexes with typical non-S-state atoms.

  3. CMOS compatible strategy based on selective atomic layer deposition of a hard mask for transferring block copolymer lithography patterns

    International Nuclear Information System (INIS)

    A generic, CMOS compatible strategy for transferring a block copolymer template to a semiconductor substrate is demonstrated. An aluminum oxide (Al2O3) hard mask is selectively deposited by atomic layer deposition in an organized array of holes obtained in a PS matrix via PS-b-PMMA self-assembly. The Al2O3 nanodots act as a highly resistant mask to plasma etching, and are used to pattern high aspect ratio (>10) silicon nanowires and nanopillars.

  4. Synthesis of Highly Branched Poly(ε-caprolactone) by Self-condensing Atom Transfer Radical Polymerization of Macroinimers

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Branched poly(ε-caprolactone) was synthesized by self-condensing atom transfer radical polymerization of macroinimer, α-acryloyoxy-ω-2-bromopropionyloxy poly(ε-caprolactone),which was prepared by enzyme-catalyzed ring-opening polymerization of ε-caprolactone with 2-hydroxylethyl acrylate as initiator and esterification of the ω-hydroxyl group of the obtained poly(ε-caprolactone) by 2-bromopropionyl bromide.

  5. Ultracold magnetically tunable interactions without radiative-charge-transfer losses between Ca+, Sr+, Ba+, and Yb+ ions and Cr atoms

    Science.gov (United States)

    Tomza, Michał

    2015-12-01

    The Ca+, Sr+, Ba+, and Yb+ ions immersed in an ultracold gas of the Cr atoms are proposed as experimentally feasible heteronuclear systems in which ion-atom interactions at ultralow temperatures can be controlled with magnetically tunable Feshbach resonances without charge transfer and radiative losses. Ab initio techniques are applied to investigate electronic-ground-state properties of the (CaCr)+, (SrCr)+, (BaCr)+, and (YbCr)+ molecular ions. The potential energy curves, permanent electric dipole moments, and static electric dipole polarizabilities are computed. The spin-restricted open-shell coupled-cluster method restricted to single, double, and noniterative triple excitations and the multireference configuration-interaction method restricted to single and double excitations are employed. The scalar relativistic effects are included within the small-core energy-consistent pseudopotentials. The leading long-range induction and dispersion interaction coefficients are also reported. Finally, magnetic Feshbach resonances between the Ca+, Sr+, Ba+, and Yb+ ions interacting with the Cr atoms are analyzed. The present proposal opens the way towards robust quantum simulations and computations with ultracold ion-atom systems free of radiative charge-transfer losses.

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

    Science.gov (United States)

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

    2016-02-10

    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. PMID:26805392

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

    Science.gov (United States)

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

    2016-02-10

    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.

  8. Numerical simulation of ultrasonic enhancement on mass transfer in liquid-solid reaction by a new computational model.

    Science.gov (United States)

    Jiao, Qingbin; Bayanheshig; Tan, Xin; Zhu, Jiwei

    2014-03-01

    Mass transfer coefficient is an important parameter in the process of mass transfer. It can reflect the degree of enhancement of mass transfer process in liquid-solid reaction and in non-reactive systems like dissolution and leaching, and further verify the issues by experiments in the reaction process. In the present paper, a new computational model quantitatively solving ultrasonic enhancement on mass transfer coefficient in liquid-solid reaction is established, and the mass transfer coefficient on silicon surface with a transducer at frequencies of 40 kHz, 60 kHz, 80 kHz and 100 kHz has been numerically simulated. The simulation results indicate that mass transfer coefficient increases with the increasing of ultrasound power, and the maximum value of mass transfer coefficient is 1.467 × 10(-4) m/s at 60 kHz and the minimum is 1.310 × 10(-4) m/s at 80 kHz in the condition when ultrasound power is 50 W (the mass transfer coefficient is 2.384 × 10(-5) m/s without ultrasound). The extrinsic factors such as temperature and transducer diameter and distance between reactor and ultrasound source also influence the mass transfer coefficient on silicon surface. Mass transfer coefficient increases with the increasing temperature, with the decreasing distance between silicon and central position, with the decreasing of transducer diameter, and with the decreasing of distance between reactor and ultrasound source at the same ultrasonic power and frequency. The simulation results indicate that the computational model can quantitatively solve the ultrasonic enhancement on mass transfer coefficient.

  9. Neutron spectroscopic factors of 55Ni hole-states from (p,d transfer reactions

    Directory of Open Access Journals (Sweden)

    A. Sanetullaev

    2014-09-01

    Full Text Available Spectroscopic information has been extracted on the hole-states of 55Ni, the least known of the quartet of nuclei (55Ni, 57Ni, 55Co and 57Cu, one nucleon away from 56Ni, the N=Z=28 double magic nucleus. Using the H1(Ni56,dNi55 transfer reaction in inverse kinematics, neutron spectroscopic factors, spins and parities have been extracted for the f7/2, p3/2 and the s1/2 hole-states of 55Ni. These new data provide a benchmark for large basis calculations that include nucleonic orbits in both the sd and pf shells. State of the art calculations have been performed to describe the excitation energies and spectroscopic factors of the s1/2 hole-state below Fermi energy.

  10. First measurement of transferred polarization in the exclusive ep-->e'K+Lambda--> reaction.

    Science.gov (United States)

    Carman, D S; Joo, K; Mestayer, M D; Raue, B A; Adams, G; Ambrozewicz, P; Anciant, E; Anghinolfi, M; Armstrong, D S; Asavapibhop, B; Audit, G; Auger, T; Avakian, H; Bagdasaryan, H; Ball, J P; Barrow, S P; Battaglieri, M; Beard, K; Bektasoglu, M; Bellis, M; Bennhold, C; Bianchi, N; Biselli, A S; Boiarinov, S; Bonner, B E; Bouchigny, S; Bradford, R; Branford, D; Briscoe, W J; Brooks, W K; Burkert, V D; Butuceanu, C; Calarco, J R; Carnahan, B; Cazes, A; Cetina, C; Ciciani, L; Clark, R; Cole, P L; Coleman, A; Cords, D; Corvisiero, P; Crabb, D; Crannell, H; Cummings, J P; DeSanctis, E; Degtyarenko, P V; Denizli, H; Dennis, L; DeVita, R; Dharmawardane, K V; Dhuga, K S; Djalali, C; Dodge, G E; Doughty, D; Dragovitsch, P; Dugger, M; Dytman, S; Dzyubak, O P; Eckhause, M; Egiyan, H; Egiyan, K S; Elouadrhiri, L; Empl, A; Eugenio, P; Fatemi, R; Fedotov, G; Feuerbach, R J; Ficenec, J; Forest, T A; Funsten, H; Gaff, S J; Gai, M; Garçon, M; Gavalian, G; Gilad, S; Gilfoyle, G P; Giovanetti, K L; Girard, P; Golovach, E; Gordon, C I O; Griffioen, K; Grimes, S; Guidal, M; Guillo, M; Guo, L; Gyurjyan, V; Hadjidakis, C; Hakobyan, R S; Hardie, J; Heddle, D; Heimberg, P; Hersman, F W; Hicks, K; Hicks, R S; Holtrop, M; Hu, J; Hyde-Wright, C E; Ishkhanov, B; Ito, M M; Jenkins, D; Kelley, J H; Kellie, J D; Khandaker, M; Kim, K Y; Kim, K; Kim, W; Klein, A; Klein, F J; Klimenko, A V; Klusman, M; Kossov, M; Kramer, L H; Kuang, Y; Kuhn, S E; Kuhn, J; Lachniet, J; Laget, J M; Lawrence, D; Li, J; Livingston, K; Longhi, A; Lukashin, K; Manak, J J; Marchand, C; Mart, T; McAleer, S; McCarthy, J; McNabb, J W C; Mecking, B A; Mehrabyan, S; Melone, J J; Meyer, C A; Mikhailov, K; Minehart, R; Mirazita, M; Miskimen, R; Mokeev, V; Morand, L; Morrow, S A; Mozer, M U; Muccifora, V; Mueller, J; Murphy, L Y; Mutchler, G S; Napolitano, J; Nasseripour, R; Nelson, S O; Niccolai, S; Niculescu, G; Niculescu, I; Niczyporuk, B B; Niyazov, R A; Nozar, M; O'Rielly, G V; Opper, A K; Osipenko, M; Park, K; Paschke, K; Pasyuk, E; Peterson, G; Pivnyuk, N; Pocanic, D; Pogorelko, O; Polli, E; Pozdniakov, S; Preedom, B M; Price, J W; Prok, Y; Protopopescu, D; Qin, L M; Riccardi, G; Ricco, G; Ripani, M; Ritchie, B G; Ronchetti, F; Rossi, P; Rowntree, D; Rubin, P; Sabatié, F; Sabourov, K; Salgado, C; Santoro, J; Sapunenko, V; Schumacher, R A; Serov, V S; Sharabian, Y G; Shaw, J; Simionatto, S; Skabelin, A V; Smith, E S; Smith, L C; Sober, D I; Spraker, M; Stavinsky, A; Stepanyan, S; Stoler, P; Taiuti, M; Taylor, S; Tedeschi, D J; Thoma, U; Thompson, R; Todor, L; Tur, C; Ungaro, M; Vineyard, M F; Vlassov, A V; Wang, K; Weinstein, L B; Weller, H; Weygand, D P; Whisnant, C S; Wolin, E; Wood, M H; Yegneswaran, A; Yun, J; Zhang, B; Zhao, J; Zhou, Z

    2003-04-01

    The first measurements of the transferred polarization for the exclusive e-->p-->e(')K+Lambda--> reaction have been performed at Jefferson Laboratory using the CLAS spectrometer. A 2.567 GeV beam was used to measure the hyperon polarization over Q2 from 0.3 to 1.5 (GeV/c)(2), W from 1.6 to 2.15 GeV, and over the full K+ center-of-mass angular range. Comparison with predictions of hadrodynamic models indicates strong sensitivity to the underlying resonance contributions. A nonrelativistic quark-model interpretation of our data suggests that the ssmacr; quark pair is produced with spins predominantly antialigned. Implications for the validity of the most widely used quark-pair creation operator are discussed. PMID:12689277

  11. Effect of phenol and halogenated phenols on energy transfer reactions of rat liver mitochondria.

    Directory of Open Access Journals (Sweden)

    Izushi,Fumio

    1988-02-01

    Full Text Available The in vitro effects of phenol and p-halogenated phenols on mitochondrial energy transfer reactions were examined using isolated rat liver mitochondria. The relationship between physiochemical properties of phenolic compounds and their effects on mitochondria were studied. Phenol and p-halogenated phenols induced the release of K+ ions from mitochondria, suggesting a change in permeability to K+ ions. A decrease in the respiratory control index, an increase in K+ release and stimulation of latent ATPase activity were observed with these compounds in the descending order of p-iodophenol, p-bromophenol, p-chlorophenol, p-fluorophenol and phenol. The concentrations of the phenolic compounds resulting in fifty percent inhibition of the respiratory control index and those resulting in fifty percent release of K+ ions significantly correlated with Hammett's substituent constant (sigma and the hydrophobic binding constant (pi of the compounds.

  12. Neutron spectroscopic factors of $^{55}$Ni hole-states from (p,d) transfer reactions

    CERN Document Server

    Sanetullaev, A; Lynch, W G; Lee, Jenny; Bazin, D; Chan, K P; Coupland, D; Henzl, V; Henzlova, D; Kilburn, M; Rogers, A M; Sun, Z Y; Youngs, M; Charity, R J; Sobotka, L G; Famiano, M; Hudan, S; Shapira, D; Peters, W A; Barbieri, C; Hjorth-Jensen, M; Horoi, M; Otsuka, T; Suzuki, T; Utsuno, Y

    2014-01-01

    Spectroscopic information has been extracted on the hole-states of $^{55}$Ni, the least known of the quartet of nuclei ($^{55}$Ni, $^{57}$Ni, $^{55}$Co and $^{57}$Co), one neutron away from $^{56}$Ni, the N=Z=28 double magic nucleus. Using the $^{1}$H($^{56}$Ni,d)$^{55}$Ni transfer reaction in inverse kinematics, neutron spectroscopic factors, spins and parities have been extracted for the f$_{7/2}$, p$_{3/2}$ and the s$_{1/2}$ hole-states of $^{55}$Ni. This new data provides a benchmark for large basis calculations that include nucleonic orbits in both the sd and pf shells. State of the art calculations have been performed to describe the excitation energies and spectroscopic factors of the s$_{1/2}$ hole-state below Fermi energy.

  13. Determination of Reactive Intermediates During Anodic Oxygen-transfer Reactions at Lead Dioxide

    Institute of Scientific and Technical Information of China (English)

    AI Shi-yun; ZHANG Wen; GAO Meng-nan; GU Fen-lin; WANG Qing-jiang; JIN Li-tong

    2004-01-01

    The anodic discharge of water to produce adsorbed hydroxyl free radicals(*OH) is considered to be a prerequisite to anodic O-transfer reactions at a PbO2 electrode. In this work, a method was studied by means of high-performance liquid chromatography(HPLC) combined with electrochemical detection(ED) so as to investigate the production of hydroxyl free radicals(*OH) in the process of the anodic discharge of H2O at a PbO2 electrode. The voltammetric data obtained at the PbO2 electrode for the oxidation of salicylic acid to salicylate hydroxylation products(DHBAs) and the detection of DHBAs by means of HPLC-ED confirm the proposed mechanism.

  14. Proton-transfer reaction dynamics and energetics in calcification and decalcification.

    Science.gov (United States)

    Suwa, Ryota; Hatta, Masayuki; Ichikawa, Kazuhiko

    2014-10-13

    CaCO3 -saturated saline waters at pH values below 8.5 are characterized by two stationary equilibrium states: reversible chemical calcification/decalcification associated with acid dissociation, Ca(2+) +HCO3 (-) ⇌CaCO3 +H(+) ; and reversible static physical precipitation/dissolution, Ca(2+) +CO3 (2-) ⇌CaCO3 . The former reversible reaction was determined using a strong base and acid titration. The saturation state described by the pH/PCO2 -independent solubility product, [Ca(2+) ][CO3 (2-) ], may not be observed at pH below 8.5 because [Ca(2+) ][CO3 (2-) ]/([Ca(2+) ][HCO3 (-) ]) ≪1. Since proton transfer dynamics controls all reversible acid dissociation reactions in saline waters, the concentrations of calcium ion and dissolved inorganic carbon (DIC) were expressed as a function of dual variables, pH and PCO2 . The negative impact of ocean acidification on marine calcifying organisms was confirmed by applying the experimental culture data of each PCO2 /pH-dependent coral polyp skeleton weight (Wskel) to the proton transfer idea. The skeleton formation of each coral polyp was performed in microspaces beneath its aboral ectoderm. This resulted in a decalcification of 14 weight %, a normalized CaCO3 saturation state Λ of 1.3 at PCO2 ≈400 ppm and pH ≈8.0, and serious decalcification of 45 % and Λ 2.5 at PCO2 ≈1000 ppm and pH ≈7.8.

  15. Three-Body Model Calculation of Spin Distribution in Two-Nucleon Transfer Reaction

    CERN Document Server

    Ogata, Kazuyuki; Chiba, Satoshi

    2011-01-01

    The differential cross sections of two-nucleon transfer reactions 238U(18O,16O)240U around 10 MeV per nucleon are calculated by one-step Born-approximation with a 16O+2n+238U three-body model. The three-body wave function in the initial channel is obtained with the continuum-discretized coupled-channels method, and that in the final channel is evaluated with adiabatic approximation. The resulting cross sections have a peak around the grazing angle, and the spin distribution, i.e., the cross section at the peak as a function of the transferred spin, is investigated. The shape of the spin distribution is found not sensitive to the incident energies, optical potentials, and treatment of the breakup channels both in the initial and final states, while it depends on the excitation energy of the residual nucleus 240U. The peak of the spin distribution moves to the large-spin direction as the excitation energy increases. To fulfill the condition that the peak position should not exceeds 10 hbar, which is necessary f...

  16. The protein's role in triplet energy transfer in bacterial reaction centers.

    Energy Technology Data Exchange (ETDEWEB)

    Laible, P. D.

    1998-08-14

    When photosynthetic organisms are subjected to high-light conditions in nature, electron transfer becomes blocked as the rate of conversion of light into charge-separated states in the reaction center (RC) exceeds the capacity of the soluble carriers involved in cyclic electron transfer. In that event, a well-characterized T{sub 0}-polarized triplet state {sup T}P, is formed on the primary donor, P, from the P{sup +}H{sub A}{sup {minus}} state (reviewed in [1]). In an aerobic or semi-aerobic environment, the major role of the carotenoid (C), also bound by the RC, is to quench {sup T}P prior to its sensitization of the {sup 1}{Delta}{sub g} singlet state of oxygen--a potentially damaging biological oxidant. The carotenoid performs this function efficiently in most bacterial RCs by rapidly accepting the triplet state from P and dissipating this excited-state energy into heat through internal conversion. The lowest-lying triplet states of P and the carotenoid are sufficiently different that {sup T}P can promote oxygen to its excited singlet state whereas {sup T}C can quench the {sup T}P state (reviewed in [2]).

  17. Effects of aluminum additions to gas atomized reaction synthesis produced oxide dispersion strengthened alloys

    Science.gov (United States)

    Spicher, Alexander Lee

    The production of an aluminum containing ferritic oxide dispersion strengthened (ODS) alloy was investigated. The production method used in this study was gas atomization reaction synthesis (GARS). GARS was chosen over the previously commercial method of mechanical alloying (MA) process due to complications from this process. The alloy compositions was determined from three main components; corrosion resistance, dispersoid formation, and additional elements. A combination of Cr and Al were necessary in order to create a protective oxide in the steam atmosphere that the boiler tubing in the next generation of coal-fired power plants would be exposed to. Hf and Y were chosen as dispersoid forming elements due to their increased thermal stability and potential to avoid decreased strength caused by additions of Al to traditional ODS materials. W was used as an additive due to benefits as a strengthener as well as its benefits for creep rupture time. The final composition chosen for the alloy was Fe-16Cr-12Al-0.9W-0.25Hf-0.2Y at%. The aforementioned alloy, GA-1-198, was created through gas atomization with atomization gas of Ar-300ppm O2. The actual composition created was found to be Fe-15Cr-12.3Al-0.9W-0.24Hf-0.19Y at%. An additional alloy that was nominally the same without the inclusion of aluminum was created as a comparison for the effects on mechanical and corrosion properties. The actual composition of the comparison alloy, GA-1-204, was Fe-16Cr-0Al-0.9W-0.25Hf-0.24Y at%. An investigation on the processing parameters for these alloys was conducted on the GA-1-198 alloy. In order to predict the necessary amount of time for heat treatment, a diffusion study was used to find the diffusion rate of oxygen in cast alloys with similar composition. The diffusion rate was found to be similar to that of other GARS compositions that have been created without the inclusion of aluminum. The effect of heat treatment time was investigated with temperatures of 950°C, 1000

  18. Multiparameter Estimation in Voltammetry When an Electron Transfer Process Is Coupled to a Chemical Reaction.

    Science.gov (United States)

    Simonov, Alexandr N; Morris, Graham P; Mashkina, Elena; Bethwaite, Blair; Gillow, Kathryn; Baker, Ruth E; Gavaghan, David J; Bond, Alan M

    2016-05-01

    Estimation of thermodynamic and kinetic parameters in electrochemical studies is usually undertaken via comparison of the experimental results with theory based on a model that mimics the experiment. The present study examines the credibility of transient d.c. and a.c. voltammetric theory-experiment comparisons for recovery of the parameters needed to model the ubiquitous mechanism when an electron transfer (E) reaction is followed by a chemical (C) step in the EC process ([Formula: see text]). The data analysis has been undertaken using optimization methods facilitated in some cases by grid computing. These techniques have been applied to the simulated (5% noise added) and experimental (reduction of trans-stilbene) voltammograms to assess the capabilities of parameter recovery of E(0) (reversible potential for the E step), k(0) (heterogeneous electron transfer rate constant at E(0)), α (charge transfer coefficient for the E step), and k(f) and k(b) (forward and backward rate constants for the C step) under different kinetic regimes. The advantages provided by the use of a.c. instead of d.c. voltammetry and data optimization methods over heuristic approaches to "experiment"-theory comparisons are discussed, as are the limitations in the efficient recovery of a unique set of parameters for the EC mechanism. In the particular experimental case examined herein, results for the protonation of the electrochemically generated stilbene dianion demonstrate that, notwithstanding significant advances in experiment and theory of voltammetric analysis, reliable recovery of the parameters for the EC mechanism with a fast chemical process remains a stiff problem. PMID:27041344

  19. The 2H(e, e' p)n reaction at large energy transfers

    Science.gov (United States)

    Willering, Hendrik Willem

    2003-04-01

    At the ELSA accelerator facillity in Bonn, Germany, we have measured the deutron breakup reaction 2H(e, e' p)n at four-momentum transfers around Q2 = -0 .20(GeV/c)2 with an electron beam energy of E0 = 1.6 GeV. The cross section has been determined for energy transfers extending from the quasielastic region to just below the Delta(1232)-resonance, and for proton polar angles up to Thetanp = 145 o in the center-of-momentum system. This angular range represents missing momenta up to pm = 1000 MeV/c. By detecting the scattered protons in two segmented 3 3 m2 scintillator time-of-flight detectors, we have covered a considerable part of the out-of-plane region. The clearly visible variation of the cross section with the proton azimuthal angle fnp has enabled us to extract values for the longitudinal-transverse interference form factor fLT and for a combination of the non-interference form factors fL and fT for proton angles up to Thetanp = 40o in the center-of-momentum system. The experimental results have been compared to the full model calculations by Arenhövel et al. For the major part of our kinematical range the shape of the cross section and of the form factors is reproduced by the model, but some differences remain in the normalization, especially at higher energy transfers. Our results corroborate the conclusions from other recent experiments concerning the importance of subnuclear degrees-of-freedom beyond the quasielastic region, but the discrepancy indicates that the model can still be improved

  20. Charge-transfer-to-solvent reactions from I- to water, methanol, and ethanol studied by time-resolved photoelectron spectroscopy of liquids

    Science.gov (United States)

    Okuyama, Haruki; Suzuki, Yoshi-Ichi; Karashima, Shutaro; Suzuki, Toshinori

    2016-08-01

    The charge-transfer-to-solvent (CTTS) reactions from iodide (I-) to H2O, D2O, methanol, and ethanol were studied by time-resolved photoelectron spectroscopy of liquid microjets using a magnetic bottle time-of-flight spectrometer with variable pass energy. Photoexcited iodide dissociates into a weak complex (a contact pair) of a solvated electron and an iodine atom in similar reaction times, 0.3 ps in H2O and D2O and 0.5 ps in methanol and ethanol, which are much shorter than their dielectric relaxation times. The results indicate that solvated electrons are formed with minimal solvent reorganization in the long-range solvent polarization field created for I-. The photoelectron spectra for CTTS in H2O and D2O—measured with higher accuracy than in our previous study [Y. I. Suzuki et al., Chem. Sci. 2, 1094 (2011)]—indicate that internal conversion yields from the photoexcited I-* (CTTS) state are less than 10%, while alcohols provide 2-3 times greater yields of internal conversion from I-*. The overall geminate recombination yields are found to be in the order of H2O > D2O > methanol > ethanol, which is opposite to the order of the mutual diffusion rates of an iodine atom and a solvated electron. This result is consistent with the transition state theory for an adiabatic outer-sphere electron transfer process, which predicts that the recombination reaction rate has a pre-exponential factor inversely proportional to a longitudinal solvent relaxation time.

  1. Pore to Core Scale Simulation of the Mass Transfer with Mineral Reaction in Porous Media

    Directory of Open Access Journals (Sweden)

    Bekri S.

    2015-04-01

    Full Text Available Pore Network Model (PNM is used to simulate mass transfer with mineral reaction in a single phase flow through porous medium which is here a sandstone sample from the reservoir formation of the Pakoslaw gas field. The void space of the porous medium is represented by an idealized geometry of pore-bodies joined by pore-throats. Parameters defining the pore-bodies and the pore-throats distribution are determined by an optimization process aiming to match the experimental Mercury Intrusion Capillary Pressure (MICP curve and petrophysical properties of the rock such as intrinsic permeability and formation factor. The generated network is used first to simulate the multiphase flow by solving Kirchhoff’s laws. The capillary pressure and relative permeability curves are derived. Then, reactive transport is addressed under asymptotic regime where the solute concentration undergoes an exponential evolution with time. The porosity/permeability relationship and the three phenomenological coefficients of transport, namely the solute velocity, the dispersion and the mean reaction rate are determined as functions of Peclet and Peclet-Damköhler dimensionless numbers. Finally, the role of the dimensionless numbers on the reactive flow properties is highlighted.

  2. Study of fluorescence characteristics of the charge-transfer reaction of quinolone agents with bromanil

    Science.gov (United States)

    Li, Wen-Ying; Chen, Xiao-Fang; Xuan, Chun-Sheng

    2009-01-01

    A spectrofluorimetric method was discussed for the determination of three antibacterial quinolone derivatives, ofloxacin (OFL), norfloxacin (NOR) and ciprofloxacin (CIP) through charge-transfer complexation (CTC) with 2,3,5,6-tetrabromo-1,4-benzoquinone (bromanil, TBBQ). The method was based on the reaction of these drugs as n-electron donors with the π-acceptor TBBQ. TBBQ was found to react with these drugs to produce a kind of yellow complexes and the fluorescence intensities of the complexes were enhanced by 29-36 times more than those of the corresponding monomers. UV-vis, 1H NMR and XPS techniques were used to study the complexes formed. The various experimental parameters affecting the fluorescence intensity were studied and optimized. Under optimal reaction conditions, the rectilinear calibration graphs were obtained in the concentration range of 0.021-2.42 μg mL -1, 0.017-2.63 μg mL -1 and 0.019-2.14 μg mL -1 for OFL, NOR and CIP, respectively. The methods developed were applied successfully to the determination of the subject drugs in their pharmaceutical dosage forms with good precision and accuracy compared to official and reported methods as revealed by t- and F-tests.

  3. Charge constrained density functional molecular dynamics for simulation of condensed phase electron transfer reactions

    CERN Document Server

    Oberhofer, H

    2009-01-01

    We present a plane-wave basis set implementation of charge constrained density functional molecular dynamics (CDFT-MD) for simulation of electron transfer reactions in condensed phase systems. Following earlier work of Wu et al. Phys. Rev. A 72, 024502 (2005), the density functional is minimized under the constraint that the charge difference between donor and acceptor is equal to a given value. The classical ion dynamics is propagated on the Born-Oppenheimer surface of the charge constrained state. We investigate the dependence of the constrained energy and of the energy gap on the definition of the charge, and present expressions for the constraint forces. The method is applied to the Ru2+-Ru3+ electron self-exchange reaction in aqueous solution. Sampling the vertical energy gap along CDFT-MD trajectories, and correcting for finite size effects, a reorganization free energy of 1.6 eV is obtained. This is 0.1-0.2 eV lower than a previous estimate based on a continuum model for solvation. smaller value for re...

  4. Pore to core scale simulation of the mass transfer with mineral reaction in porous media

    International Nuclear Information System (INIS)

    Pore Network Model (PNM) is used to simulate mass transfer with mineral reaction in a single phase flow through porous medium which is here a sandstone sample from the reservoir formation of the Pakoslaw gas field. The void space of the porous medium is represented by an idealized geometry of pore-bodies joined by pore-throats. Parameters defining the pore-bodies and the pore-throats distribution are determined by an optimization process aiming to match the experimental Mercury Intrusion Capillary Pressure (MICP) curve and petrophysical properties of the rock such as intrinsic permeability and formation factor. The generated network is used first to simulate the multiphase flow by solving Kirchhoff's laws. The capillary pressure and relative permeability curves are derived. Then, reactive transport is addressed under asymptotic regime where the solute concentration undergoes an exponential evolution with time. The porosity/ permeability relationship and the three phenomenological coefficients of transport, namely the solute velocity, the dispersion and the mean reaction rate are determined as functions of Peclet and Peclet-Damkohler dimensionless numbers. Finally, the role of the dimensionless numbers on the reactive flow properties is highlighted. (authors)

  5. Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts.

    Science.gov (United States)

    Yin, Peiqun; Yao, Tao; Wu, Yuen; Zheng, Lirong; Lin, Yue; Liu, Wei; Ju, Huanxin; Zhu, Junfa; Hong, Xun; Deng, Zhaoxiang; Zhou, Gang; Wei, Shiqiang; Li, Yadong

    2016-08-26

    A new strategy for achieving stable Co single atoms (SAs) on nitrogen-doped porous carbon with high metal loading over 4 wt % is reported. The strategy is based on a pyrolysis process of predesigned bimetallic Zn/Co metal-organic frameworks, during which Co can be reduced by carbonization of the organic linker and Zn is selectively evaporated away at high temperatures above 800 °C. The spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements both confirm the atomic dispersion of Co atoms stabilized by as-generated N-doped porous carbon. Surprisingly, the obtained Co-Nx single sites exhibit superior ORR performance with a half-wave potential (0.881 V) that is more positive than commercial Pt/C (0.811 V) and most reported non-precious metal catalysts. Durability tests revealed that the Co single atoms exhibit outstanding chemical stability during electrocatalysis and thermal stability that resists sintering at 900 °C. Our findings open up a new routine for general and practical synthesis of a variety of materials bearing single atoms, which could facilitate new discoveries at the atomic scale in condensed materials. PMID:27491018

  6. Measurement of atmospheric sesquiterpenes by proton transfer reaction-mass spectrometry (PTR-MS

    Directory of Open Access Journals (Sweden)

    A. Guenther

    2009-04-01

    Full Text Available The ability to measure sesquiterpenes (SQT; C15H24 by a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS was investigated. SQT calibration standards were prepared by a capillary diffusion method and the PTR-MS-estimated mixing ratios were derived from the counts of product ions and proton transfer reaction constants. These values were compared with mixing ratios determined by a calibrated Gas Chromatograph (GC coupled to a Flame Ionization Detector (GC-FID. Product ion distributions from soft-ionization occurring in a selected ion drift tube via proton transfer were measured as a function of collision energies. Results after the consideration of the mass discrimination of the PTR-MS system suggest that quantitative SQT measurements within 20% accuracy can be achieved with PTR-MS if two major product ions (m/z 149+ and 205+, out of seven major product ions (m/z 81+, 95+, 109+, 123+, 135+, 149+ and 205+, are accounted for. Considerable fragmentation of bicyclic sesquiterpenes, i.e. β-caryophyllene and α-humulene, cause the accuracy to be reduced to 50% if only the parent ion (m/z 205+ is considered. These findings were applied to a field dataset collected above a deciduous forest at the PROPHET (Program for Research on Oxidants: Photochemistry, Emissions, and Transport research station in 2005. Inferred average daytime ecosystem scale mixing ratios (fluxes of isoprene, sum of monoterpenes (MT, and sum of SQT exhibited values of 15 μg m−3 (4.5 mg m−2 h−1, 1.2 μg m−3 (0.21 mg m−2 h−1, and 0.0016 μg m−3 (0.10 mg m−2 h−1, respectively. A range of MT and SQT reactivities with respect to the OH radical was calculated and compared to an earlier study inferring significantly

  7. Measurement of atmospheric sesquiterpenes by proton transfer reaction-mass spectrometry (PTR-MS

    Directory of Open Access Journals (Sweden)

    S. Kim

    2008-12-01

    Full Text Available The ability to measure sesquiterpenes (SQT; C15H24 by a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS was investigated with SQT standards, prepared by a capillary diffusion method, and the estimated mixing ratios, derived from the counts of product ions and proton transfer reaction constants were intercompared with measured mixing ratios, measured by a complementary Gas Chromatograph (GC coupled to a Flame Ionization Detector (GC-FID. Product ion distributions due to soft-ionization occurring in a selected ion drift tube via proton transfer were measured as a function of collision energies. Results after the consideration of the mass discrimination of the PTR-MS system suggest that quantitative SQT measurements within 20% accuracy can be achieved with PTR-MS if two major product ions (m/z 149+ and 205+ out of seven major product ions (m/z 81+, 95+, 109+, 123+, 135+, 149+ and 205+ are accounted for. Bicyclic sesquiterpenes, i.e. β-caryophyllene and α-humulene, showed considerable fragmentation causing the accuracy of their analysis to be reduced to 50% if only the parent ion (m/z 205 is considered. These findings were applied to a field dataset collected above a deciduous forest at the PROPHET (Program for Research on Oxidants: Photochemistry, Emissions, and Transport research station in 2005. Inferred Average daytime ecosystem scale mixing ratios (fluxes of isoprene, sum of monoterpenes (MT, and sum of SQT exhibited values of 15 μg m−3 (4.5 mg m−2 h−1, 1.2 μg m−3 (0.21 mg m−2 h−1 and 0.0016 μg m−3 (0.10 mgm−2 h−1 respectively. A range of MT and SQT reactivities with respect to the OH radical was calculated and compared to an earlier study inferring significantly underestimated OH

  8. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1978--February 14, 1979

    International Nuclear Information System (INIS)

    High energy reactions of halogen atoms or ions, activated by nuclear transformations, were studied in gaseous, high pressure and condensed phase saturated and unsaturated hydrocarbons, halomethanes and other organic systems in order to better understand the mechanisms and dynamics of high energy monovalent species. The experimental and theoretical program consists of six interrelated areas: (1) the reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure and liquid systems; (2) the gas to condensed state transition in halogen high chemistry, involving bromine activated by the (n,γ) and (I.T.) processes in ethane was investigated in more detail; (3) systematics of halogen hot atom reactions. The reactions of 80Br/sup m/, 80Br, 82Br/sup m/ + 82Br, 82Br, 128I, 130I, and 130I/sup m/ + 130I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators; (4) kinetic theory applications of high energy reactions and mathematical development of caging mechanisms were developed; (5) the sterochemistry of 38Cl substitution reactions involving diastereomeric 1,2-dichloro-1,2-difluorethane in liquid mixtures was completed, suggesting that the stereochemical course of the substitution process is controlled by the properties of the solvent molecules; and (6) the applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems was continued, especially involving aluminum and vanadium trace determinations

  9. Nucleon-nucleon correlations in heavy ion transfer reactions: Recent investigations at energies far below the Coulomb barrier

    Energy Technology Data Exchange (ETDEWEB)

    Corradi, Lorenzo, E-mail: corradi@lnl.infn.it [INFN, Laboratori Nazionali di Legnaro, Viale dell’Universita’ 2 - 35020, Legnaro (Padova) - Italy (Italy)

    2015-10-15

    Excitation functions of one- and two-neutron transfer channels have been measured for the {sup 96}Zr+{sup 40}Ca and {sup 116}Sn+{sup 60}Ni systems at bombarding energies ranging from the Coulomb barrier to ∼25% below. Target-like recoils have been identified in A, Z and velocity with the large solid angle magnetic spectrometer PRISMA. The experimental transfer probabilities have been compared, in absolute values and in slope, with semiclassical microscopic calculations which incorporate nucleon-nucleon pairing correlations. For the first time in a heavy ion collision, one was able to provide a consistent description of one and two neutron transfer reactions by incorporating, in the reaction mechanism, all known structure information of entrance and exit channels nuclei. In particular, there is no need to introduce any enhancement factor for the description of two neutron transfer, of course very important are the correlations induced by the pairing interaction.

  10. Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.

    Science.gov (United States)

    Reinhardt, Clorice R; Jaglinski, Tanner C; Kastenschmidt, Ashly M; Song, Eun H; Gross, Adam K; Krause, Alyssa J; Gollmar, Jonathan M; Meise, Kristin J; Stenerson, Zachary S; Weibel, Tyler J; Dison, Andrew; Finnegan, Mackenzie R; Griesi, Daniel S; Heltne, Michael D; Hughes, Tom G; Hunt, Connor D; Jansen, Kayla A; Xiong, Adam H; Hati, Sanchita; Bhattacharyya, Sudeep

    2016-09-01

    The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes. PMID:27491848

  11. Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.

    Science.gov (United States)

    Reinhardt, Clorice R; Jaglinski, Tanner C; Kastenschmidt, Ashly M; Song, Eun H; Gross, Adam K; Krause, Alyssa J; Gollmar, Jonathan M; Meise, Kristin J; Stenerson, Zachary S; Weibel, Tyler J; Dison, Andrew; Finnegan, Mackenzie R; Griesi, Daniel S; Heltne, Michael D; Hughes, Tom G; Hunt, Connor D; Jansen, Kayla A; Xiong, Adam H; Hati, Sanchita; Bhattacharyya, Sudeep

    2016-09-01

    The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes.

  12. Side chain effects in reactions of the potassium-tyrosine charge transfer complex

    Science.gov (United States)

    da Silva, F. Ferreira; Meneses, G.; Ingólfsson, O.; Limão-Vieira, P.

    2016-10-01

    Fragmentation of transient negative ions of tyrosine formed through electron transfer in collisions with neutral potassium atoms is presented in the collision energy range from 30 to 75 eV. At low collision energies the dominating side chain channel observed corresponds to the cleavage of the bond from the para-position of the phenyl ring to the β-C of the remaining moiety, but cleavage of the Cαsbnd Cβ bond is also observed. Further fragments are formed through cleavage of the Cα bond to the carbonyl group, through decomposition of the carboxyl group or through significant decomposition of the backbone. The dehydrogenated molecular anion is also observed with appreciable intensity. These results are discussed in the context of earlier studies on dissociative electron attachment to tyrosine and other amino acids, as well as within the role of the side chain in electron induced decomposition of this aromatic amino acid. Stabilization of the temporary molecular anion in the transient collision complex is discussed and we argue that this may have significant influence on the branching ratios observed.

  13. Optical pumping and population transfer of nuclear-spin states of caesium atoms in high magnetic fields

    Institute of Scientific and Technical Information of China (English)

    Luo Jun; Sun Xian-Ping; Zeng Xi-Zhi; Zhan Ming-Sheng

    2007-01-01

    Nuclear-spin states of gaseous-state Cs atoms in the ground state are optically manipulated using a Ti:sapphire laser in a magnetic field of 1.516 T, in which optical coupling of the nuclear-spin states is achieved through hyperfine interactions between electrons and nuclei. The steady-state population distribution in the hyperfine Zeeman sublevels of the ground state is detected by using a tunable diode laser. Furthermore, the state population transfer among the of Cs in the ground state due to stochastic collisions between Cs atoms and buffer-gas molecules, is studied at different of the hyperfine interaction can strongly cause the state population transfer and spin-state interchange among the hyperfine Zeeman sublevels. The calculated results maybe explain the steady-state population in hyperfine Zeeman sublevels in terms of rates of optical-pumping, electron-spin flip, nuclear spin flip, and electron-nuclear spin flip-flop transitions among the hyperfine Zeeman sublevels of the ground state of Cs atoms. This method may be applied to the nuclear-spin-based solid-state quantum computation.

  14. Matter, energy, and heat transfer in a classical ballistic atom pump.

    Science.gov (United States)

    Byrd, Tommy A; Das, Kunal K; Mitchell, Kevin A; Aubin, Seth; Delos, John B

    2014-11-01

    A ballistic atom pump is a system containing two reservoirs of neutral atoms or molecules and a junction connecting them containing a localized time-varying potential. Atoms move through the pump as independent particles. Under certain conditions, these pumps can create net transport of atoms from one reservoir to the other. While such systems are sometimes called "quantum pumps," they are also models of classical chaotic transport, and their quantum behavior cannot be understood without study of the corresponding classical behavior. Here we examine classically such a pump's effect on energy and temperature in the reservoirs, in addition to net particle transport. We show that the changes in particle number, of energy in each reservoir, and of temperature in each reservoir vary in unexpected ways as the incident particle energy is varied.

  15. Mechanisms for Two-Step Proton Transfer Reactions in the Outward-Facing Form of MATE Transporter.

    Science.gov (United States)

    Nishima, Wataru; Mizukami, Wataru; Tanaka, Yoshiki; Ishitani, Ryuichiro; Nureki, Osamu; Sugita, Yuji

    2016-03-29

    Bacterial pathogens or cancer cells can acquire multidrug resistance, which causes serious clinical problems. In cells with multidrug resistance, various drugs or antibiotics are extruded across the cell membrane by multidrug transporters. The multidrug and toxic compound extrusion (MATE) transporter is one of the five families of multidrug transporters. MATE from Pyrococcus furiosus uses H(+) to transport a substrate from the cytoplasm to the outside of a cell. Crystal structures of MATE from P. furiosus provide essential information on the relevant H(+)-binding sites (D41 and D184). Hybrid quantum mechanical/molecular mechanical simulations and continuum electrostatic calculations on the crystal structures predict that D41 is protonated in one structure (Straight) and, both D41 and D184 protonated in another (Bent). All-atom molecular dynamics simulations suggest a dynamic equilibrium between the protonation states of the two aspartic acids and that the protonation state affects hydration in the substrate binding cavity and lipid intrusion in the cleft between the N- and C-lobes. This hypothesis is examined in more detail by quantum mechanical/molecular mechanical calculations on snapshots taken from the molecular dynamics trajectories. We find the possibility of two proton transfer (PT) reactions in Straight: the 1st PT takes place between side-chains D41 and D184 through a transient formation of low-barrier hydrogen bonds and the 2nd through another H(+) from the headgroup of a lipid that intrudes into the cleft resulting in a doubly protonated (both D41 and D184) state. The 1st PT affects the local hydrogen bond network and hydration in the N-lobe cavity, which would impinge on the substrate-binding affinity. The 2nd PT would drive the conformational change from Straight to Bent. This model may be applicable to several prokaryotic H(+)-coupled MATE multidrug transporters with the relevant aspartic acids. PMID:27028644

  16. Quasi-Steady-State Voltammetry of Rapid Electron Transfer Reactions at the Macroscopic Substrate of the Scanning Electrochemical Microscope

    OpenAIRE

    Nioradze, Nikoloz; Kim, Jiyeon; Amemiya, Shigeru

    2010-01-01

    We report on novel theory and experiment for scanning electrochemical microscopy (SECM) to enable quasi-steady-state voltammetry of rapid electron transfer (ET) reactions at macroscopic substrates. With this powerful approach, substrate potential is cycled widely across the formal potential of a redox couple while the reactant or product of a substrate reaction is amperometrically detected at the tip in the feedback or substrate generation/tip collection mode, respectively. The plot of tip cu...

  17. Using positive-ion electrospray ionization mass spectrometry and H/D exchange study phosphoryl group transfer reactions involved in amino acid ester isopropyl phosphoramidates of Brefeldin A

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Mei-Juan; Zhang, He; Liao, Chao; Qiu, Ying-Kun [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China); Fang, Hua [The Third Institute of Oceanography of the State Oceanic Administration, Xiamen 361005 (China); Zheng, Zhen-Yu [College of Chemistry and Chemical Engineering, Department of Chemistry, Xiamen University, Xiamen 361005 (China); Gao, Xiang [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China); Zhao, Yu-Fen [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China); College of Chemistry and Chemical Engineering, Department of Chemistry, Xiamen University, Xiamen 361005 (China); Wu, Zhen, E-mail: wuzhen@xmu.edu.cn [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China)

    2015-01-01

    Highlights: • ESI-MS{sup n}, HRMS and H/D exchange were used. • The fragmentation pathways of NPAAE-BFA in ESI-MS{sup n} were described. • Fragment ions involved in phosphorus group’s rearrangement reactions were observed. • Two rearrangement mechanisms about phosphorylation–dephosphorylation were proposed. - Abstract: As mini-chemical models, amino acid ester isopropyl phosphoramidates of Brefeldin A (compounds 2a–2d) were synthesized and investigated by electrospray ionization tandem mass spectrometry in combination with H/D exchange. To further confirm the fragments’s structures, off-line Fourier transform resonance tandem mass spectrometry (FT-ICR-MS/MS) was also performed. The fragmentation rules of compounds 2a–2d have been summarized and the plausible schemes for the fragmentation pathways were proposed. In this study, one dephosphorylated ion and two phosphorylated ions were observed in ESI-MS{sup 2} spectra of [M + Na]{sup +} ions for compounds 2a–2d. The possible mechanisms about phosphorylation and dephosphorylation were proposed and confirmed by H/D exchange. For the “dephosphorylation” rearrangement, a nitrogen atom was migrated from the phosphoryl group to the carbon atom of Brefeldin A’s backbone with losing a molecule of C{sub 3}H{sub 7}PO{sub 3} (122 Da). For the “phosphorylation” rearrangement, an oxygen atom of one phosphoryl group attacked the sideward phosphorus atom to form a nine-member ring intermediate, then two steps of C-H covalent bond cleavage with consecutive migration of hydrogen atom to lose a molecule of C{sub 16}H{sub 20}O{sub 2} (244 Da). The two proposed rearrangement mechanisms about phosphoryl group transfer might be valuable for the structure analysis of other analogs and provide insights into elucidating the dynamic process of the phosphorylation–dephosphorylation of proteins.

  18. Hydrogen-transfer and charge-transfer in photochemical and radiation induced reactions. Progress report, November 1, 1975--October 31, 1976

    International Nuclear Information System (INIS)

    The relative importance of light absorption, quenching of triplet, and hydrogen transfer repair has been examined in retardation by mercaptans of photoreduction of aromatic ketones by alcohols. In the reduction of benzophenone by 2-propanol, retardation is efficient and, after correction for the first two effects, is due entirely to hydrogen-transfer repair, as indicated by deuterium labeling. In reduction of acetophenone by α-methylbenzyl alcohol, repair by hydrogen transfer is also operative. In reduction of benzophenone by benzhydrol, retardation is less efficient and is due to quenching, as the ketyl radical does not abstract hydrogen from mercaptan rapidly in competition with coupling. Deuterium isotope effects are discussed in terms of competitive reactions. Photoreduction of benzophenone by 2-butylamine and by triethylamine is retarded by aromatic mercaptans and disulfides. Of the retardation not due to light absorption and triplet quenching by the sulfur compounds, half is due to hydrogen-transfer repair, as indicated by racemization and deuterium labeling. The remainder is attributed to quenching by the sulfur compound of the charge-transfer-complex intermediate. Photoreduction by primary and secondary amines, but not by tertiary amines, is accelerated by aliphatic mercaptans. The acceleration is attributed to catalysis of hydrogen transfer by the mercaptan in the charge-transfer complex. The effect is large in hydrocarbon solvent, less in polar organic solvents and absent in water

  19. Controlling Interfacial Reactions and Intermetallic Compound Growth at the Interface of a Lead-free Solder Joint with Layer-by-Layer Transferred Graphene.

    Science.gov (United States)

    Ko, Yong-Ho; Lee, Jong-Dae; Yoon, Taeshik; Lee, Chang-Woo; Kim, Taek-Soo

    2016-03-01

    The immoderate growth of intermetallic compounds (IMCs) formed at the interface of a solder metal and the substrate during soldering can degrade the mechanical properties and reliability of a solder joint in electronic packaging. Therefore, it is critical to control IMC growth at the solder joints between the solder and the substrate. In this study, we investigated the control of interfacial reactions and IMC growth by the layer-by-layer transfer of graphene during the reflow process at the interface between Sn-3.0Ag-0.5Cu (in wt %) lead-free solder and Cu. As the number of graphene layers transferred onto the surface of the Cu substrate increased, the thickness of the total IMC (Cu6Sn5 and Cu3Sn) layer decreased. After 10 repetitions of the reflow process for 50 s above 217 °C, the melting temperature of Sn-3.0Ag-0.5Cu, with a peak temperature of 250 °C, the increase in thickness of the total IMC layer at the interface with multiple layers of graphene was decreased by more than 20% compared to that at the interface of bare Cu without graphene. Furthermore, the average diameter of the Cu6Sn5 scallops at the interface with multiple layers of graphene was smaller than that at the interface without graphene. Despite 10 repetitions of the reflow process, the growth of Cu3Sn at the interface with multiple layers of graphene was suppressed by more than 20% compared with that at the interface without graphene. The multiple layers of graphene at the interface between the solder metal and the Cu substrate hindered the diffusion of Cu atoms from the Cu substrate and suppressed the reactions between Cu and Sn in the solder. Thus, the multiple layers of graphene transferred at the interface between dissimilar metals can control the interfacial reaction and IMC growth occurring at the joining interface. PMID:26856638

  20. Atomic-scale study of transformation paths in unmixing and ordering reactions

    Energy Technology Data Exchange (ETDEWEB)

    Blavette, D.; Pareige-Schmuck, C.; Danoix, F. [CNRS, Mont Saint Aignan (France). Fac. des Sci. de Rouen; Stiller, K.

    1997-06-01

    The tomographic atom-probe (TAP) is a new high resolution nanoanalytical microscope, which provides three-dimensional maps of chemical heterogeneities in a metallic material on a near-atomic scale. Application of the TAP to unmixing and ordering in metallic alloys is discussed and illustrated through various examples (spinodal decomposition in FeCr ferritic phases, nucleation and growth of LI{sub 2} ordered precipitates in nickel based alloys, precipitation in maraging steels). The role of the TAP in the investigation of transformation paths in these systems is discussed. (orig.). 17 refs.

  1. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1979-February 14, 1980

    International Nuclear Information System (INIS)

    The program consists of six interrelated areas: (1) Reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure, and liquid systems. Special attention was given to the reactivity of excited complex formation and structural effects of electrophilic iodine attack on various pi-bond systems. (2) The gas-to-condensed phase transition in halogen high energy chemistry. Current interest involves the study of caging effects of an ice lattice on recombination reactions involving neutron-irradiated frozen aqueous solutions of halogenated organic and biochemical solutes in order to learn more about kinetic energy effects, halogen size, solute molecule size, steric effects and hydrogen bonding within an ice lattice cage. (3) Systematics of halogen hot atom reactions. The reactions of /sup 80m/Br, 80Br, /sup 82m/Br + 82Br, 82Br, 82Br, 128I, 130I, and /sup 130m/I + 130I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators are currently being studied. (4) Mathematical and computer simulation studies of caging events within an ice lattice are being investigated. (5) At Brookhaven National Laboratory, cyclotron-produced chlorine and fluorine hot atoms substitution reactions with molecules possessing a single chiral center are under investigation. (6) The applications of high energy techniques and concepts to neutron activation analysis for trace elements and trace molecule determinations in biological systems was continued

  2. Dynamics of interfacial reactions between O({sup 3} P) atoms and long-chain liquid hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Allan, Mhairi [School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom); Bagot, Paul A J [School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom); Koehler, Sven P K [School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom); Reed, Stewart K [Department of Physics and Astronomy, University of Edinburgh, The King' s Buildings, Edinburgh EH9 3JZ (United Kingdom); Westacott, Robin E [School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom); Costen, Matthew L [School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom); McKendrick, Kenneth G [School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom)

    2007-09-15

    Recent progress that has been made towards understanding the dynamics of collisions at the gas-liquid interface is summarized briefly. We describe in this context a promising new approach to the experimental study of gas-liquid interfacial reactions that we have introduced. This is based on laser-photolytic production of reactive gas-phase atoms above the liquid surface and laser-spectroscopic probing of the resulting nascent products. This technique is illustrated for reaction of O({sup 3}P) atoms at the surface of the long-chain liquid hydrocarbon squalane (2,6,10,15,19,23-hexamethyltetracosane). Laser-induced fluorescence detection of the nascent OH has revealed mechanistically diagnostic correlations between its internal and translational energy distributions. Vibrationally excited OH molecules are able to escape the surface. At least two contributions to the product rotational distributions are identified, confirming and extending previous hypotheses of the participation of both direct and trapping-desorption mechanisms. We speculate briefly on future experimental and theoretical developments that might be necessary to address the many currently unanswered mechanistic questions for this, and other, classes of gas-liquid interfacial reaction.

  3. The ^2H(e,e'p)n Reaction at High Four-Momentum Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Hassan Ibrahim

    2006-12-31

    This dissertation presents the highest four-momentum transfer, Q^2,quasielastic (x_Bj = 1) results from Experiment E01-020 which systematically explored the 2He(e,e'p)n reaction ("Electro-disintegration" of the deuteron) at three different four-momentum transfers, Q^2 = 0.8, 2.1, and 3.5 GeV^2 and missing momenta, P_miss = 0, 100, 200, 300, 400, and 500 GeV including separations of the longitudinal-transverse interference response function, R_LT, and extractoin of the longitudinal-transverse asymmetry, A_LT. This systematic approach will help to understand the reaction mechanism and the deuteron structure down to the short range part of the nucleon-nucleon interaction which is one of the fundamental missions of nuclear physics. By studying the very short distance structure of the deuteron, one may also determine whether or to what extent the description of nuclei in terms of nucleon/meson degrees of freedom must be supplemented by inclusion of explicit quark effects. The unique combination of energy, current, duty factor, and control of systematics for Hall A at Jefferson Lab made Jefferson Lab the only facility in the world where these systematic studies of the deuteron can be undertaken. This is especially true when we want to understand the short range structure of the deuteron where high energies and high luminosity/duty factor are needed. All these features of Jefferson Lab allow us to examine large missing momenta (short range scales) at kinematics where the effects of final state interactions (FSI), meson exchange currents (MEC), and isobar currents (IC) are minimal, making the extraction of the deuteron structure less model-dependent. Jefferson Lab also provides the kinematical flexibility to perform the separation of R_LT over a broad range of missing momenta and momentum transfers. Experiment E01-020 use the standard Hall A equipment in coincidence configuration in addition to the cryogenic target system. The low and middle Q^2 kinematics were

  4. Effect of different hand positions on trunk and shoulder kinematics and reaction forces in sitting pivot transfer.

    Science.gov (United States)

    Kim, Sung Shin; Her, Jin Gan; Ko, Tae Sung

    2015-07-01

    [Purpose] The purpose of this study was to compare the changes in trunk and shoulder angles, and reaction forces under the two hands elicited by different hand base of support positions during sitting pivot transfer. [Subjects and Methods] Eighteen unimpaired subjects performed independent sitting pivot transfer. Subjects performed sitting pivot transfer between an initial seat to a target seat by only using their hands positioned at the same height as and lower than the seat position. Trunk and shoulder kinematics, and reaction forces on the trailing and leading hands were calculated. Mean peak joint angles and forces were compared between the hand positions using the pared t-test for the lift phase of the transfer. [Results] There were significant increases in the trunk angles of forward and lateral flexion, even though rotation decreased while transferring in the lower hand position. Increased shoulder flexion, anterior/posterior forces and reduced lateral forces were also shown. [Conclusion] Placing the hands of the supporting arms lower than the seat position during sitting pivot transfer was identified as having biomechanical advantages. Therefore, the lower hand position can be recommended as an effective and safe method for sitting pivot transfer by patients with spinal cord injury and can be utilized as a reference data for considering the appropriate height of aids for a wheelchair. PMID:26310994

  5. Calculated coupling of electron and proton transfer in the photosynthetic reaction center of Rhodopseudomonas viridis.

    Science.gov (United States)

    Lancaster, C R; Michel, H; Honig, B; Gunner, M R

    1996-06-01

    Based on new Rhodopseudomonas (Rp.) viridis reaction center (RC) coordinates with a reliable structure of the secondary acceptor quinone (QB) site, a continuum dielectric model and finite difference technique have been used to identify clusters of electrostatically interacting ionizable residues. Twenty-three residues within a distance of 25 A from QB (QB cluster) have been shown to be strongly electrostatically coupled to QB, either directly or indirectly. An analogous cluster of 24 residues is found to interact with QA (QA cluster). Both clusters extend to the cytoplasmic surface in at least two directions. However, the QB cluster differs from the QA cluster in that it has a surplus of acidic residues, more strong electrostatic interactions, is less solvated, and experiences a strong positive electrostatic field arising from the polypeptide backbone. Consequently, upon reduction of QA or QB, it is the QB cluster, and not the QA cluster, which is responsible for substoichiometric proton uptake at neutral pH. The bulk of the changes in the QB cluster are calculated to be due to the protonation of a tightly coupled cluster of the three Glu residues (L212, H177, and M234) within the QB cluster. If the lifetime of the doubly reduced state QB2- is long enough, Asp M43 and Ser L223 are predicted to also become protonated. The calculated complex titration behavior of the strongly interacting residues of the QB cluster and the resulting electrostatic response to electron transfer may be a common feature in proton-transferring membrane protein complexes. PMID:8744288

  6. Kinetics of acyl transfer reactions in organic media catalysed by Candida antarctica lipase B.

    Science.gov (United States)

    Martinelle, M; Hult, K

    1995-09-01

    The acyl transfer reactions catalysed by Candida antartica lipase B in organic media followed a bi-bi ping-pong mechanism, with competitive substrate inhibition by the alcohols used as acyl acceptors. The effect of organic solvents on Vm and Km was investigated. The Vm values in acetonitrile was 40-50% of those in heptane. High Km values in acetonitrile compared to those in heptane could partly be explained by an increased solvation of the substrates in acetonitrile. Substrate solvation caused a 10-fold change in substrate specificity, defined as (Vm/Km)ethyl octanoate/(Vm/Km)octanoic acid, going from heptane to acetonitrile. Deacylation was the rate determining step for the acyl transfer in heptane with vinyl- and ethyl octanoate as acyl donors and (R)-2-octanol as acyl acceptor. With 1-octanol, a rate determining deacylation step in heptane was indicated using the same acyl donors. Using 1-octanol as acceptor in heptane, S-ethyl thiooctanoate had a 25- to 30-fold lower Vm/Km value and vinyl octanoate a 4-fold higher Vm/Km value than that for ethyl octanoate. The difference showed to be a Km effect for vinyl octanoate and mainly a Km effect for S-ethyl thiooctanoate. The Vm values of the esterification of octanoic acid with different alcohols was 10-30-times lower than those for the corresponding transesterification of ethyl octanoate. The low activity could be explained by a low pH around the enzyme caused by the acid or a withdrawing of active enzyme by nonproductive binding by the acid.

  7. Quantification of diesel exhaust gas phase organics by a thermal desorption proton transfer reaction mass spectrometer

    Directory of Open Access Journals (Sweden)

    M. H. Erickson

    2012-02-01

    Full Text Available A new approach was developed to measure the total abundance of long chain alkanes (C12 and above in urban air using thermal desorption with a proton transfer reaction mass spectrometer (PTR-MS. These species are emitted in diesel exhaust and may be important precursors to secondary organic aerosol production in urban areas. Long chain alkanes undergo dissociative proton transfer reactions forming a series of fragment ions with formula CnH2n+1. The yield of the fragment ions is a function of drift conditions. At a drift field strength of 80 Townsends, the most abundant ion fragments from C10 to C16 n-alkanes were m/z 57, 71 and 85. The PTR-MS is insensitive to n-alkanes less than C8 but displays an increasing sensitivity for larger alkanes. Higher drift field strengths yield greater normalized sensitivity implying that the proton affinity of the long chain n-alkanes is less than H2O. Analysis of diesel fuel shows the mass spectrum was dominated by alkanes (CnH2n+1, monocyclic aromatics, and an ion group with formula CnH2n−1 (m/z 97, 111, 125, 139. The PTR-MS was deployed in Sacramento, CA during the Carbonaceous Aerosols and Radiative Effects Study field experiment in June 2010. The ratio of the m/z 97 to 85 ion intensities in ambient air matched that found in diesel fuel. Total diesel exhaust alkane concentrations calculated from the measured abundance of m/z 85 ranged from the method detection limit of ~1 μg m−3 to 100 μg m−3 in several air pollution episodes. The total diesel exhaust alkane concentration determined by this method was on average a factor of 10 greater than the sum of alkylbenzenes associated with spark ignition vehicle exhaust.

  8. Eddy covariance flux measurements of ammonia by electron transfer reaction-mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. Sintermann

    2010-11-01

    Full Text Available A system for fast ammonia (NH3 measurements based on a commercial Proton Transfer Reaction-Mass Spectrometer is presented. It uses electron transfer reaction (eTR as ionisation pathway and features a drift tube of polyetheretherketone (PEEK and silica-coated steel. Heating the instrumental inlet and the drift tube to 180° C enabled an effective time resolution of ~1 s and made it possible to apply the eTR-MS for eddy covariance (EC measurements. EC fluxes of NH3 were measured over two agricultural fields in Oensingen, Switzerland, following fertilisations with cattle slurry. Air was aspirated close to a sonic anemometer at a flow of 100 STP L min−1 and was directed through a 23 m long 1/2" PFA tube heated to 150°C to an air-conditioned trailer where the eTR-MS sub-sampled from the large bypass stream. This setup minimised damping of fast NH3 concentration changes between the sampling point and the actual measurement. High-frequency attenuation loss of the NH3 fluxes of 20 to 40% was quantified and corrected for using an empirical ogive method. The instrumental NH3 background signal showed a minor interference with H2O which was characterised in the laboratory. The resulting correction of the NH3 flux after slurry spreading was less than 1‰. The flux detection limit of the EC system was about 5 ng m−2 s−1 while the accuracy of individual flux measurements was estimated 16% for the high-flux regime during these experiments. The NH3 emissions after broad spreading of the slurry showed an initial maximum of 150 μg m2 s−1 with a fast decline in the following hours.

  9. Control and Automation of Fluid Flow, Mass Transfer and Chemical Reactions in Microscale Segmented Flow

    Science.gov (United States)

    Abolhasani, Milad

    Flowing trains of uniformly sized bubbles/droplets (i.e., segmented flows) and the associated mass transfer enhancement over their single-phase counterparts have been studied extensively during the past fifty years. Although the scaling behaviour of segmented flow formation is increasingly well understood, the predictive adjustment of the desired flow characteristics that influence the mixing and residence times, remains a challenge. Currently, a time consuming, slow and often inconsistent manual manipulation of experimental conditions is required to address this task. In my thesis, I have overcome the above-mentioned challenges and developed an experimental strategy that for the first time provided predictive control over segmented flows in a hands-off manner. A computer-controlled platform that consisted of a real-time image processing module within an integral controller, a silicon-based microreactor and automated fluid delivery technique was designed, implemented and validated. In a first part of my thesis I utilized this approach for the automated screening of physical mass transfer and solubility characteristics of carbon dioxide (CO2) in a physical solvent at a well-defined temperature and pressure and a throughput of 12 conditions per hour. Second, by applying the segmented flow approach to a recently discovered CO2 chemical absorbent, frustrated Lewis pairs (FLPs), I determined the thermodynamic characteristics of the CO2-FLP reaction. Finally, the segmented flow approach was employed for characterization and investigation of CO2-governed liquid-liquid phase separation process. The second part of my thesis utilized the segmented flow platform for the preparation and shape control of high quality colloidal nanomaterials (e.g., CdSe/CdS) via the automated control of residence times up to approximately 5 minutes. By introducing a novel oscillatory segmented flow concept, I was able to further extend the residence time limitation to 24 hours. A case study of a

  10. Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid

    Directory of Open Access Journals (Sweden)

    Andri Cahyo Kumoro

    2015-03-01

    Full Text Available Acetylation is one of the common methods of modifying starch properties by introducing acetil (CH3CO groups to starch molecules at low temperatures. While most acetylation is conducted using starch as anhidroglucose source and acetic anhydride or vinyl acetate as nucleophilic agents, this work employ reactants, namely flour and glacial acetic acid. The purpose of this work are to study the effect of pH reaction and GAA/GF mass ratio on the rate of acetylation reaction and to determine its rate constants. The acetylation of gadung flour with glacial acetic acid in the presence of sodium hydroxide as a homogenous catalyst was studied at ambient temperature with pH ranging from 8-10 and different mass ratio of acetic acid : gadung flour (1:3; 1:4; and 1:5. It was found that increasing pH, lead to increase the degree of substitution, while increasing GAA/GF mass ratio caused such decreases in the degree of substitution, due to the hydrolysis of the acetylated starch. The desired starch acetylation reaction is accompanied by undesirable hydrolysis reaction of the acetylated starch after 40-50 minutes reaction time. Investigation of kinetics of the reaction observed that the value of mass transfer rate constant (Kcs is smaller than the surface reaction rate constant (k. Thus, it can be concluded that rate controlling step is mass transfer.  © 2015 BCREC UNDIP. All rights reservedReceived: 7th August 2014; Revised: 8th September 2014; Accepted: 14th September 2014How to Cite: Kumoro, A.C., Amelia, R. (2015. Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 30-37. (doi:10.9767/bcrec.10.1.7181.30-37Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7181.30-37

  11. Ultracold magnetically tunable interactions without radiative charge transfer losses between Ca$^+$, Sr$^+$, Ba$^+$, and Yb$^+$ ions and Cr atoms

    CERN Document Server

    Tomza, Michał

    2015-01-01

    The Ca$^+$, Sr$^+$, Ba$^+$, and Yb$^+$ ions immersed in an ultracold gas of the Cr atoms are proposed as experimentally feasible heteronuclear systems in which ion-atom interactions at ultralow temperatures can be controlled with magnetically tunable Feshbach resonances without charge transfer and radiative losses. \\textit{Ab initio} techniques are applied to investigate electronic-ground-state properties of the (CaCr)$^+$, (SrCr)$^+$, (BaCr)$^+$, and (YbCr)$^+$ molecular ions. The potential energy curves, permanent electric dipole moments, and static electric dipole polarizabilities are computed. The spin restricted open-shell coupled cluster method restricted to single, double, and noniterative triple excitations, RCCSD(T), and the multireference configuration interaction method restricted to single and double excitations, MRCISD, are employed. The scalar relativistic effects are included within the small-core energy-consistent pseudopotentials. The leading long-range induction and dispersion interaction co...

  12. An ion cyclotron resonance study of reactions of some atomic and simple polyatomic ions with water

    Science.gov (United States)

    Karpas, Z.; Anicich, V. G.; Huntress, W. T., Jr.

    1978-01-01

    Reactions of various positive ions with water vapor were studied by ion cyclotron resonance mass spectrometric techniques. Rate constants and product distributions were determined for reactions of the ions: Ar(+), Co(+), N2(+), and CO2(+), CH2(+), and CH4(+), CH2Cl(+), HCO(+), H2CO(+), H2COH(+), H2S(+) and HS(+). The results obtained in this work are compared with earlier reported data where available.

  13. Heat transfer enhancement using air-atomized spray cooling with water-Al2O3 nano-fluid

    International Nuclear Information System (INIS)

    The study deals with the air-atomized spray cooling using nano-fluid as the cooling media for high heat flux applications. The nano-fluid has been prepared by commercial Al2O3 particles of diameter less than 13 nm and water. Heat transfer study has been carried out on a pre-heated steel specimen of dimensions 100 mm x 100 mm x 6 mm. The initial temperature of the plate which was subjected to air-atomized spray cooling was over 900 deg. C. Various coolants consisting of 0.1% volumetric concentration of water -Al2O3 mixture, with or without a dispersing agent (surfactant) were used for the study. The dispersing agents used are sodium dodecyl sulphate (SDS) and polyoxyethylene (20) sorbitan monolaurate (Tween 20). Inverse heat conduction software INTEMP has been used for estimating the surface heat flux and temperatures taking into account the measured internal temperature histories by the thermocouples during the cooling process. The results obtained using nano-fluid coolants are compared with that of the results where pure water (filtered potable water) is used as a coolant. The analyses reveal that the cooling rate, critical heat flux and heat transfer coefficients are significantly enhanced when nano-fluids are used as coolants in air-atomized spray process. Also, the nano-fluid coolants with dispersing agent shows a better enhancement of heat transfer over that of the nano-fluid without the dispersing media. The nano-fluid with dispersing agent Tween 20 is found more effective than that of its counterpart. Overall, the percentage enhancement in cooling rate of all these nano-fluids compared with pure water (filtered potable water) is 10.2% for water-Al2O3, 18.6% for water-Al2O3-SDS, and up to 32.3% for water-Al2O3 -Tween 20. (authors)

  14. Fusion and neutron transfer reactions with weakly bound nuclei within time-dependent and coupled channel approaches

    Science.gov (United States)

    Samarin, V. V.

    2016-05-01

    The time-dependent Schrödinger equation and the coupled channel approach based on the method of perturbed stationary two-center states are used to describe nucleon transfers and fusion in low-energy nuclear reactions. Results of the cross sections calculation for the formation of the 198Au and fusion in the 6He+197Au reaction and for the formation of the 65Zn in 6He+64Zn reaction agree satisfactorily with the experimental data near the barrier. The Feynman's continual integrals calculations for a few-body systems were used for the proposal of the new form of the shell model mean field for helium isotopes.

  15. CMOS compatible strategy based on selective atomic layer deposition of a hard mask for transferring block copolymer lithography patterns

    Energy Technology Data Exchange (ETDEWEB)

    Gay, G; Grampeix, H; Martin, F; Jalaguier, E; De Salvo, B [CEA LETI MINATEC, 17 rue des Martyrs, 38054 Grenoble (France); Baron, T; Agraffeil, C; Salhi, B; Chevolleau, T; Cunge, G; Tortai, J-H, E-mail: guillaume.gay@cea.fr, E-mail: thierry.baron@cea.fr [CNRS-LTM, 17 rue des Martyrs, 38054 Grenoble (France)

    2010-10-29

    A generic, CMOS compatible strategy for transferring a block copolymer template to a semiconductor substrate is demonstrated. An aluminum oxide (Al{sub 2}O{sub 3}) hard mask is selectively deposited by atomic layer deposition in an organized array of holes obtained in a PS matrix via PS-b-PMMA self-assembly. The Al{sub 2}O{sub 3} nanodots act as a highly resistant mask to plasma etching, and are used to pattern high aspect ratio (>10) silicon nanowires and nanopillars.

  16. Iodinated (Perfluoro)alkyl Quinoxalines by Atom Transfer Radical Addition Using ortho-Diisocyanoarenes as Radical Acceptors.

    Science.gov (United States)

    Leifert, Dirk; Studer, Armido

    2016-09-12

    A simple method for the preparation of functionalized quinoxalines is reported. Starting from readily accessible ortho-diisocyanoarenes and (perfluoro)alkyl iodides, the quinoxaline core is constructed during (perfluoro)alkylation by atom transfer radical addition (ATRA), resulting in 2-iodo-3-(perfluoro)alkylquinoxalines. The radical cascades are readily initiated either with visible light or by using α,α'-azobisisobutyronitrile (AIBN). The heteroarene products are obtained in high yields (up to 94 %), and the method can be readily scaled up. Useful follow-up chemistry documents the value of the novel radical quinoxaline synthesis.

  17. Direct visualization of triplex DNA molecular dynamics by fluorescence resonance energy transfer and atomic force microscopy measurements

    Science.gov (United States)

    Chang, Chia-Ching; Lin, Po-Yen; Chen, Yen-Fu; Chang, Chia-Seng; Kan, Lou-Sing

    2007-11-01

    We have detected the dynamics of 17-mer DNA triplex dissociation mechanism at the molecular level. Fluorescence resonance energy transfer (FRET) was used as an indicator of intermolecular interaction in nanometer range, whereas atomic force microscopy (AFM) was employed to address single molecule with sub-angstrom precision. The maximum rupture force of DNA triplex was found at pH 4.65, consistent with macroscopic observations. These results indicated that the FRET together with an AFM detection system could be used to reveal the DNA triplex interaction in nanometer scale unambiguously.

  18. Suppression of angular momentum transfer in cold collisions of transition metal atoms in ground States with nonzero orbital angular momentum.

    Science.gov (United States)

    Hancox, Cindy I; Doret, S Charles; Hummon, Matthew T; Krems, Roman V; Doyle, John M

    2005-01-14

    The Zeeman relaxation rate in cold collisions of Ti(3d(2)4s(2) 3F2) with He is measured. We find that collisional transfer of angular momentum is dramatically suppressed due to the presence of the filled 4s(2) shell. The degree of electronic interaction anisotropy, which is responsible for Zeeman relaxation, is estimated to be about 200 times smaller in the Ti-He complex than in He complexes with typical non-S-state atoms. PMID:15698077

  19. Dramatic Influence of an Anionic Donor on the Oxygen-Atom Transfer Reactivity of a MnV–Oxo Complex

    OpenAIRE

    Neu, Heather M.; Quesne, Matthew G; Yang, Tzuhsiung; Prokop-Prigge, Katharine A; Lancaster, Kyle M.; Donohoe, James; DeBeer, Serena; de Visser, Sam P; Goldberg, David P.

    2014-01-01

    Addition of an anionic donor to an MnV(O) porphyrinoid complex causes a dramatic increase in 2-electron oxygen-atom-transfer (OAT) chemistry. The 6-coordinate [MnV(O)(TBP8Cz)(CN)]− was generated from addition of Bu4N+CN− to the 5-coordinate MnV(O) precursor. The cyanide-ligated complex was characterized for the first time by Mn K-edge X-ray absorption spectroscopy (XAS) and gives Mn–O=1.53 Å, Mn–CN=2.21 Å. In combination with computational studies these distances were shown to correlate with ...

  20. Diffusion-regulated phase-transfer catalysis for atom transfer radical polymerization of methyl methacrylate in an aqueous/organic biphasic system.

    Science.gov (United States)

    Ding, Mingqiang; Jiang, Xiaowu; Peng, Jinying; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

    2015-03-01

    A concept based on diffusion-regulated phase-transfer catalysis (DRPTC) in an aqueous-organic biphasic system with copper-mediated initiators for continuous activator regeneration is successfully developed for atom transfer radical polymerization (ICAR ATRP) (termed DRPTC-based ICAR ATRP here), using methyl methacrylate (MMA) as a model monomer, ethyl α-bromophenylacetate (EBrPA) as an initiator, and tris(2-pyridylmethyl)amine (TPMA) as a ligand. In this system, the monomer and initiating species in toluene (organic phase) and the catalyst complexes in water (aqueous phase) are simply mixed under stirring at room temperature. The trace catalyst complexes transfer into the organic phase via diffusion to trigger ICAR ATRP of MMA with ppm level catalyst content once the system is heated to the polymerization temperature (75 °C). It is found that well-defined PMMA with controlled molecular weights and narrow molecular weight distributions can be obtained easily. Furthermore, the polymerization can be conducted in the presence of limited amounts of air without using tedious degassed procedures. After cooling to room temperature, the upper organic phase is decanted and the lower aqueous phase is reused for another 10 recycling turnovers with ultra low loss of catalyst and ligand loading. At the same time, all the recycled catalyst complexes retain nearly perfect catalytic activity and controllability, indicating a facile and economical strategy for catalyst removal and recycling.