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Sample records for direct reactions spectroscopy

  1. Direct reactions and nuclear spectroscopy; forward into the 21st century

    International Nuclear Information System (INIS)

    Keeley, N.

    2006-01-01

    The use of direct reactions of the (d,p) (3He,d) etc. type in nuclear spectroscopy has a long history. The availability of beams of exotic nuclei has seen a resurgence of interest in the technique as a means of probing the structure of nuclei close to, or even beyond, the driplines. Analysis of these reactions to extract spectroscopic information has usually been performed with standard DWBA. However, while the DWBA is still useful, as it is based on first-order perturbation theory it should only be used where couplings are weak and proceed predominantly in a single step. Examples where either or both of these conditions are violated, with important consequences for the spectroscopic information extracted, are presented. Some of the sources of uncertainty that remain in the derived quantities are also discussed, along with possible means of reducing them

  2. Direct Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Austern, N. [University of Pittsburgh, Pittsburgh, PA (United States)

    1963-01-15

    In order to give a unified presentation of one point of view, these lectures are devoted only to a detailed development of the standard theories of direct reactions, starting from basic principles. Discussion is given of the present status of the theories, of the techniques used for practical calculation, and of possible future developments. The direct interaction (DI) aspects of a reaction are those which involve only a few of the many degrees of freedom of a nucleus. In fact the minimum number of degrees of freedom which must be involved in a reaction are those required to describe the initial and final channels, and DI studies typically consider these degrees of freedom and no others. Because of this simplicity DI theories may be worked out in painstaking detail. DI processes concern only part of the wave function for a problem. The other part involves complicated excitations of many degrees of freedom, and gives the compound nucleus (CN) effects. While it is extremely interesting to learn how to separate DI and CN effects in an orderly manner, if they are both present in a reaction, no suitable method has yet been found. Instead, current work stresses the kinds of reactions and the kinds of final states in which DI effects dominate and in which CN effects may almost be forgotten. The DI cross-sections which are studied are often extremely large, comparable to elastic scattering cross-sections. (author)

  3. The Reaction Mechanism of Claisen Rearrangement Obtained by Transition State Spectroscopy and Single Direct-Dynamics Trajectory

    Directory of Open Access Journals (Sweden)

    Takayoshi Kobayashi

    2013-02-01

    Full Text Available Chemical bond breaking and formation during chemical reactions can be observed using “transition state spectroscopy”. Comparing the measurement result of the transition state spectroscopy with the simulation result of single direct-dynamics trajectory, we have elucidated the reaction dynamics of Claisen rearrangement of allyl vinyl ether. Observed the reaction of the neat sample liquid, we have estimated the time constants of transformation from straight-chain structure to aromatic-like six-membered ring structure forming the C1-C6 bond. The result clarifies that the reaction proceeds via three steps taking longer time than expected from the gas phase calculation. This finding provides new hypothesis and discussions, helping the development of the field of reaction mechanism analysis.

  4. Giant resonance spectroscopy of 40Ca with the (e,e'x) reaction (III): Direct versus statistical decay

    International Nuclear Information System (INIS)

    Carter, J.; Diesener, H.; Helm, U.; Herbert, G.; Neumann-Cosel, P. von; Richter, A.; Schrieder, G.; Strauch, S.

    2001-01-01

    The present article is the third out of three on a study of the 40 Ca(e,e'x) reaction discussing the role of direct and statistical contributions to the decay of the observed giant resonance strengths. The proton and α decay modes leading to low-lying final states in 36 Ar and 39 K were investigated. The branching ratios for the p 0 , p 123 , α 0 and α 1 channels are compared to statistical model calculations. In the excitation region of dominant isoscalar E2 strength (E x =12-18 MeV) good agreement is observed. Model predictions of direct E2 decay for the (α 0 +α 1 )/(p 0 +p 1 ) ratio describe the data poorly. In the isovector E1 excitation region large excess strength is found in the population of low-lying states in 39 K. A fluctuation analysis shows the direct contributions to the p 0 , p 1 channels to be ≥85%. The presence of preequilibrium components is indicated by the significant nonstatistical decay to the p 3 level which has a dominant 'phonon·hole' structure. Cross correlations reveal no significant branching between the different channels. The correlations between different electron scattering angles in the p 0 , p 1 and p 3 decay result in an interaction radius compatible with the whole nucleus acting as an emitting source

  5. Nuclear spectroscopy with direct relations II. Proceedings

    International Nuclear Information System (INIS)

    Throw, F. E.

    1964-01-01

    The Symposium on Nuclear Spectroscopy with Direct Reactions, sponsored and organized by Argonne National Laboratory under the auspices of the U. S. Atomic Energy Commission, was held on 9-11 March 1964 at the Center for Continuing Education, University of Chicago. The present volume contains the invited papers along with abstracts or summaries of the few short papers selected for their special relevance to the topics of the invited lecturers . Edited versions of the discussions are also included

  6. Exchange effects in direct reactions

    International Nuclear Information System (INIS)

    LeMere, M.; Kanellopoulos, E.J.; Suenkel, W.; Tang, Y.C.

    1979-01-01

    The effect of antisymmetrization in direct reactions is examined by studying the properties of the coupling-normalization kernel function occurring in a resonating-group formulation. From this study, one obtains useful information concerning the general behavior of direct-reactiion processes and some justification for the use of three-body models in phenomenological analyses

  7. Medium effects in direct reactions

    International Nuclear Information System (INIS)

    Karakoc, M; Bertulani, C

    2013-01-01

    We discuss medium corrections of the nucleon-nucleon (NN) cross sections and their influence on direct reactions at intermediate energies ≳50 MeV/nucleon. The results obtained with free NN cross sections are compared with those obtained with a geometrical treatment of Pauli-blocking and Dirac-Bruecker methods. We show that medium corrections may lead to sizable modifications for collisions at intermediate energies and that they are more pronounced in reactions involving weakly bound nuclei.

  8. Future Directions in Ultraviolet Spectroscopy

    Science.gov (United States)

    Sonneborn, George (Editor); Moos, Warren; VanSteenberg, Michael

    2009-01-01

    The 'Future Directions in Ultraviolet Spectroscopy' conference was inspired by the accomplishments of the Far Ultraviolet Spectroscopic Explorer (FUSE) Mission. The FUSE mission was launched in June 1999 and spent over eight years exploring the far-ultraviolet universe, gathering over 64 million seconds of high-resolution spectral data on nearly 3000 astronomical targets. The goal of this conference was not only to celebrate the accomplishments of FUSE, but to look toward the future and understand the major scientific drivers for the ultraviolet capabilities of the next generation fo space observatories. Invited speakers presented discussions based on measurements made by FUSE and other ultraviolet instruments, assessed their connection with measurements made with other techniques and, where appropriate, discussed the implications of low-z measurements for high-z phenomena. In addition to the oral presentations, many participants presented poster papers. The breadth of these presentation made it clear that much good science is still in progress with FUSE data and that these result will continue to have relevance in many scientific areas.

  9. Nuclear spectroscopy using the neutron capture reaction

    International Nuclear Information System (INIS)

    Egidy, T.

    1982-01-01

    Experimental methods using neutron spectroscopy as a means to study the nucleus structure are described. Since reactions of neutron capture (n, γ) are non-selective, they permit to study the nature of excitation (monoparticle and collective) of nuclear levels, the nature of vibrational excitations, to check the connection between shell model and liquid drop model etc. In many cases (n, γ) reactions are the only way to check the forecast of nuclear models. Advantages of (n, γ) spectroscopy, possessing a high precision of measurement and high sensitivity, are underlined. Using neutron spectroscopy on facilities with a high density of neutron flux the structures of energy levels of a large group of nuclei are studied. In different laboratories complete schemes of energy levels of nuclei are obtained, a great number of new levels are found, the evergy level densities are determined, multipolarities of γ-transitions, spins, level parities are considered. StrUctures of rotational bands of heavy deformed nuclei are studied. The study of the structure of high-spin states is possible only using the methods of (n, γ) spectroscopy Investigation results of the nuclei 24 Na, 114 Cd, 154 Eu, 155 Cd, 155 Sm, 233 Th are considered as examples. The most interesting aspects of the investigations using neutron spectroscopy are discUssed

  10. Multi-step direct reactions

    International Nuclear Information System (INIS)

    Koning, A.J.

    1992-07-01

    In recent years a variety of statistical theories has been developed concerning multistep direct (MSD) nuclear reactions. In addition, dominant in applications is a whole class of semiclassical models that may be subsumed under the heading of 'generalized exciton models'; these are basically MSD-type extensions on top of compound-like concepts. In this report the relation between their underlying statistical MSD-postulates are highlighted. A command framework is sketched that enables to generate the various MSD theories through assigning statistical properties to different parts of the nuclear Hamiltonian. Then it is shown that distinct forms of nuclear randomness are embodied in the mentioned theories. All these theories appear to be very similar at a qualitative level. In order to explain the high energy-tails and forward-peaked angular distribution typical for particles emitted in MSD reactions, it is imagined that the incident continuum particle stepwise looses its energy and direction in a sequence of collisions, thereby creating new particle-hole pairs in the target system. At each step emission may take place. The statistical aspect comes in because many continuum states are involved in the process. These are supposed to display chaotic behavior, the associated randomness assumption giving rise to important simplifications in the expression for MSD emission cross sections. This picture suggests that mentioned MSD models can be interpreted as a variant of essentially one and the same theory. 113 refs.; 25 figs.; 9 tabs

  11. Spectroscopy and reaction kinetics of HCO

    International Nuclear Information System (INIS)

    Guo, Yili.

    1989-01-01

    The high-resolution infrared spectrum of the C-H stretching fundamental of HCO has been studied by means of infrared flash kinetic spectroscopy. HCO was generated by flash photolysis of acetaldehyde or formaldehyde using a 308 nm (XeCl) excimer laser. The transient absorption was probed with an infrared difference frequency laser system. The high resolution spectra obtained were assigned and fitted with rotational, spin-rotational, and centrifugal distortion constants. The ν 1 band origin is 2434.48 cm/sup /minus/1/. New ground state constants have been derived from a least-squares fit combining the ν 1 data with previous microwave and FIR LMR measurements. A new set of spectroscopic constants for the (1, 0, 0) state, the equilibrium rotational constants, and the orientation of the transition dipole moment are also reported. The kinetics and product branching ratios of the HCO + NO 2 reaction have been studied using visible and infrared laser flash kinetic spectroscopy. The rate constant for the disappearance of HCO radical at 296 K is (5.7 +- 0.9) /times/ 10/sup /minus/11/ cm 3 molec/sup /minus/1/ sec/sup /minus/1/, and it is independent of the pressure of SF 6 buffer gas up to 700 torr. Less than 10% of the reaction goes through the most exothermic product channel, HNO + CO 2 . The product channel, H + CO 2 + NO, is responsible for 52% of the reaction. HONO has been observed, though not quantitatively, as a reaction product corresponding to the HONO + CO channel. 51 refs., 21 figs., 8 tabs

  12. Dispersion Theory of Direct Nuclear Reactions

    International Nuclear Information System (INIS)

    Shapiro, I.S.

    1963-01-01

    reasons for the agreement if it is not accidental. In short, the theory behaves like an unpredictable person. A major success in the application of perturbation theory to direct processes in the Butler theory of deuteron stripping ((d, p), (d, n)) and pick-up ((p, d), (n, d)). The Butler theory satisfactorily predicts the position of the first maximum (by the increase of the angle) in the angular distribution of reaction products as a function of the orbital momentum of the nucleon captured by the nucleus (stripping reaction) or picked up by an incident particle (pick- up reaction). This result permitted the use of stripping and pick-up reactions in nuclear spectroscopy. At the same time this led to the problem of understanding the true meaning of the Butler approximation. This problem was also essential because the Butler theory inadequately describes several other features of the stripping and pick-up reactions (such as the change of angular distribution with the energy of incident particles, the relation of intensities at the maxima of angular distributions, absolute values of. cross-sections and, sometimes, the relative probabilities for the excitation of different states of residual nuclei). A new method in direct process theory was offered not so long ago (in 1961). The method is based on fairly general properties of the reaction amplitudes and is free from the un-justified assumptions, of the form er theory, in particular the application of perturbation theory. This method makes it possible to obtain several new results and obtain a uniform description cf a great variety of processes (such as direct reactions of the conventional type at low and medium energies, the transfer of nucleons in the bombardment of nuclei by multi-charged ions and the processes of fragmentation at high energies). At the same time the new approach explains, with surprising simplicity, the causes of the form erly enigmatic success of the Butler theory and indicates the limits of its

  13. Dispersion Theory of Direct Nuclear Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Shapiro, I. S. [Institute Of Theoretical And Experimental Physics, Moscow, USSR (Russian Federation)

    1963-01-15

    reasons for the agreement if it is not accidental. In short, the theory behaves like an unpredictable person. A major success in the application of perturbation theory to direct processes in the Butler theory of deuteron stripping ((d, p), (d, n)) and pick-up ((p, d), (n, d)). The Butler theory satisfactorily predicts the position of the first maximum (by the increase of the angle) in the angular distribution of reaction products as a function of the orbital momentum of the nucleon captured by the nucleus (stripping reaction) or picked up by an incident particle (pick- up reaction). This result permitted the use of stripping and pick-up reactions in nuclear spectroscopy. At the same time this led to the problem of understanding the true meaning of the Butler approximation. This problem was also essential because the Butler theory inadequately describes several other features of the stripping and pick-up reactions (such as the change of angular distribution with the energy of incident particles, the relation of intensities at the maxima of angular distributions, absolute values of. cross-sections and, sometimes, the relative probabilities for the excitation of different states of residual nuclei). A new method in direct process theory was offered not so long ago (in 1961). The method is based on fairly general properties of the reaction amplitudes and is free from the un-justified assumptions, of the form er theory, in particular the application of perturbation theory. This method makes it possible to obtain several new results and obtain a uniform description cf a great variety of processes (such as direct reactions of the conventional type at low and medium energies, the transfer of nucleons in the bombardment of nuclei by multi-charged ions and the processes of fragmentation at high energies). At the same time the new approach explains, with surprising simplicity, the causes of the form erly enigmatic success of the Butler theory and indicates the limits of its

  14. Conformational heterogeneity of the bacteriopheophytin electron acceptor HA in reaction centers from Rhodopseudomonas viridis revealed by Fourier transform infrared spectroscopy and site-directed mutagenesis.

    Science.gov (United States)

    Breton, J; Bibikova, M; Oesterhelt, D; Nabedryk, E

    1999-08-31

    The light-induced Fourier transform infrared (FTIR) difference spectra corresponding to the photoreduction of either the HA bacteriopheophytin electron acceptor (HA-/HA spectrum) or the QA primary quinone (QA-/QA spectrum) in photosynthetic reaction centers (RCs) of Rhodopseudomonas viridis are reported. These spectra have been compared for wild-type (WT) RCs and for two site-directed mutants in which the proposed interactions between the carbonyls on ring V of HA and the RC protein have been altered. In the mutant EQ(L104), the putative hydrogen bond between the protein and the 9-keto C=O of HA should be affected by changing Glu L104 to a Gln. In the mutant WF(M250), the van der Waals interactions between Trp M250 and the 10a-ester C=O of HA should be modified. The characteristic effects of both mutations on the FTIR spectra support the proposed interactions and allow the IR modes of the 9-keto and 10a-ester C=O of HA and HA- to be assigned. Comparison of the HA-/HA and QA-/QA spectra leads us to conclude that the QA-/QA IR signals in the spectral range above 1700 cm-1 are largely dominated by contributions from the electrostatic response of the 10a-ester C=O mode of HA upon QA photoreduction. A heterogeneity in the conformation of the 10a-ester C=O mode of HA in WT RCs, leading to three distinct populations of HA, appears to be related to differences in the hydrogen-bonding interactions between the carbonyls of ring V of HA and the RC protein. The possibility that this structural heterogeneity is related to the observed multiexponential kinetics of electron transfer and the implications for primary processes are discussed. The effect of 1H/2H exchange on the QA-/QA spectra of the WT and mutant RCs shows that neither Glu L104 nor any other exchangeable carboxylic residue changes appreciably its protonation state upon QA reduction.

  15. Substrate-Directed Catalytic Selective Chemical Reactions.

    Science.gov (United States)

    Sawano, Takahiro; Yamamoto, Hisashi

    2018-05-04

    The development of highly efficient reactions at only the desired position is one of the most important subjects in organic chemistry. Most of the reactions in current organic chemistry are reagent- or catalyst-controlled reactions, and the regio- and stereoselectivity of the reactions are determined by the inherent nature of the reagent or catalyst. In sharp contrast, substrate-directed reaction determines the selectivity of the reactions by the functional group on the substrate and can strictly distinguish sterically and electronically similar multiple reaction sites in the substrate. In this Perspective, three topics of substrate-directed reaction are mainly reviewed: (1) directing group-assisted epoxidation of alkenes, (2) ring-opening reactions of epoxides by various nucleophiles, and (3) catalytic peptide synthesis. Our newly developed synthetic methods with new ligands including hydroxamic acid derived ligands realized not only highly efficient reactions but also pinpointed reactions at the expected position, demonstrating the substrate-directed reaction as a powerful method to achieve the desired regio- and stereoselective functionalization of molecules from different viewpoints of reagent- or catalyst-controlled reactions.

  16. Generation and reactivity of the phenyl cation in cryogenic argon matrices: monitoring the reactions with nitrogen and carbon monoxide directly by IR spectroscopy.

    Science.gov (United States)

    Winkler, Michael; Sander, Wolfram

    2006-08-18

    The phenyl cation 1 has been prepared by co-deposition of iodobenzene 6 or bromobenzene 7 with a microwave-induced argon plasma and characterized by IR spectroscopy in cryogenic argon matrices. The cation can clearly be identified by its strongest absorption at 3110 cm(-1) that is rapidly bleached upon visible light irradiation. This characteristic band is observed neither in the conventional photochemistry of 6 or 7 nor in discharge experiments with alkyl halides or chlorobenzene. The latter finding is in line with energetic considerations. According to density functional theory (DFT) computations, the strongest absorption of 1 is caused by a C-H stretching vibration that involves almost entirely the ortho-hydrogens. This is confirmed by isotopic labeling experiments. Co-deposition of halobenzene/N2 mixtures leads to a decrease of the 3110 cm(-1) absorption, whereas several new signals are detected in the 2200-2400 cm(-1) range of the IR spectrum. Annealing of a matrix that contains 1 and 1% N2 leads to an increase of a broad band at 2260 cm(-1) that is assigned to the benzenediazonium ion 2. A sharp signal at 2327 cm(-1) that had previously been assigned to the N-N stretching vibration of 2 is due to molecular nitrogen. The mechanism that triggers the IR activity of N2 is not yet understood. Annealing of a matrix that contains 1 and 0.5% CO leads to an increase of a broad band at 2217 cm(-1) that is considerably stronger than the 2260 cm(-1) absorption of 2. This signal is assigned to the C-O stretching vibration of the benzoyl cation 12, in excellent agreement with previous investigations of 12 in superacidic media. Some consequences of the measured frequencies with regard to bonding in 2 and 12 are discussed.

  17. Direct angle resolved photoemission spectroscopy and ...

    Indian Academy of Sciences (India)

    Since 1997 we systematically perform direct angle resolved photoemission spectroscopy (ARPES) on in-situ grown thin (< 30 nm) cuprate films. Specifically, we probe low-energy electronic structure and properties of high-c superconductors (HTSC) under different degrees of epitaxial (compressive vs. tensile) strain.

  18. Progress in microscopic direct reaction modeling of nucleon induced reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dupuis, M.; Bauge, E.; Hilaire, S.; Lechaftois, F.; Peru, S.; Pillet, N.; Robin, C. [CEA, DAM, DIF, Arpajon (France)

    2015-12-15

    A microscopic nuclear reaction model is applied to neutron elastic and direct inelastic scatterings, and pre-equilibrium reaction. The JLM folding model is used with nuclear structure information calculated within the quasi-particle random phase approximation implemented with the Gogny D1S interaction. The folding model for direct inelastic scattering is extended to include rearrangement corrections stemming from both isoscalar and isovector density variations occurring during a transition. The quality of the predicted (n,n), (n,n{sup '}), (n,xn) and (n,n{sup '}γ) cross sections, as well as the generality of the present microscopic approach, shows that it is a powerful tool that can help improving nuclear reactions data quality. Short- and long-term perspectives are drawn to extend the present approach to more systems, to include missing reactions mechanisms, and to consistently treat both structure and reaction problems. (orig.)

  19. Direct Frequency Comb Spectroscopy of Alkali Atoms

    Science.gov (United States)

    Pradhananga, Trinity; Palm, Christopher; Nguyen, Khoa; Guttikonda, Srikanth; Kimball, Derek Jackson

    2011-11-01

    We are using direct frequency comb spectroscopy to study transition frequencies and excited state hyperfine structure in potassium and rubidium using 2-photon transitions excited directly with the frequency-doubled output of a erbium fiber optical frequency comb. The frequency comb output is directed in two counterpropagating directions through a vapor cell containing the atomic vapor of interest. A pair of optical filters is used to select teeth of the comb in order to identify the transition wavelengths. A photomultiplier tube (PMT) measures fluorescence from a decay channel wavelength selected with another optical filter. Using different combinations of filters enables a wide range of transitions to be investigated. By scanning the repetition rate, a Doppler-free spectrum can be obtained enabling kHz-resolution spectral measurements. The thermal motion of the atoms in the vapor cell actually eliminates the need to fine-tune the offset frequency and repetition rate, alleviating a somewhat challenging requirement for spectroscopy of cold atoms. Our investigations are laying the groundwork for a long-term research program to use direct frequency comb spectroscopy to understand the complex spectra of rare-earth atoms.

  20. Induced isospin mixing in direct nuclear reactions

    International Nuclear Information System (INIS)

    Lenske, H.

    1979-07-01

    The effect of charge-dependent interactions on nuclear reactions is investigated. First, a survey is given on the most important results concerning the charge dependence of the nucleon-nucleon interaction. The isospin symmetry and invariance principles are discussed. Violations of the isospin symmetry occuring in direct nuclear reactions are analysed using the soupled channel theory, the folding model and microscopic descriptions. Finally, induced isospin mixing in isospin-forbidden direct reactions is considered using the example of the inelastic scattering of deuterons on 12 C. (KBE)

  1. Cross sections for multistep direct reactions

    International Nuclear Information System (INIS)

    Demetriou, Paraskevi; Marcinkowski, Andrzej; Marianski, Bohdan

    2002-01-01

    Inelastic scattering and charge-exchange reactions have been analysed at energies ranging from 14 to 27 MeV using the modified multistep direct reaction theory (MSD) of Feshbach, Kerman and Koonin. The modified theory considers the non-DWBA matrix elements in the MSD cross section formulae and includes both incoherent particle-hole excitations and coherent collective excitations in the continuum, according to the prescriptions. The results show important contributions from multistep processes at all energies considered. (author)

  2. Direct catalytic asymmetric aldol-Tishchenko reaction.

    Science.gov (United States)

    Gnanadesikan, Vijay; Horiuchi, Yoshihiro; Ohshima, Takashi; Shibasaki, Masakatsu

    2004-06-30

    A direct catalytic asymmetric aldol reaction of propionate equivalent was achieved via the aldol-Tishchenko reaction. Coupling an irreversible Tishchenko reaction to a reversible aldol reaction overcame the retro-aldol reaction problem and thereby afforded the products in high enantio and diastereoselectivity using 10 mol % of the asymmetric catalyst. A variety of ketones and aldehydes, including propyl and butyl ketones, were coupled efficiently, yielding the corresponding aldol-Tishchenko products in up to 96% yield and 95% ee. Diastereoselectivity was generally below the detection limit of 1H NMR (>98:2). Preliminary studies performed to clarify the mechanism revealed that the aldol products were racemic with no diastereoselectivity. On the other hand, the Tishchenko products were obtained in a highly enantiocontrolled manner.

  3. Direct processes in heavy ion reactions

    International Nuclear Information System (INIS)

    Bunakov, V.E.; Zagrebaev, V.I.

    1983-01-01

    Direct processes in heavy ion reactions are investigated. Relative theoretical contributions in the inclusive spectrum of α particles on processes of stripping breakup and inelastic breakup are estimated using the 22 Ne+ 181 Ta reaction as an example. The consideration is performed taking into account Coulomb and nuclear distortions in the inlet and outlet ion channels. It is shown that the hard edge of α spectrum and its maximum are well described by peripheral direct processes. The hard spectrum edge is conditioned by the pure process of ''incomplete fussion'' bringing about the production af a compound nucleus. The main part of inclusive spectrum is conditioned by reactions of inelastic and elastic breakup not connected with the production of a compound nucleus

  4. Direct interaction in nuclear reactions: a theory

    International Nuclear Information System (INIS)

    Dominicis, C.T. de

    1959-01-01

    General treatment of the foundations of direct interaction in nuclear reactions; representation of the instantaneous elastic scattering amplitude by the scattering amplitude due to a complex potential; expansion of the instantaneous inelastic scattering amplitude and discussion of the 1. Bohr approximation (distorted waves) contribution to individual and collective states of excitation. (author) [fr

  5. MONITORING REACTIONS IN ALKALINE DIRECT ETHANOL FUEL CELLS ASSEMBLED WITH NON-PT-CATALYST

    OpenAIRE

    Gülzow, Erich; Beyer, Monique; Friedrich, K. Andreas; Pengel, Stefanie; Fischer, Peter; Bettermann, Hans

    2011-01-01

    This contribution shows how Raman spectroscopy can be used to pursue chemical reactions within fuel cells. For this, the oxidation of ethanol occurring in an alkaline direct ethanolic fuel cell was investigated. The analysis of a sequence of Raman spectra recorded during the reaction shows that ethanol was solely oxidized to acetate in a unique reaction.

  6. In situ Observation of Direct Electron Transfer Reaction of Cytochrome c Immobilized on ITO Electrode Modified with 11-{2-[2-(2-Methoxyethoxy)ethoxy]ethoxy}undecylphosphonic Acid Self-assembled Monolayer Film by Electrochemical Slab Optical Waveguide Spectroscopy.

    Science.gov (United States)

    Matsuda, Naoki; Okabe, Hirotaka; Omura, Ayako; Nakano, Miki; Miyake, Koji

    2017-01-01

    To immobilize cytochrome c (cyt.c) on an ITO electrode while keeping its direct electron transfer (DET) functionality, the ITO electrode surface was modified with 11-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}undecylphosphonic acid (CH 3 O (CH 2 CH 2 O) 3 C 11 H 22 PO(OH) 2 , M-EG 3 -UPA) self-assembled monolayer (SAM) film. After a 100-times washing process to exchange a phosphate buffer saline solution surrounding cyt.c and ITO electrode to a fresh one, an in situ observation of visible absorption spectral change with slab optical waveguide (SOWG) spectroscopy showed that 87.7% of the cyt.c adsorbed on the M-EG 3 -UPA modified ITO electrode remained on the ITO electrode. The SOWG absorption spectra corresponding to oxidized and reduced cyt.c were observed with setting the ITO electrode potential at 0.3 and -0.3 V vs. Ag/AgCl, respectively, while probing the DET reaction between cyt.c and ITO electrode occurred. The amount of cyt.c was evaluated to be about 19.4% of a monolayer coverage based on the coulomb amount in oxidation and reduction peaks on cyclic voltammetry (CV) data. The CV peak current maintained to be 83.4% compared with the initial value for a M-EG 3 -UPA modified ITO electrode after 60 min continuous scan with 0.1 V/s between 0.3 and -0.3 V vs. Ag/AgCl.

  7. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    Energy Technology Data Exchange (ETDEWEB)

    Bradforth, S.E.

    1992-11-01

    The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound [yields] bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN[sup [minus

  8. Graphene Charge Transfer, Spectroscopy, and Photochemical Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Brus, Louis [Columbia Univ., New York, NY (United States)

    2017-01-31

    This project focused on the special electronic and optical properties of graphene and adsorbed molecular species. Graphene makes an excellent substrate for current collection in nanostructured photovoltaic designs. Graphene is almost transparent, and can be used as a solar cell window. It also has no surface states, and thus current is efficiently transported over long distances. Progress in graphene synthesis indicates that there will soon be practical methods for making large pieces of graphene for devices. We now need to understand exactly what happens to both ground state and electronically excited molecules and Qdots near graphene, if we are going to use them to absorb light in a nano-structured photovoltaic device using graphene to collect photocurrent. We also need to understand how to shift the graphene Fermi level, to optimize the kinetics of electron transfer to graphene. And we need to learn how to convert local graphene areas to semiconductor structure, to make useful spatially patterned graphenes. In this final report, we describe how we addressed these goals. We explored the question of possible Surface Enhanced Raman spectroscopy from molecular Charge Transfer onto Graphene substrates. We observed strong hole doping of graphene by adsorbed halogens as indicated by the shift of the graphene G Raman band. In the case of iodine adsorption, we also observed the anionic species made by hole doping. At low frequency in the Raman spectrum, we saw quite intense lines from I3- and I5- , suggesting possible SERS. We reported on Fresnel calculations on this thin film system, which did not show any net electromagnetic field enhancement.

  9. Randomness in multi-step direct reactions

    International Nuclear Information System (INIS)

    Koning, A.J.; Akkermans, J.M.

    1991-01-01

    The authors propose a quantum-statistical framework that provides an integrated perspective on the differences and similarities between the many current models for multi-step direct reactions in the continuum. It is argued that to obtain a statistical theory two physically different approaches are conceivable to postulate randomness, respectively called leading-particle statistics and residual-system statistics. They present a new leading-particle statistics theory for multi-step direct reactions. It is shown that the model of Feshbach et al. can be derived as a simplification of this theory and thus can be founded solely upon leading-particle statistics. The models developed by Tamura et al. and Nishioka et al. are based upon residual-system statistics and hence fall into a physically different class of multi-step direct theories, although the resulting cross-section formulae for the important first step are shown to be the same. The widely used semi-classical models such as the generalized exciton model can be interpreted as further phenomenological simplification of the leading-particle statistics theory

  10. Amyloplast Distribution Directs a Root Gravitropic Reaction

    Science.gov (United States)

    Kordyum, Elizabeth

    Immobile higher plants are oriented in the gravitational field due to gravitropim that is a physiological growth reaction and consists of three phases: reception of a gravitational signal by statocytes, its transduction to the elongation zone, and finally the organ bending. As it is known, roots are characterized with positive gravitropism, i. e. they grow in the direction of a gravitational vector, stems - with negative gravitropism, i. e. they grow in the direction opposite to a gravitational vector. According to the Nemec’s and Haberlandt’s starch-statolith hypothesis, amyloplasts in diameter of 1.5 - 3 μ in average, which appear to act as gravity sensors and fulfill a statolythic function in the specialized graviperceptive cells - statocytes, sediment in the direction of a gravitational vector in the distal part of a cell, while a nucleus is in the proximal one. There are reasonable data that confirm the amyloplasts-statoliths participation in gravity perception: 1) correlation between the statoliths localization and the site of gravity sensing, 2) significant redistribution (sedimentation) of amyloplasts in statocytes under gravistimulation in comparison with other cell organelles, 3) root decreased ability to react on gravity under starch removal from amyloplasts, 4) starchless Arabidopsis thaliana mutants are agravitropic, 5) amyloplasts-statoliths do not sediment in the absence of the gravitational vector and are in different parts or more concentrated in the center of statocytes. Plant tropisms have been intensively studied for many decades and continue to be investigated. Nevertheless, the mechanisms by which plants do so is still not clearly explained and many questions on gravisensing and graviresponse remain unanswered. Even accepted hypotheses are now being questioned and recent data are critically evaluated. Although the available data show the Ca2+ and cytoskeleton participation in graviperception and signal transduction, the clear evidence

  11. Erratum: Back reaction, emission spectrum and entropy spectroscopy

    Science.gov (United States)

    Jiang, Qing-Quan; Cai, Xu

    2012-06-01

    In our paper [Qing-Quan Jiang and Xu Cai, Back reaction, emission spectrum and entropy spectroscopy, JHEP 11 (2010) 066], there was an error in using the first law of black hole thermodynamic and the Bohr-Sommerfeld quantization rule. In this erratum, we attempt to rectify them.

  12. Hypernuclear spectroscopy with the (e, e-prime K+) reaction

    Energy Technology Data Exchange (ETDEWEB)

    Yu Fujii

    2003-06-16

    Experimental conditions of the (e,e'K+) reaction for hypernuclear spectroscopy at Jefferson Lab Hall C are considered. Then two hypernuclear experiments at Hall C, Jlab E89-009 and E01-011 are introduced and compared, and possibility to extract information on hypernuclear states are discussed by referring expected spectra obtained with a DWIA calculation.

  13. Spectroscopy and reactions of vibrationally excited transient molecules

    Energy Technology Data Exchange (ETDEWEB)

    Dai, H.L. [Univ. of Pennsylvania, Philadelphia (United States)

    1993-12-01

    Spectroscopy, energy transfer and reactions of vibrationally excited transient molecules are studied through a combination of laser-based excitation techniques and efficient detection of emission from the energized molecules with frequency and time resolution. Specifically, a Time-resolved Fourier Transform Emission Spectroscopy technique has been developed for detecting dispersed laser-induced fluorescence in the IR, visible and UV regions. The structure and spectroscopy of the excited vibrational levels in the electronic ground state, as well as energy relaxation and reactions induced by specific vibronic excitations of a transient molecule can be characterized from time-resolved dispersed fluorescence in the visible and UV region. IR emissions from highly vibrational excited levels, on the other hand, reveal the pathways and rates of collision induced vibrational energy transfer.

  14. Characterization of alkali silica reaction gels using Raman spectroscopy

    International Nuclear Information System (INIS)

    Balachandran, C.; Muñoz, J.F.; Arnold, T.

    2017-01-01

    The ability of Raman spectroscopy to characterize amorphous materials makes this technique ideal to study alkali silica reaction (ASR) gels. The structure of several synthetic ASR gels was thoroughly characterized using Raman Spectroscopy. The results were validated with additional techniques such as Fourier transmission infrared spectroscopy, X-ray powder diffraction and thermogravimetric analysis. The Raman spectra were found to have two broad bands in the 800 to 1200 cm −1 range and the 400 to 700 cm −1 range indicating the amorphous nature of the gel. Important information regarding the silicate polymerization was deduced from both of these spectral regions. An increase in alkali content of the gels caused a depolymerization in the silicate framework which manifested in the Raman spectra as a gradual shift of predominant peaks in both regions. The trends in silicate depolymerization were in agreement with results from a NMR spectroscopy study on similar synthetic ASR gels.

  15. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    Energy Technology Data Exchange (ETDEWEB)

    Bradforth, Stephen Edmund [Univ. of California, Berkeley, CA (United States)

    1992-11-01

    The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound {yields} bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN-, NCO- and NCS-. Transition state photoelectron spectra are presented for the following systems Br + HI, Cl + HI, F + HI, F + CH30H,F + C2H5OH,F + OH and F + H2. A time dependent framework for the simulation and interpretation of the bound → free transition state photoelectron spectra is subsequently developed and applied to the hydrogen transfer reactions Br + HI, F + OH → O(3P, 1D) + HF and F + H2. The theoretical approach for the simulations is a fully quantum-mechanical wave packet propagation on a collinear model reaction potential surface. The connection between the wavepacket time evolution and the photoelectron spectrum is given by the time autocorrelation function. For the benchmark F + H2 system, comparisons with three-dimensional quantum calculations are made.

  16. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    International Nuclear Information System (INIS)

    Bradforth, S.E.

    1992-11-01

    The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound → bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN - , NCO - and NCS - . Transition state photoelectron spectra are presented for the following systems Br + HI, Cl + HI, F + HI, F + CH 3 0H,F + C 2 H 5 OH,F + OH and F + H 2 . A time dependent framework for the simulation and interpretation of the bound → free transition state photoelectron spectra is subsequently developed and applied to the hydrogen transfer reactions Br + HI, F + OH → O( 3 P, 1 D) + HF and F + H 2 . The theoretical approach for the simulations is a fully quantum-mechanical wave packet propagation on a collinear model reaction potential surface. The connection between the wavepacket time evolution and the photoelectron spectrum is given by the time autocorrelation function. For the benchmark F + H 2 system, comparisons with three-dimensional quantum calculations are made

  17. Direct interaction in nuclear reactions: a theory; L'interaction directe dans les reactions nucleaires: theorie

    Energy Technology Data Exchange (ETDEWEB)

    Dominicis, C.T. de [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1959-07-01

    General treatment of the foundations of direct interaction in nuclear reactions; representation of the instantaneous elastic scattering amplitude by the scattering amplitude due to a complex potential; expansion of the instantaneous inelastic scattering amplitude and discussion of the 1. Bohr approximation (distorted waves) contribution to individual and collective states of excitation. (author) [French] Expose general sur les fondements de l'interaction directe dans les reactions nucleaires; representation de l'amplitude de diffusion instantanee elastique par celle due a un potentiel complexe; developpement de l'amplitude de diffusion instantanee inelastique et discussion de la contribution de la premiere approximation de Bohr (sur des distendues) a l'excitation d'etats individuels et collectifs. (auteur)

  18. Modeling membrane protein structure through site-directed ESR spectroscopy

    NARCIS (Netherlands)

    Kavalenka, A.A.

    2009-01-01

    Site-directed spin labeling (SDSL) electron spin resonance (ESR) spectroscopy is a
    relatively new biophysical tool for obtaining structural information about proteins. This
    thesis presents a novel approach, based on powerful spectral analysis techniques (multicomponent
    spectral

  19. Droplet heat transfer and chemical reactions during direct containment heating

    International Nuclear Information System (INIS)

    Baker, L. Jr.

    1986-01-01

    A simplified model of heat transfer and chemical reaction has been adapted to evaluate the expected behavior of droplets containing unreacted Zircaloy and stainless steel moving through the containment atmosphere during postulated accidents involving direct containment heating. The model includes internal and external diffusive resistances to reaction. The results indicate that reactions will be incomplete for many conditions characteristic of direct containment heating sequences

  20. Systematic uncertainties in direct reaction theories

    International Nuclear Information System (INIS)

    Lovell, A E; Nunes, F M

    2015-01-01

    Nuclear reactions are common probes to study nuclei and in particular, nuclei at the limits of stability. The data from reaction measurements depend strongly on theory for a reliable interpretation. Even when using state-of-the-art reaction theories, there are a number of sources of systematic uncertainties. These uncertainties are often unquantified or estimated in a very crude manner. It is clear that for theory to be useful, a quantitative understanding of the uncertainties is critical. Here, we discuss major sources of uncertainties in a variety of reaction theories used to analyze (d,p) nuclear reactions in the energy range E d = 10–20 MeV, and we provide a critical view on how these have been handled in the past and how estimates can be improved. (paper)

  1. Monitoring emulsion homopolymerization reactions using FT-Raman spectroscopy

    Directory of Open Access Journals (Sweden)

    M. M. Reis

    2005-03-01

    Full Text Available The present work describes a methodology for estimation of monomer concentration during homopolymerization reactions by Raman spectroscopy. The estimation is done using linear models based on two different approaches: a univariate approach and a multivariate approach (with principal component regression, PCR, or partial least squares regression, PLS. The linear models are fitted with data from spectra collected from synthetic samples, i.e., samples prepared by dispersing a known concentration of monomer in polymer emulsions. Homopolymerizations of butyl acrylate and of vinyl acetate were monitored by collecting samples from the reactor, and results show that the methodology is efficient for the model fitting and that Raman spectroscopy is a promising technique for on-line monitoring of the emulsion polymerization process.

  2. Direct nuclear reaction experiments for stellar nucleosynthesis

    International Nuclear Information System (INIS)

    Cherubini, S.

    2016-01-01

    During the last two decades indirect methods where proposed and used in many experiments in order to measure nuclear cross sections between charged particles at stellar energies. These are among the lowest to be measured in nuclear physics. One of these methods, the Trojan Horse method, is based on the Quasi- Free reaction mechanism and has proved to be particularly flexible and reliable. It allowed for the measurement of the cross sections of various reactions of astrophysical interest using stable beams. The use and reliability of indirect methods become even more important when reactions induced by Radioactive Ion Beams are considered, given the much lower intensity generally available for these beams. The first Trojan Horse measurement of a process involving the use of a Radioactive Ion Beam dealt with the "1"8F(p,α)"1"5O process in Nova conditions. To obtain pieces of information on this process, in particular about its cross section at Nova energies, the Trojan Horse method was applied to the "1"8F(d,α "1"5O)n three body reaction. In order to establish the reliability of the Trojan Horse method approach, the Treiman-Yang criterion is an important test and it will be addressed briefly in this paper.

  3. Directed Neutron Beams From Inverse Kinematic Reactions

    Science.gov (United States)

    Vanhoy, J. R.; Guardala, N. A.; Glass, G. A.

    2011-06-01

    Kinematic focusing of an emitted fairly mono-energetic neutron beam by the use of inverse-kinematic reactions, i.e. where the projectile mass is greater than the target atom's mass, can provide for the utilization of a significant fraction of the fast neutron yield and also provide for a safer radiation environment. We examine the merit of various neutron production reactions and consider the practicalities of producing the primary beam using the suitable accelerator technologies. Preliminary progress at the NSWC-Carderock Positive Ion Accelerator Facility is described. Possible important applications for this type of neutron-based system can be both advanced medical imaging techniques and active "stand-off" interrogation of contraband items.

  4. Chemical reactions directed Peptide self-assembly.

    Science.gov (United States)

    Rasale, Dnyaneshwar B; Das, Apurba K

    2015-05-13

    Fabrication of self-assembled nanostructures is one of the important aspects in nanoscience and nanotechnology. The study of self-assembled soft materials remains an area of interest due to their potential applications in biomedicine. The versatile properties of soft materials can be tuned using a bottom up approach of small molecules. Peptide based self-assembly has significant impact in biology because of its unique features such as biocompatibility, straight peptide chain and the presence of different side chain functionality. These unique features explore peptides in various self-assembly process. In this review, we briefly introduce chemical reaction-mediated peptide self-assembly. Herein, we have emphasised enzymes, native chemical ligation and photochemical reactions in the exploration of peptide self-assembly.

  5. Toward Direct Reaction-in-Flight Measurements

    Science.gov (United States)

    Wilhelmy, Jerry; Bredeweg, Todd; Fowler, Malcolm; Gooden, Matthew; Hayes, Anna; Rusev, Gencho; Caggiano, Joseph; Hatarik, Robert; Henry, Eugene; Tonchev, Anton; Yeaman, Charles; Bhike, Megha; Krishichayan, Krishi; Tornow, Werner

    2016-03-01

    At the National Ignition Facility (NIF) neutrons having energies greater than the equilibrium 14.1 MeV value can be produced via Reaction-in-Flight (RIF) interactions between plasma atoms and upscattered D or T ions. The yield and spectrum of these RIF produced neutrons carry information on the plasma properties as well as information on the stopping power of ions under plasma conditions. At NIF the yield of these RIF neutrons is predicted to be 4-7 orders of magnitude below the peak 14 MeV neutron yield. The current generation of neutron time of flight (nTOF) instrumentation has so far been incapable of detecting these low-yield neutrons primarily due to high photon backgrounds. To date, information on RIF neutrons has been obtained in integral activation experiments using reactions with high energy thresholds such as 169Tm(n,3n)167Tm and 209Bi(n,4n) 206Bi. Initial experiments to selectively suppress photon backgrounds have been performed at TUNL using pulsed monoenergetic neutron beams of 14.9, 18.5, 24.2, and 28.5 MeV impinging on a Bibenzyl scintillator. By placing 5 cm of Pb before the scintillator we were able to selectively suppress the photons from the flash occurring at the production target and enhance the n/_signal by ~6 times.

  6. Direct reactions for nuclear structure and nuclear astrophysics

    International Nuclear Information System (INIS)

    Jones, Katherine Louise

    2014-01-01

    Direct reactions are powerful probes for studying the atomic nucleus. Modern direct reaction studies are illuminating both the fundamental nature of the nucleus and its role in nucleosynthetic processes occurring in the cosmos. This report covers experiments using knockout reactions on neutron-deficient fragmentation beams, transfer reactions on fission fragment beams, and theoretical sensitivity studies relating to the astrophysical r-process. Results from experiments on 108,106 Sn at the NSCL, and on 131 Sn at HRIBF are presented as well as the results from the nucleosynthesis study.

  7. Direct Reactions for Nuclear Structure and Nuclear Astrophysics

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Katherine Louise [Univ. of Tennessee, Knoxville, TN (United States). Experimental Low-Energy Nuclear Physics Group

    2014-12-18

    Direct reactions are powerful probes for studying the atomic nucleus. Modern direct reaction studies are illuminating both the fundamental nature of the nucleus and its role in nucleosynthetic processes occurring in the cosmos. This report covers experiments using knockout reactions on neutron-deficient fragmentation beams, transfer reactions on fission fragment beams, and theoretical sensitivity studies relating to the astrophysical r-process. Results from experiments on 108,106Sn at the NSCL, and on 131Sn at HRIBF are presented as well as the results from the nucleosynthesis study.

  8. The use of direct geometry spectrometers in molecular spectroscopy

    International Nuclear Information System (INIS)

    Parker, Stewart F; Ramirez-Cuesta, Anibal J; Albers, Peter W; Lennon, David

    2014-01-01

    The advantages and disadvantages of the use of direct geometry spectrometers for molecular spectroscopy and catalysis studies are described. We show that both direct and indirect geometry INS spectrometers are important tools for the study of industrially relevant areas such as catalysis, proton conductors and gas separation. We propose a novel hybrid instrument, Cerberus, that would offer high sensitivity and high-to-reasonable resolution across the entire 'mid-infrared' spectral range that would effectively advance research in these areas

  9. Cytosine Radical Cations: A Gas-Phase Study Combining IRMPD Spectroscopy, UVPD Spectroscopy, Ion-Molecule Reactions, and Theoretical Calculations

    Czech Academy of Sciences Publication Activity Database

    Lesslie, M.; Lawler, J. T.; Dang, A.; Korn, J. A.; Bím, Daniel; Steinmetz, V.; Maitre, P.; Tureček, F.; Ryzhov, V.

    2017-01-01

    Roč. 18, č. 10 (2017), s. 1293-1301 ISSN 1439-4235 Institutional support: RVO:61388963 Keywords : ion-molecule reactions * IRMPD spectroscopy * nucleobases * radical ions * UVPD spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 3.075, year: 2016

  10. On the treatment of exchange effects in direct reactions

    International Nuclear Information System (INIS)

    Bencze, G.; Chandler, C.; Argonne National Lab., IL; New Mexico Univ., Albuquerque

    1985-01-01

    Exchange effects in direct reactions are investigated in the framework of the general algebraic theory of identical particle scattering. It is shown that effects due to the permutation symmetry of the system can be separated from the treatment of reaction dynamics. Dynamical aspects of the problem are investigated within the framework of the channel coupling class of N-body theories. (orig.)

  11. Fusion and direct reactions for strongly and weakly bound projectiles

    International Nuclear Information System (INIS)

    Hugi, M.; Lang, J.; Mueller, R.; Ungricht, E.; Bodek, K.; Jarczyk, L.; Kamys, B.; Magiera, A.; Strzalkowski, A.; Willim, G.

    1981-01-01

    The interaction of 6 Li, 9 Be and 12 C projectiles with a 28 Si target was investigated by measuring the angular distributions of the elasitcally scattered projectiles and of the emitted protons, deuterons and α-particles. The experiment was perfomred in order to deduce direct and compound nucleus process contributions to the total reaction cross section and to study the influence of the projectile structure on the relative importance of these two mechanisms. Optical model parameters and therefore the total reaction cross section are strongly influenced by the binding energy of the projectile. The parameters of the Glas-Mosel describing the fusion reaction vary smoothly with the atomic number. In the system 9 B + 28 Si around 50% of all reactions are direct processes even at energies near the Coulomb barrier, whereas in the other systeme the direct part amounts to 15% ( 12 C) and 30% ( 6 Li) only. (orig.)

  12. Moessbauer spectroscopy on the reaction center of Rhodopseudomonas viridis

    International Nuclear Information System (INIS)

    Frolov, E.; Goldanskii, V.I.; Birk, A.; Parak, F.; Fritzsch, G.; Sinning, I.; Michel, H.

    1992-01-01

    Proteins called 'reaction centers' (RC) can be isolated from many photosynthetic bacteria. They have one non-heme iron in a quinone acceptor region. The RC of Rhodopseudomonas viridis contains an additional tightly bound tetra-heme cytochrome c subunit. The electronic configuration of both cytochrome and the non-heme iron has been studied in the crystallized protein by Moessbauer spectroscopy at different redox potentials, pH-values, and with an addition of o-phenanthroline. At high potentials (E h =+500 mV) all heme irons are in the low spin Fe 3+ -state, and at low potential (E h = 1 50 mV) they are low spin Fe 2+ with the same Moessbauer parameters for all hemes independent of pH. Redox titrations change the relative area of the reduced and oxidized states in agreement with other methods. The non-heme iron shows a high spin Fe 2+ configuration independent of E h and pH with parameters comparable to those of Rhodopseudomonas sphaeroides. Surprisingly, there is strong evidence for another non-heme iron species in part of the molecules with a Fe 2+ low spin configuration. Incubation with o-phenanthroline decreases the relative Fe 2+ hs-area and increases the contribution of Fe 2+ ls-area. Above 210 K the mean square displacement, 2 >, of the RC-crystals increases more than linearly with temperature. This may be correlated with the increase of the electron transfer rate and indicates that intramolecular mobility influences the functional activity of a protein. (orig.)

  13. Statistical theory of multi-step compound and direct reactions

    International Nuclear Information System (INIS)

    Feshbach, H.; Kerman, A.; Koonin, S.

    1980-01-01

    The theory of nuclear reactions is extended so as to include a statistical treatment of multi-step processes. Two types are distinguished, the multi-step compound and the multi-step direct. The wave functions for the system are grouped according to their complexity. The multi-step direct process involves explicitly those states which are open, while the multi-step compound involves those which are bound. In addition to the random phase assumption which is applied differently to the multi-step direct and to the multi-step compound cross-sections, it is assumed that the residual interaction will have non-vanishing matrix elements between states whose complexities differ by at most one unit. This is referred to as the chaining hypothesis. Explicit expressions for the double differential cross-section giving the angular distribution and energy spectrum are obtained for both reaction types. The statistical multi-step compound cross-sections are symmetric about 90 0 . The classical statistical theory of nuclear reactions is a special limiting case. The cross-section for the statistical multi-step direct reaction consists of a set of convolutions of single-step direct cross-sections. For the many step case it is possible to derive a diffusion equation in momentum space. Application is made to the reaction 181 Ta(p,n) 181 W using the statistical multi-step compound formalism

  14. Direct inner shell ionization accompanying heavy ion fusion reactions

    International Nuclear Information System (INIS)

    Sujkowski, Z.

    1987-07-01

    51 V+ 40 Ar (180 MeV) fusion reaction is studied by means of K X-ray-particle-γ-ray coincidences. K X-ray yields associated with various evaporation residues are determined separately for two ionization processes: the direct ionization by the projectile prior to the nuclear interaction and the postcollisional ionization due to the internal conversion of γ-rays. Implications for possible measurements of nuclear reaction times are discussed. 24 refs., 9 figs., 2 tabs. (author)

  15. Directed transverse flow and its disappearance for asymmetric reactions

    International Nuclear Information System (INIS)

    Lovejot; Gautam, S.

    2014-01-01

    We study the directed transverse flow for mass asymmetry reactions. This is done by keeping the target fixed and varying the projectile mass from 4 He to 131 Xe. We find that directed transverse flow is sensitive to the mass of the projectile. We also study the disappearance of flow at a particular impact parameter called Geometry of Vanishing Flow (GVF) for such mass asymmetry reactions. Our results indicate that GVF is sensitive to the beam energy as well as to the mass of the projectile.

  16. Direct observation of multistep energy transfer in LHCII with fifth-order 3D electronic spectroscopy.

    Science.gov (United States)

    Zhang, Zhengyang; Lambrev, Petar H; Wells, Kym L; Garab, Győző; Tan, Howe-Siang

    2015-07-31

    During photosynthesis, sunlight is efficiently captured by light-harvesting complexes, and the excitation energy is then funneled towards the reaction centre. These photosynthetic excitation energy transfer (EET) pathways are complex and proceed in a multistep fashion. Ultrafast two-dimensional electronic spectroscopy (2DES) is an important tool to study EET processes in photosynthetic complexes. However, the multistep EET processes can only be indirectly inferred by correlating different cross peaks from a series of 2DES spectra. Here we directly observe multistep EET processes in LHCII using ultrafast fifth-order three-dimensional electronic spectroscopy (3DES). We measure cross peaks in 3DES spectra of LHCII that directly indicate energy transfer from excitons in the chlorophyll b (Chl b) manifold to the low-energy level chlorophyll a (Chl a) via mid-level Chl a energy states. This new spectroscopic technique allows scientists to move a step towards mapping the complete complex EET processes in photosynthetic systems.

  17. Studies of the reactions of hydrogen atoms by time-resolved E. S. R. spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Fessenden, R W; Verma, N C [Carnegie-Mellon Univ., Pittsburgh, Pa. (USA). Dept. of Chemistry

    1977-01-01

    Time-resolved e.s.r. spectroscopy has been used to follow directly the reactions of H atoms produced by pulse radiolysis of acid solutions. Detailed analysis of the time profile of the e.s.r. signal was carried out by means of modified Bloch equations. The increased signal found when a scavenger for OH such as t-butyl alcohol is present is shown to be mainly the result of slower H atom decay by radical-radical reaction. The reaction H + OH does not appear to produce any signal polarization. The decay curves observed in the presence of solute are readily accounted for by the treatment, and good plots of pseudo first-order rate constant against solute concentration are obtained. The absolute rate constants for reaction with H atoms are for methanol 2.5 x10/sup 6/, for ethanol 2.1 X 10/sup 7/, for isopropanol 6.8 x 10/sup 7/, and for succinic acid 3.0 x 10/sup 6/ dm/sup 3/ mol/sup -1/s/sup -1/. These values are in good agreement with the earlier chemical measurements.

  18. Characterization of low energy radioactive beams using direct reactions

    DEFF Research Database (Denmark)

    Johansen, J.G.; Fraser, M.A.; Bildstein, V.

    2013-01-01

    We demonstrate a new technique to determine the beam structure of low energy radioactive beams using coincidence events from a direct reaction. The technique will be described and tested using Geant4 simulations. We use the technique to determine for the first time the width, divergence and energy...

  19. Direct activation of allylic alcohols in palladium catalyzed coupling reactions

    NARCIS (Netherlands)

    Gümrükçü, Y.

    2014-01-01

    The direct use of allylic alcohols in substitution reactions without pre-activation of the hydroxyl-group into a better leaving group or the use of additional stoichiometric in situ activators remains challenging due to the poor leaving group ability of the hydroxyl-group. Hence, it is important to

  20. Direct injection of superheated steam for continuous hydrolysis reaction

    KAUST Repository

    Wang, Weicheng

    2012-09-01

    The primary intent for previous continuous hydrolysis studies was to minimize the reaction temperature and reaction time. In this work, hydrolysis is the first step of a proprietary chemical process to convert lipids to sustainable, drop-in replacements for petroleum based fuels. To improve the economics of the process, attention is now focused on optimizing the energy efficiency of the process, maximizing the reaction rate, and improving the recovery of the glycerol by-product. A laboratory-scale reactor system has been designed and built with this goal in mind.Sweet water (water with glycerol from the hydrolysis reaction) is routed to a distillation column and heated above the boiling point of water at the reaction pressure. The steam pressure allows the steam to return to the reactor without pumping. Direct injection of steam into the hydrolysis reactor is shown to provide favorable equilibrium conditions resulting in a high quality of FFA product and rapid reaction rate, even without preheating the inlet water and oil and with lower reactor temperatures and lower fresh water demand. The high enthalpy of the steam provides energy for the hydrolysis reaction. Steam injection offers enhanced conditions for continuous hydrolysis of triglycerides to high-purity streams of FFA and glycerol. © 2012 Elsevier B.V.

  1. On the treatment of exchange effects in direct reactions

    International Nuclear Information System (INIS)

    Bencze, Gy.

    1984-11-01

    In the theoretical description of direct nuclear reactions the dynamic effects are combined with 'kinematical' effects due to the quantum mechanical exchange interaction caused by the Pauli principle governing the mechanics of identical particles. In the present paper it is shown that in the frame of general algebraic theory of identical particle scattering the effects of the permutational symmetry of nucleons can be separated on an exact way from the treatment of reaction dynamics. Dynamical approximations may be used only after the separation of permutational effects. (D.Gy.)

  2. Two-photon direct frequency comb spectroscopy of alkali atoms

    Science.gov (United States)

    Palm, Christopher; Pradhananga, Trinity; Nguyen, Khoa; Montcrieffe, Caitlin; Kimball, Derek

    2012-11-01

    We have studied transition frequencies and excited state hyperfine structure in rubidium using 2-photon transitions excited directly with the frequency-doubled output of a erbium fiber optical frequency comb. The frequency comb output is directed in two counterpropagating directions through a vapor cell containing the rubidium vapor. A pair of optical filters is used to select teeth of the comb in order to identify the transition wavelengths. A photomultiplier tube (PMT) measures fluorescence from a decay channel wavelength selected with another optical filter. Using different combinations of filters enables a wide range of transitions to be investigated. By scanning the repetition rate, a Doppler-free spectrum can be obtained enabling kHz-resolution spectral measurements. An interesting dependence of the 2-photon spectrum on the energy of the intermediate state of the 2-photon transition is discussed. Our investigations are laying the groundwork for a long-term research program to use direct frequency comb spectroscopy to understand the complex spectra of rare-earth atoms.

  3. Two-component multistep direct reactions: A microscopic approach

    International Nuclear Information System (INIS)

    Koning, A.J.; Chadwick, M.B.

    1998-03-01

    The authors present two principal advances in multistep direct theory: (1) A two-component formulation of multistep direct reactions, where neutron and proton excitations are explicitly accounted for in the evolution of the reaction, for all orders of scattering. While this may at first seem to be a formidable task, especially for multistep processes where the many possible reaction pathways becomes large in a two-component formalism, the authors show that this is not so -- a rather simple generalization of the FKK convolution expression 1 automatically generates these pathways. Such considerations are particularly relevant when simultaneously analyzing both neutron and proton emission spectra, which is always important since these processes represent competing decay channels. (2) A new, and fully microscopic, method for calculating MSD cross sections which does not make use of particle-hole state densities but instead directly calculates cross sections for all possible particle-hole excitations (again including an exact book-keeping of the neutron/proton type of the particle and hole at all stages of the reaction) determined from a simple non-interacting shell model. This is in contrast to all previous numerical approaches which sample only a small number of such states to estimate the DWBA strength, and utilize simple analytical formulae for the partial state density, based on the equidistant spacing model. The new approach has been applied, along with theories for multistep compound, compound, and collective reactions, to analyze experimental emission spectra for a range of targets and energies. The authors show that the theory correctly accounts for double-differential nucleon spectra

  4. Indirect glyphosate detection based on ninhydrin reaction and surface-enhanced Raman scattering spectroscopy

    Science.gov (United States)

    Xu, Meng-Lei; Gao, Yu; Li, Yali; Li, Xueliang; Zhang, Huanjie; Han, Xiao Xia; Zhao, Bing; Su, Liang

    2018-05-01

    Glyphosate is one of the most commonly-used and non-selective herbicides in agriculture, which may directly pollute the environment and threaten human health. A simple and effective approach to assessment of its damage to the natural environment is thus quite necessary. However, traditional chromatography-based detection methods usually suffer from complex pretreatment procedures. Herein, we propose a simple and sensitive method for the determination of glyphosate by combining ninhydrin reaction and surface-enhanced Raman scattering (SERS) spectroscopy. The product (purple color dye, PD) of the ninhydrin reaction is found to SERS-active and directly correlate with the glyphosate concentration. The limit of detection of the proposed method for glyphosate is as low as 1.43 × 10- 8 mol·L- 1 with a relatively wider linear concentration range (1.0 × 10- 7-1.0 × 10- 4 mol·L- 1), which demonstrates its great potential in rapid, highly sensitive concentration determination of glyphosate in practical applications for safety assessment of food and environment.

  5. Direct single-molecule dynamic detection of chemical reactions.

    Science.gov (United States)

    Guan, Jianxin; Jia, Chuancheng; Li, Yanwei; Liu, Zitong; Wang, Jinying; Yang, Zhongyue; Gu, Chunhui; Su, Dingkai; Houk, Kendall N; Zhang, Deqing; Guo, Xuefeng

    2018-02-01

    Single-molecule detection can reveal time trajectories and reaction pathways of individual intermediates/transition states in chemical reactions and biological processes, which is of fundamental importance to elucidate their intrinsic mechanisms. We present a reliable, label-free single-molecule approach that allows us to directly explore the dynamic process of basic chemical reactions at the single-event level by using stable graphene-molecule single-molecule junctions. These junctions are constructed by covalently connecting a single molecule with a 9-fluorenone center to nanogapped graphene electrodes. For the first time, real-time single-molecule electrical measurements unambiguously show reproducible large-amplitude two-level fluctuations that are highly dependent on solvent environments in a nucleophilic addition reaction of hydroxylamine to a carbonyl group. Both theoretical simulations and ensemble experiments prove that this observation originates from the reversible transition between the reactant and a new intermediate state within a time scale of a few microseconds. These investigations open up a new route that is able to be immediately applied to probe fast single-molecule physics or biophysics with high time resolution, making an important contribution to broad fields beyond reaction chemistry.

  6. Coherent radio-frequency detection for narrowband direct comb spectroscopy.

    Science.gov (United States)

    Anstie, James D; Perrella, Christopher; Light, Philip S; Luiten, Andre N

    2016-02-22

    We demonstrate a scheme for coherent narrowband direct optical frequency comb spectroscopy. An extended cavity diode laser is injection locked to a single mode of an optical frequency comb, frequency shifted, and used as a local oscillator to optically down-mix the interrogating comb on a fast photodetector. The high spectral coherence of the injection lock generates a microwave frequency comb at the output of the photodiode with very narrow features, enabling spectral information to be further down-mixed to RF frequencies, allowing optical transmittance and phase to be obtained using electronics commonly found in the lab. We demonstrate two methods for achieving this step: a serial mode-by-mode approach and a parallel dual-comb approach, with the Cs D1 transition at 894 nm as a test case.

  7. Directional scanning tunneling spectroscopy in MgB2

    International Nuclear Information System (INIS)

    Iavarone, M.; Karapetrov, G.; Koshelev, A.E.; Kwok, W.K.; Crabtree, G.W.; Hinks, D.G.; Cook, R.; Kang, W.N.; Choi, E.M.; Kim, H.J.; Lee, S.I.

    2003-01-01

    The superconductivity in MgB 2 has a two-band character with the dominating band having a 2D character and the second band being isotropic in the three dimensions. We use tunneling microscopy and spectroscopy to reveal the two distinct energy gaps at Δ 1 =2.3 meV and Δ 2 =7.1 meV. Different spectral weights of the partial superconducting density of states are a reflection of different tunneling directions in this multi-band system. The results are consistent with the existence of two-band superconductivity in the presence of strong interband superconducting pair interaction and quasiparticle scattering. The temperature evolution of the tunneling spectra shows both gaps vanishing at the bulk T c

  8. Antenna Design for Directivity-Enhanced Raman Spectroscopy

    Directory of Open Access Journals (Sweden)

    Aftab Ahmed

    2012-01-01

    Full Text Available Antenna performance can be described by two fundamental parameters: directivity and radiation efficiency. Here, we demonstrate nanoantenna designs in terms of improved directivity. Performance of the antennas is demonstrated in Raman scattering experiments. The radiated beam is directed out of the plane by using a ground plane reflector for easy integration with commercial microscopes. Parasitic elements and parabolic and waveguide nanoantennas with a ground plane are explored. The nanoantennas were fabricated by a series of electron beam evaporation steps and focused ion beam milling. As we have shown previously, the circular waveguide nanoantenna boosts the measured Raman signal by 5.5x with respect to a dipole antenna over a ground plane; here, we present the design process that led to the development of that circular waveguide nanoantenna. This work also shows that the parabolic nanoantenna produces a further fourfold improvement in the measured Raman signal with respect to a circular waveguide nanoantenna. The present designs are nearly optimal in the sense that almost all the beam power is coupled into the numerical aperture of the microscope. These designs can find applications in microscopy, spectroscopy, light-emitting devices, photovoltaics, single-photon sources, and sensing.

  9. Reactions of laser ablated uranium with nitrogen studied using matrix isolation spectroscopy

    International Nuclear Information System (INIS)

    Sankaran, K.; Sundararajan, K.; Viswanathan, K.S.

    1999-01-01

    Unusual reactions were found to occur when uranium was laser ablated in the presence of nitrogen. The reaction products were trapped in a rigid inert gas matrix and studied using infrared spectroscopy. The species formed were strongly dependent on the partial pressure of nitrogen in the matrix gas used during the ablation process; at low nitrogen partial pressures uranium dinitride (NUN) was the major reaction product, while at high partial pressures of nitrogen the mononitride, UN, was the predominant product. (author)

  10. Direct Observation of Energy Detrapping in LH1-RC Complex by Two-Dimensional Electronic Spectroscopy.

    Science.gov (United States)

    Ma, Fei; Yu, Long-Jiang; Hendrikx, Ruud; Wang-Otomo, Zheng-Yu; van Grondelle, Rienk

    2017-01-18

    The purple bacterial core light harvesting antenna-reaction center (LH1-RC) complex is the simplest system able to achieve the entire primary function of photosynthesis. During the past decade, a variety of photosynthetic proteins were studied by a powerful technique, two-dimensional electronic spectroscopy (2DES). However, little attention has been paid to LH1-RC, although its reversible uphill energy transfer, trapping, and backward detrapping processes, represent a crucial step in the early photosynthetic reaction dynamics. Thus, in this work, we employed 2DES to study two LH1-RC complexes of Thermochromatium (Tch.) tepidum. By direct observation of detrapping, the complex reversible process was clearly identified and an overall scheme of the excitation evolution in LH1-RC was obtained.

  11. LEAD SLOWING DOWN SPECTROSCOPY FOR DIRECT Pu MASS MEASUREMENTS

    International Nuclear Information System (INIS)

    Ressler, Jennifer J.; Smith, Leon E.; Anderson, Kevin K.

    2008-01-01

    The direct measurement of Pu in previously irradiated fuel assemblies is a recognized need in the international safeguards community. A suitable technology could support more timely and independent material control and accounting (MC and A) measurements at nuclear fuel storage areas, the head-end of reprocessing facilities, and at the product-end of recycled fuel fabrication. Lead slowing down spectroscopy (LSDS) may be a viable solution for directly measuring not only the mass of 239Pu in fuel assemblies, but also the masses of other fissile isotopes such as 235U and 241Pu. To assess the potential viability of LSDS, an LSDS spectrometer was modeled in MCNP5 and 'virtual assays' of nominal PWR assemblies ranging from 0 to 60 GWd/MTU burnup were completed. Signal extraction methods, including the incorporation of nonlinear fitting to account for self-shielding effects in strong resonance regions, are described. Quantitative estimates of Pu uncertainty are given for simplistic and more realistic fuel isotopic inventories calculated using ORIGEN. A discussion of additional signal-perturbing effects that will be addressed in future work, and potential signal extraction approaches that could improve Pu mass uncertainties, are also discussed

  12. Direct nuclear reactions and the structure of atomic nuclei

    International Nuclear Information System (INIS)

    Osterfeld, F.

    1985-01-01

    The present thesis deals with two different aspects of direct nuclear reactions, namely on the one hand with the microscopic calculation of the imaginary optical potential for the elastic nucleon-nucleus scattering as well as on the other hand with the microscopic analysis of giant magnetic resonances in atomic nuclei which are excited by (p,n) charge-exchange reactions. In the first part of the thesis the imaginary part of the optical potential for the elastic proton- and neutron-nucleus scattering is microscopically calculated in the framework of the so called nuclear-structure approximation to the optical potential. The calculations are performed in the Feshbach formalism in second-order perturbation theory corresponding to an effective projectile-target-nucleon interaction. In the second part of this thesis in the framework of microscopic nuclear models a complete analysis of different A(p,n)B charge-exchange reactions at high incident energies 160 MeV 90 Zr(p,n) reaction three collective spin-isospin resonances could be uniquely identified. (orig./HSI) [de

  13. Multi-step direct reactions at low energies

    International Nuclear Information System (INIS)

    Marcinkowski, A.; Marianski, B.

    2001-01-01

    Full text: The theory of the multistep direct (MSD) reactions of Feshbach, Kerman and Koonin has for quite some time become a subject of controversy due to the bi orthogonal distorted waves involved in the transition amplitudes describing the MSD cross sections. The bi orthogonal wave functions result in non-normal DWBA matrix elements, that can be expressed in terms of normal DWBA matrix elements multiplied by the inverse elastic scattering S-matrix. It has been argued that the enhancing inverse S-factors are washed out by averaging over energy in the continuum. As a result normal DWBA matrix elements are commonly used in practical calculations. Almost all analyses of inelastic scattering and charge-exchange reactions using the DWBA matrix elements have concluded that nucleon emission at low energies can be described as one-step reaction mainly. On the other hand, it has been shown that the limits imposed by the energy weighted sum rules (EWSR's) on transition of given angular momentum transfer lead to a significant reduction of the one step cross section that can be compensated by the enhanced MSD cross sections obtained with the use of the non-normal DWBA matrix elements. Very recently the MSD theory of FKK was modified to include collective excitations and the non-normal DWBA matrix elements and the prescription for calculations of the cross sections for the MSD reactions was given. In the present paper we present the results of the modified theory used for describing the 93 Nb (n,xn) 93 Nb reaction at incident energy of 20 MeV and the 65 Cu (p,xn) 65 Zn reaction at 27 MeV. The results show enhanced contributions from two-, three- and four step reactions. We investigate the importance of the multi-phonon, multi particle hole and the mixed particle hole-phonon excitations in neutron scattering to the continuum. We also show the importance of the different sequences of collisions of the leading continuum nucleon that contribute to the MSD (p,n) reaction. When all

  14. Action and reaction in the theories of direct interparticle action

    International Nuclear Information System (INIS)

    Narlikar, J.V.

    1975-01-01

    Newton's third law of motion is examined in the context of the theories of direct interpaticle action. In such theories, interactions between particles travel backward and forward in time at speeds not exceeding the speed of light. It is shown that while in the flat spacetime the equality of action and reaction can be clearly demonstrated, the situation is considerably more complicated in the curved spacetime. The phenomenon of gravitational scattering intervenes to destroy the equality of action and reaction. Nevertheless, when gravitation is taken into account, there is no violation of the conservation law of energy and momentum. These results are discussed in the framework of general relativity for the case of the electromagnetic interaction

  15. Direct Reaction Experimental Studies with Beams of Radioactive Tin Ions

    Energy Technology Data Exchange (ETDEWEB)

    Jones, K. L. [University of Tennessee, Knoxville (UTK); Ahn, S.H. [University of Tennessee, Knoxville (UTK); Allmond, James M [ORNL; Ayres, A. [University of Tennessee, Knoxville (UTK); Bardayan, Daniel W [ORNL; Baugher, T. [Michigan State University, East Lansing; Bazin, D. [Michigan State University, National Superconducting Cyclotron Laboratory (NSCL); Beene, James R [ORNL; Berryman, J. S. [Michigan State University, East Lansing; Bey, A. [University of Tennessee, Knoxville (UTK); Bingham, C. R. [University of Tennessee, Knoxville (UTK); Cartegni, L. [University of Tennessee, Knoxville (UTK); Chae, K. Y. [University of Tennessee, Knoxville (UTK)/Sungkyunkwan University, Korea; Cizewski, J. A. [Rutgers University; Gade, A. [Michigan State University, National Superconducting Cyclotron Laboratory (NSCL); Galindo-Uribarri, Alfredo {nmn} [ORNL; Garcia-Ruiz, R.F. [Instituut voor Kernen Stralingsfysica, KU Leuven, B-3001, Leuven, Belgium; Grzywacz, Robert Kazimierz [ORNL; Howard, Meredith E [ORNL; Kozub, R. L. [Tennessee Technological University (TTU); Liang, J Felix [ORNL; Manning, Brett M [ORNL; Matos, M. [Louisiana State University; McDaniel, S. [Michigan State University, East Lansing; Miller, D. [University of Tennessee, Knoxville (UTK); Nesaraja, Caroline D [ORNL; O' Malley, Patrick [Rutgers University; Padgett, S [University of Tennessee, Knoxville (UTK); Padilla-Rodal, Elizabeth [Universidad Nacional Autonoma de Mexico (UNAM); Pain, Steven D [ORNL; Pittman, S. T. [University of Tennessee (UTK) and Oak Ridge National Laboratory (ORNL); Radford, David C [ORNL; Ratkiewicz, Andrew J [ORNL; Schmitt, Kyle [ORNL; Smith, Michael Scott [ORNL; Stracener, Daniel W [ORNL; Stroberg, S. [Michigan State University, East Lansing; Tostevin, Jeffrey A [ORNL; Varner Jr, Robert L [ORNL; Weisshaar, D. [Michigan State University, East Lansing; Wimmer, K. [Michigan State University, National Superconducting Cyclotron Laboratory (NSCL)/Central Michigan University; Winkler, R. [Michigan State University, East Lansing

    2015-01-01

    The tin chain of isotopes provides a unique region in which to investigate the evolution of single-particle structure, spreading from N = 50 at Sn-100, through 10 stable isotopes and the N = 82 shell closure at Sn-132 out into the r-process path. Direct reactions performed on radioactive ion beams are sensitive spectroscopic tools for studying exotic nuclei. Here we present one experiment knocking out neutrons from tin isotopes that are already neutron deficient and two reactions that add a neutron to neutron-rich Sn-130. Both techniques rely on selective particle identification and the measurement of gamma rays in coincidence with charged ions. We present the goals of the two experiments and the particle identification for the channels of interest. The final results will be presented in future publications.

  16. The statistics of multi-step direct reactions

    International Nuclear Information System (INIS)

    Koning, A.J.; Akkermans, J.M.

    1991-01-01

    We propose a quantum-statistical framework that provides an integrated perspective on the differences and similarities between the many current models for multi-step direct reactions in the continuum. It is argued that to obtain a statistical theory two physically different approaches are conceivable to postulate randomness, respectively called leading-particle statistics and residual-system statistics. We present a new leading-particle statistics theory for multi-step direct reactions. It is shown that the model of Feshbach et al. can be derived as a simplification of this theory and thus can be founded solely upon leading-particle statistics. The models developed by Tamura et al. and Nishioka et al. are based upon residual-system statistics and hence fall into a physically different class of multi-step direct theories, although the resulting cross-section formulae for the important first step are shown to be the same. The widely used semi-classical models such as the generalized exciton model can be interpreted as further phenomenological simplifications of the leading-particle statistics theory. A more comprehensive exposition will appear before long. (author). 32 refs, 4 figs

  17. Reaction mechanism studies of unsaturated molecules using photofragment translational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Longfellow, C.A. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley National Lab., CA (United States). Chemical Sciences Div.

    1996-05-01

    A number of molecules have been studied using the technique of photofragment translational spectroscopy. In Chapter One a brief introduction to the experimental technique is given. In Chapter Two the infrared multiphoton dissociation (IRMPD) of acetic acid is discussed. Carbon dioxide and methane were observed for the first time as products from dissociation under collisionless conditions. Chapter Three relates an IRMPD experiment of hexafluoropropene. The predominant channel produces CFCF{sub 3} or C{sub 2}F{sub 4} and CF{sub 2}, with the heavier species undergoing further dissociation to two CF{sub 2} fragments. In Chapter Four the ultraviolet (UV) dissociation of hexafluoropropene is investigated. Chapter Five explores the IRMPD of octafluoro-1-butene and octafluoro-2-butene.

  18. Pico-second laser spectroscopy and reaction dynamics in liquids

    International Nuclear Information System (INIS)

    Mialocq, Jean-Claude

    1984-01-01

    The dynamic relaxation of excited singlet states of molecules and ions in liquid solution is investigated using picosecond laser spectroscopy. The more efficient process for the deactivation of the first excited singlet state of pinacyanol is internal conversion S 1 → S 0 between iso-energetic states. At low viscosity, the rate constant is inversely proportional to the macroscopic viscosity and depends on the relaxation of the angle between the quinoline end groups around the polymethinic chain. Electron photodetachment by 265 nm excitation of the ferrocyanide and phenolate anions and photoionisation of neutral molecules, phenol, indole and tryptophan in polar solvents give rise to the solvated electron formation. The mono-or bi-photonic nature of the ejection process and the solvent relaxation around the excess electron are analyzed. (author) [fr

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

    Science.gov (United States)

    2015-01-01

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

  20. Elucidating the design principles of photosynthetic electron-transfer proteins by site-directed spin labeling EPR spectroscopy.

    Science.gov (United States)

    Ishara Silva, K; Jagannathan, Bharat; Golbeck, John H; Lakshmi, K V

    2016-05-01

    Site-directed spin labeling electron paramagnetic resonance (SDSL EPR) spectroscopy is a powerful tool to determine solvent accessibility, side-chain dynamics, and inter-spin distances at specific sites in biological macromolecules. This information provides important insights into the structure and dynamics of both natural and designed proteins and protein complexes. Here, we discuss the application of SDSL EPR spectroscopy in probing the charge-transfer cofactors in photosynthetic reaction centers (RC) such as photosystem I (PSI) and the bacterial reaction center (bRC). Photosynthetic RCs are large multi-subunit proteins (molecular weight≥300 kDa) that perform light-driven charge transfer reactions in photosynthesis. These reactions are carried out by cofactors that are paramagnetic in one of their oxidation states. This renders the RCs unsuitable for conventional nuclear magnetic resonance spectroscopy investigations. However, the presence of native paramagnetic centers and the ability to covalently attach site-directed spin labels in RCs makes them ideally suited for the application of SDSL EPR spectroscopy. The paramagnetic centers serve as probes of conformational changes, dynamics of subunit assembly, and the relative motion of cofactors and peptide subunits. In this review, we describe novel applications of SDSL EPR spectroscopy for elucidating the effects of local structure and dynamics on the electron-transfer cofactors of photosynthetic RCs. Because SDSL EPR Spectroscopy is uniquely suited to provide dynamic information on protein motion, it is a particularly useful method in the engineering and analysis of designed electron transfer proteins and protein networks. This article is part of a Special Issue entitled Biodesign for Bioenergetics--the design and engineering of electronic transfer cofactors, proteins and protein networks, edited by Ronald L. Koder and J.L. Ross Anderson. Copyright © 2016. Published by Elsevier B.V.

  1. Spectroscopy of 17C via one-neutron knockout reaction

    Directory of Open Access Journals (Sweden)

    Kim Sunji

    2016-01-01

    Full Text Available A spectroscopic study of 17C was performed via the one-neutron knockout reaction of 18C on a carbon target at RIKEN-RIBF. Three unbound states at excitation energies of 2.66(2, 3.16(5, and 3.97(3 MeV (preliminary were observed. The energies are compared with shell-model calculations and existing measurements to deduce their spin-parities. From the comparison, the states at 2.66(2 and 3.97(3 MeV are suggested to be 1/2− and 3/2−, respectively. From its decay property, the state at 3.16(5 MeV is indicated to be 9/2+.

  2. Gamma spectroscopy of multiple nucleon transfer reactions in Sn

    International Nuclear Information System (INIS)

    Grabowski, Z.W.; Mayer, R.H.; Fornal, B.; Nisius, D.T.; Bearden, I.G.; Daly, P.J.; Broda, R.; Carpenter, M.P.; Janssens, R.V.F.; Khoo, T.L.; Lauritsen, T.

    1992-01-01

    The decay of (πh 11/2 ) n yrast isomers was studied in a series of proton-rich N = 82 isotones culminating in determination of B(E2) values in 153 Lu and 154 Hf. In the N = 82 isotones however, it seems unlikely that the measurements could be extended beyond 154 Hf (n = 8). The opportunity to investigate the (h 11/2 ) n ) isomers across the whole h 11/2 subshell exists, at least in principle, in Sn isotopes where the counterpart νh 11/2 subshell is being filled with neutrons starting at 116 Sn. Before our measurements were initiated, the (νh 11/2 ) n 10 + isomers were known to exist in 116, 118, 120 Sn, where the νh 11/2 subshell begins to fill, and in 128,130 Sn at the other end. Important information, however, was missing about the 10 + isomers in 122,124,126 Sn where the long lifetimes are expected. The υ = 3 (h 11/2 ) isomers in odd tin isomers for A ≥ 119 were also not identified. A serious experimental difficulty in populating high spin states in heavier Sn isotopes is that they are not accessible by fusion-evaporation reactions. We decided to search for these missing tin isotopes among the products of heavy ion reactions on 122,124 Sn targets. Using this approach we were able to identify the isomeric decays and measure the lifetimes of the (νh 11/2 n ) υ = 2 isomeric states in 122,124 Sn. In odd tin isotopes we identified new I = 19/2 + yrast isomers in 119,121,123 Sn and measured their lifetimes. In addition (νh 11/2 ) n υ = 3, I = 27/2 - isomers in 119,121 Sn were observed for the first time

  3. Chemical reactions on platinum-group metal surfaces studied by synchrotron-radiation-based spectroscopy

    International Nuclear Information System (INIS)

    Kondoh, Hiroshi; Nakai, Ikuyo; Nagasaka, Masanari; Amemiya, Kenta; Ohta, Toshiaki

    2009-01-01

    A new version of synchrotron-radiation-based x-ray spectroscopy, wave-length-dispersive near-edge x-ray absorption fine structure (dispersive-NEXAFS), and fast x-ray photoelectron spectroscopy have been applied to mechanistic studies on several surface catalytic reactions on platinum-group-metal surfaces. In this review, our approach using above techniques to understand the reaction mechanism and actual application studies on three well-known catalytic surface reactions, CO oxidation on Pt(111) and Pd(111), NO reduction on Rh(111), and H 2 O formation on Pt(111), are introduced. Spectroscopic monitoring of the progress of the surface reactions enabled us to detect reaction intermediates and analyze the reaction kinetics quantitatively which provides information on reaction order, rate constant, pre-exponential factor, activation energy and etc. Such quantitative analyses combined with scanning tunneling microscopy and kinetic Monte Carlo simulations revealed significant contribution of the adsorbate configurations and their dynamic changes to the reaction mechanisms of the above fundamental catalytic surface reactions. (author)

  4. Investigation of organometallic reaction mechanisms with one and two dimensional vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cahoon, James Francis [Univ. of California, Berkeley, CA (United States)

    2008-12-01

    One and two dimensional time-resolved vibrational spectroscopy has been used to investigate the elementary reactions of several prototypical organometallic complexes in room temperature solution. The electron transfer and ligand substitution reactions of photogenerated 17-electron organometallic radicals CpW(CO)3 and CpFe(CO)2 have been examined with one dimensional spectroscopy on the picosecond through microsecond time-scales, revealing the importance of caging effects and odd-electron intermediates in these reactions. Similarly, an investigation of the photophysics of the simple Fischer carbene complex Cr(CO)5[CMe(OMe)] showed that this class of molecule undergoes an unusual molecular rearrangement on the picosecond time-scale, briefly forming a metal-ketene complex. Although time-resolved spectroscopy has long been used for these types of photoinitiated reactions, the advent of two dimensional vibrational spectroscopy (2D-IR) opens the possibility to examine the ultrafast dynamics of molecules under thermal equilibrium conditions. Using this method, the picosecond fluxional rearrangements of the model metal carbonyl Fe(CO)5 have been examined, revealing the mechanism, time-scale, and transition state of the fluxional reaction. The success of this experiment demonstrates that 2D-IR is a powerful technique to examine the thermally-driven, ultrafast rearrangements of organometallic molecules in solution.

  5. Coadsorption and reaction of H2 and CO on Raney nickel: Neutron vibrational spectroscopy

    International Nuclear Information System (INIS)

    Kelley, R.D.; Kernforschungsanlage Juelich G.m.b.H.

    1983-01-01

    Neutron vibration spectroscopy is used to study the adsorption and reaction of H 2 and Co on a catalytic nickel surface. The sample was first exposed to H 2 and than to CO. At low temperatures there is no change of vibrational modes of H in the three-fold site; at a higher temperature changes occur. Some conclusions are drawn on the reaction product. (G.Q.)

  6. Insights into reaction mechanisms in heterogeneous catalysis revealed by in situ NMR spectroscopy.

    Science.gov (United States)

    Blasco, Teresa

    2010-12-01

    This tutorial review intends to show the possibilities of in situ solid state NMR spectroscopy in the elucidation of reaction mechanisms and the nature of the active sites in heterogeneous catalysis. After a brief overview of the more usual experimental devices used for in situ solid state NMR spectroscopy measurements, some examples of applications taken from the recent literature will be presented. It will be shown that in situ NMR spectroscopy allows: (i) the identification of stable intermediates and transient species using indirect methods, (ii) to prove shape selectivity in zeolites, (iii) the study of reaction kinetics, and (iv) the determination of the nature and the role played by the active sites in a catalytic reaction. The approaches and methodology used to get this information will be illustrated here summarizing the most relevant contributions on the investigation of the mechanisms of a series of reactions of industrial interest: aromatization of alkanes on bifunctional catalysts, carbonylation reaction of methanol with carbon monoxide, ethylbenzene disproportionation, and the Beckmann rearrangement reaction. Special attention is paid to the research carried out on the role played by carbenium ions and alkoxy as intermediate species in the transformation of hydrocarbon molecules on solid acid catalysts.

  7. The hydroxylation of passive oxide films on X-70 steel by dissolved hydrogen studied by nuclear reaction analysis, Auger electron spectroscopy, X-ray photoelectron spectroscopy and secondary ion mass spectroscopy

    International Nuclear Information System (INIS)

    Zhang Chunsi; Luo Jingli; Munoz-Paniagua, David; Norton, Peter R.

    2006-01-01

    Dissolved hydrogen is known to reduce the corrosion resistance of a passive oxide film on iron and its alloys, especially towards pitting corrosion. Electrochemical techniques have been used to show that the passive films are changed by dissolved hydrogen in an alloy substrate, but direct confirmation of the chemical and compositional profiles and changes has been missing. In this paper we report the direct profiling and compositional analysis of the 4 nm passive film on X-70 steel by Auger electron spectroscopy (AES), secondary ion mass spectrometry (SIMS), X-ray photoelectron spectroscopy (XPS) and nuclear reaction analysis (NRA) while hydrogen (deuterium) is charged into the alloy samples from the reverse, unpassivated side. The only route for D to the passive film is therefore by dissolution and diffusion. We show that the original duplex structure of the passive film is converted to a more continuous film containing hydroxyl groups, by reaction with the dissolved hydrogen. This conversion of the oxide ions to hydroxyl groups can lead to more rapid reaction and replacement with (e.g.) Cl - , which is known to enhance pitting. These results are entirely consistent with previous electrochemical studies and provide the first direct confirmation of models on the formation and role of hydroxyl groups derived from these earlier studies

  8. Illumination of Nanoliter-NMR Spectroscopy Chips for Real-Time Photochemical Reaction Monitoring

    NARCIS (Netherlands)

    Gomez, M.V.; Juan, Alberto; Jiménez-Márquez, Francisco; La Hoz, De Antonio; Velders, Aldrik H.

    2018-01-01

    We report the use of a small-volume nuclear-magnetic-resonance (NMR)-spectroscopy device with integrated fiber-optics for the real-time detection of UV-vis-light-assisted chemical reactions. An optical fiber is used to guide the light from LEDs or a laser diode positioned safely outside the magnet

  9. Surface reactions during atomic layer deposition of Pt derived from gas phase infrared spectroscopy

    NARCIS (Netherlands)

    Kessels, W.M.M.; Knoops, H.C.M.; Dielissen, S.A.F.; Mackus, A.J.M.; Sanden, van de M.C.M.

    2009-01-01

    Infrared spectroscopy was used to obtain absolute number information on the reaction products during atomic layer deposition of Pt from (methylcyclopentadienyl)trimethylplatinum [(MeCp)PtMe3] and O2. From the detection of CO2 and H2O it was established that the precursor ligands are oxidatively

  10. Form factors in (HI,HI') direct reactions

    International Nuclear Information System (INIS)

    Chu, Y.H.

    1981-01-01

    Using the semiclassical theory, the inelastic transition form factors are analyzed. For the first order form factors, we find that: (i) In the strong absorption limit, the Austern-Blair theory is a good approximation to the inelastic form factor--even in highly mismatched reactions. (ii) In weak to moderate absorption, the amplitude of the inelastic form factor oscillates due to overlapping potential resonances. The internal part of the form factor can be expressed in a simple form, which may easily be used to analyze heavy-ion inelastic scattering. (iii) In the presence of an isolated resonance, the inelastic form factor is enhanced greatly at the resonance due to multiple reflections inside the potential well. The second order form factors contain two terms, i.e. the one-step direct process (OSD) term and the two-step process (TS) term. It is found that: (i) In the strong absorption limit, OSD and TS form factors are equally important and interfere destructively near the grazing angular momentum. The Austern-Blair theory gives satisfactory results for well-matched reactions. The angular distributions of the mutual and double excitations are out of phase compared with that of the single excitation. (ii) For the weak absorption case, the internal part of the TS form factor is so enhanced that the OSD form factor can simply be neglected. The internal TS form factor can be parameterized in a form proportional to the internal-wave elastic Smatrix, where the angular distribution shows characteristically refractive phenomenon

  11. Alternative statistics in multi-step direct reaction theory

    International Nuclear Information System (INIS)

    Koning, A.J.

    1990-06-01

    In recent years a variety of statistical theories have been developed concerning multistep direct (MSD) nuclear reactions. In addition, dominant in applications is a whole class of semiclassical models that may be subsumed under the heading of 'generalized exciton model': these are basically MSD-type extensions on top of compound-like concepts. In this report the relationship between their underlying statistical MSD-postulates are highlighted. A common framework is sketched that enables to generate the various MSD theories through assigning statistical properties to different parts of the nuclear Hamiltonian. Then it is shown that distinct forms of nuclear randomness are embodied in the mentioned theories. All these theories appear to be very similar at a qualitative level. In order to explain the high-energy tails and forward-peaked angular distribution typical for particles emitted in MSD reactions, it is imaged that the incident continuum particle stepwise looses its energy and direction in a sequence of collisions, thereby creating new particle-hole pairs in the target system. At each step emission may take place. The statistical aspect comes in because many continuum states are involved in the process. These are supposed to display chaotic behavior, the associated randomness assumption giving rise to important simplifications in the expressions for the MSD emission cross sections. This picture suggests that the mentioned MSD models can be interpreted as variants of essentially one and the same theory. However, this appears not to be the case. To show this the usual MSD distinction within the composite reacting nucleus between the fast continuum particle and the residual system is introduced. One implication is that the mutual residual interactions of the nucleons of the residual core are to be distinguished from those of the leading particle with the residual system. This distinction will turn out to be central to the present analysis. (author). 14 refs.; 4

  12. Determination of Free Fatty Acid by FT-NIR Spectroscopy in Esterification Reaction for Biodiesel Production

    Directory of Open Access Journals (Sweden)

    Djéssica Tatiana Raspe

    2013-01-01

    Full Text Available This work reports the use of FT-NIR spectroscopy coupled with multivariate calibration to determine the percentage of free fatty acids (FFA in samples obtained by the esterification of FFA in vegetable oils. The analytical method used as calibration matrix samples of the reaction medium of esterification of oleic acid in soybean oil in proportions of 0.3 to 40 wt% (by weight of oleic acid obtained under different experimental conditions and utilized the partial least squares (PLS regression. The efficiency of the method was tested to predict the content of FFA in reactions of esterification of oleic acid in soybean oil catalysed by KSF clay and Amberlyst 15 commercial resin, both in a batch mode. Good Correlations were observed between the FT-NIR/PLS method and the reference method (AOCS. The results confirm that FT-NIR spectroscopy, in combination with multivariate calibration, is a promising technique for monitoring esterification reaction for biodiesel production.

  13. Application of multi-step direct reaction theory to 14 MeV neutron reaction, 3 (n,. cap alpha. )

    Energy Technology Data Exchange (ETDEWEB)

    Kumabe, I.; Matoba, M.; Fukuda, K. [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering; Ikegami, H.; Muraoka, M [eds.

    1980-01-01

    Multi-step direct-reaction theory proposed by Tamura et al. has been applied to continuous spectra of the 14 MeV (n, ..cap alpha..) reaction with some modifications. Calculated results reproduce well the experimental energy and angular distributions of the 14 MeV (n, ..cap alpha..) reactions.

  14. Theoretical intercomparison of multi-step direct reaction models and computational intercomparison of multi-step direct reaction models

    International Nuclear Information System (INIS)

    Koning, A.J.

    1992-08-01

    In recent years several statistical theories have been developed concerning multistep direct (MSD) nuclear reactions. In addition, dominant in applications is a whole class of semiclassical models that may be subsumed under the heading of 'generalized exciton models'. These are basically MSD-type extensions on top of compound-like concepts. In this report the relationship between their underlying statistical MSD-postulates is highlighted. A command framework is outlined that enables to generate the various MSD theories through assigning statistical properties to different parts of the nuclear Hamiltonian. Then it is shown that distinct forms of nuclear randomness are embodied in the mentioned theories. All these theories appear to be very similar at a qualitative level. In order to explain the high energy-tails and forward-peaked angular distribution typical for particles emitted in MSD reactions, it is imagined that the incident continuum particle stepwise looses its energy and direction in a sequence of collisions, thereby creating new particle-hole pairs in the target system. At each step emission may take place. The statistical aspect comes in because many continuum states are involved in the process. These are supposed to display chaotic behavior, the associated randomness assumption giving rise to important simplifications in the expression for MSD emission cross sections. This picture suggests that mentioned MSD models can be interpreted as a variant of essentially one and the same theory. However, this appears not to be the case. To show this usual MSD distinction within the composite reacting nucleus between the fast continuum particle and the residual interactions, the nucleons of the residual core are to be distinguished from those of the leading particle with the residual system. This distinction will turn out to be crucial to present analysis. 27 refs.; 5 figs.; 1 tab

  15. Reaction mechanism and spectroscopy of transfer reactions induced by heavy ions

    International Nuclear Information System (INIS)

    Lemaire, M.-C.

    1977-01-01

    The specific features displayed by data on heavy ion elastic and inelastic angular distributions are discussed, and their physical origin is pointed out from semi-classical calculations in counterpart ambiguities in the phenomenological description of the optical potential appear. Two nucleon transfer reactions induced by heavy ions successfully point out important contributions of a two-step process where the transfer is proceeding via target and residual nucleus inelastic excitation. At incident energies not too high above the Coulomb barrier, such process produces clear shape changes between different final state angular distributions. At higher incident energy, the angular distributions are forward peaked and display oscillations for both mechanisms. As for four-nucleon transfer reactions, the existing data suggest that the nucleons are well transferred into a Os relative

  16. Theory of nuclear heavy-ion direct transfer reactions

    International Nuclear Information System (INIS)

    Crowley, B.J.B.

    1979-01-01

    We review the distorted-wave approach to direct transfer reactions and draw attention to some of the shortcomings of current theories. We show that a reformulated form of the distorted-wave Born approximation (DWBA) for transfer can lead to important simplifications of the theory, which are valid for nuclear heavy-ion induced reactions at energies > or approx. =MeV/nucleon. In particular, in the semiclassical limit, it leads to a new and simple formula for the transfer t-matrix which includes all the essential physics while offering several important advantages over standard ''full-recoil finite-range'' DWBA. One such advantage is that the new formula is more transparent in that it is amendable to interpretation and analytical manipulation. At high-energy it is shown to reduce to one earlier deduced using eikonal-DWBA. The conditions for the validity of the new theory are discussed in detail. They are shown to be generally well satisfied for small-mass transfer between heavy-ions at energies at or above those particularly favour transfer (> or approx. =10 MeV/nucleon for transfer of valence nucleons). The restriction to small mass is not due to any recoil approximation; in fact, it is only a necessary restriction at certain energies. The theory treats recoil exactly. Consideration of the optimum dynamical conditions for transfer leads to a set of matching conditions. The presence of hitherto neglected absorption, arising from dynamical effects of poor matching, it suggested and qualitatively discussed. Condition under which such absorption may be neglected are derived. Results of numerical calculations are presented showing that the theory is capable of good agreement with standard full-recoil finite-range DWBA, and that it is capable of giving at least as good an account of experimental data for nucleon-transfer between heavy-ions at energies approx.10 MeV/nucleon

  17. Delta-electron spectroscopy: An aid for the determination of reaction times in heavy ion reactions

    International Nuclear Information System (INIS)

    Skapa, H.

    1983-01-01

    For the systems I->Au and I->Bi at an incident energy of 6.2 MeV/u (I->Au) and 6.6 MeV/u (I->Bi) the emission probability of delta electrons was determined. In an energy range from 150 KeV to 1000 KeV electrons were spectroscoped in coincidence to elastically, quasielastically, and deep inelastically scattered ions. In deep inelastic reaction between reaction products with high and without a mean mass drift was discriminated. The contribution of the conversion electrons, determined from gamma spectra, extends in the range of deep inelastic reactions of about 60%. While the ratio of conversion electrons for deep inelastic events with large to such without mass drift shows a flat, monotoneous growth for the ratio of the measured emission probabilities a oscillation-like structure with about 400 KeV width results. An interpretation of this structure as interference effect by nuclear time delay yields for the case of large mass drift a nuclear retention time of 7.5 x 10 -21 s. (orig./HSI) [de

  18. Direct injection of superheated steam for continuous hydrolysis reaction

    KAUST Repository

    Wang, Weicheng; Turner, Timothy L.; Roberts, William L.; Stikeleather, Larry F.

    2012-01-01

    The primary intent for previous continuous hydrolysis studies was to minimize the reaction temperature and reaction time. In this work, hydrolysis is the first step of a proprietary chemical process to convert lipids to sustainable, drop

  19. Kinetic study on bonding reaction of gelatin with CdS nanopaticles by UV-visible spectroscopy.

    Science.gov (United States)

    Tang, Shihua; Wang, Baiyang; Li, Youqun

    2015-04-15

    The chemical kinetics on gelatin-CdS direct conjugates has been systematically investigated as a function of different temperature and reactant concentration (i.e. Cd(2+), S(2-) and gelatin) by UV-visible spectroscopy, for the first time. The nonlinear fitting and the differential method were used to calculate the initial rate based on the absorbance-time data. A double logarithmic linear equation for calculating the rate constant (k) and the reaction order (n) was introduced. The reaction kinetic parameters (n, k, Ea, and Z) and activation thermodynamic parameters (ΔG(≠), ΔH(≠), and ΔS(≠)) were obtained from variable temperature kinetic studies. The overall rate equation allowing evaluation of conditions that provide required reaction rate could be expressed as: r = 1.11 × 10(8) exp(-4971/T)[Cd(2+)][gelatin](0.6)[S(2-)](0.6) (M/S) The calculated values of the reaction rate are well coincide with the experimental results. A suitable kinetic model is also proposed. This work will provide guidance for the rational design of gelatin-directed syntheses of metal sulfide materials, and help to understand the biological effects of nanoparticles at the molecular level. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Quantum state-resolved gas/surface reaction dynamics probed by reflection absorption infrared spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Chen Li [Department of Dynamics at Surfaces, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11, Goettingen (Germany); Ueta, Hirokazu; Beck, Rainer D. [Laboratoire de Chimie Physique Moleculaire, Ecole Polytechnique Federale de Lausanne (Switzerland); Bisson, Regis [Aix-Marseille Universite, PIIM, CNRS, UMR 7345, 13397 Marseille (France)

    2013-05-15

    We report the design and characterization of a new molecular-beam/surface-science apparatus for quantum state-resolved studies of gas/surface reaction dynamics combining optical state-specific reactant preparation in a molecular beam by rapid adiabatic passage with detection of surface-bound reaction products by reflection absorption infrared spectroscopy (RAIRS). RAIRS is a non-invasive infrared spectroscopic detection technique that enables online monitoring of the buildup of reaction products on the target surface during reactant deposition by a molecular beam. The product uptake rate obtained by calibrated RAIRS detection yields the coverage dependent state-resolved reaction probability S({theta}). Furthermore, the infrared absorption spectra of the adsorbed products obtained by the RAIRS technique provide structural information, which help to identify nascent reaction products, investigate reaction pathways, and determine branching ratios for different pathways of a chemisorption reaction. Measurements of the dissociative chemisorption of methane on Pt(111) with this new apparatus are presented to illustrate the utility of RAIRS detection for highly detailed studies of chemical reactions at the gas/surface interface.

  1. Future directions in electron momentum spectroscopy of matter

    International Nuclear Information System (INIS)

    Weigold, E.

    1998-01-01

    The development of coincidence spectrometers with multivariable detection techniques, higher energy kinematics, monochromated and spin-polarised electron sources, will usher in a new generation of electron momentum spectroscopy revealing new electronic phenomena in atoms, molecules and solids. This will be enhanced by developments in target preparation, such as spin polarised, oriented and aligned atoms and molecules, radicals, surfaces and strongly correlated systems in condensed matter. Copyright (1998) CSIRO Australia

  2. [Studies on the oxidation reaction of octanol-2 with nitric acid by infrared spectroscopy].

    Science.gov (United States)

    Zhang, G; Zhao, G; Wang, Y; Zhang, Q; Zhang, S; Lu, F

    1998-04-01

    In this paper, the reaction process of oxidation of octanol-2 with nitric acid has been studied by IR spectroscopy. It is found that the main components of non-sapoifiable matter are different in different oxidation degrees. The relation between oxidation products and the amount of nitric acid are investigated,the reaction mechanism has also been studied. Experimental results show that the oxidation process of octanol-2 is as follows: first, octanol-2 is oxidated to octanone-2, or to nitrate, nitrite and nitrile copmpounds, then these compounds are reoxidated to caproic acid in the meantime some by-products, such as valeric, enanthic acids are also found in oxidated products.

  3. Time-resolved resonance fluorescence spectroscopy for study of chemical reactions in laser-induced plasmas.

    Science.gov (United States)

    Liu, Lei; Deng, Leimin; Fan, Lisha; Huang, Xi; Lu, Yao; Shen, Xiaokang; Jiang, Lan; Silvain, Jean-François; Lu, Yongfeng

    2017-10-30

    Identification of chemical intermediates and study of chemical reaction pathways and mechanisms in laser-induced plasmas are important for laser-ablated applications. Laser-induced breakdown spectroscopy (LIBS), as a promising spectroscopic technique, is efficient for elemental analyses but can only provide limited information about chemical products in laser-induced plasmas. In this work, time-resolved resonance fluorescence spectroscopy was studied as a promising tool for the study of chemical reactions in laser-induced plasmas. Resonance fluorescence excitation of diatomic aluminum monoxide (AlO) and triatomic dialuminum monoxide (Al 2 O) was used to identify these chemical intermediates. Time-resolved fluorescence spectra of AlO and Al 2 O were used to observe the temporal evolution in laser-induced Al plasmas and to study their formation in the Al-O 2 chemistry in air.

  4. Study of 16O-induced deep inelastic nuclear reactions on 27Al, 48Ti, and 58Ni by spectroscopy of the gamma radiation from the reaction products

    International Nuclear Information System (INIS)

    Puchta, H.

    1980-01-01

    The present thesis deals with the spectroscopy of the gamma radiation from the reaction fragments after binary reactions in the systems 16 O + 27 Al, 48 Ti, and 58 Ni at incident energies from 90 to 100 MeV, i.e. far above the Coulomb threshold. ΔE-E telescopes, which were located at 35 0 to the beam direction, detected the projectile-like fragments and defined the reaction channel and the scattering plane. In coincidence to this the gamma quanta in a 120-cm 3 -Ge(Li)-diode and a 27 x 33-cm-NaI-spectrometer were observed. The gamma spectra are equal to those observed hitherto in fusion reactions except for the high energetic gamma lines from the ejectiles, which are raised from the gamma continuum of the heavy fragments. From the spectroscoped gamma radiation for the light as for the heavy fragments the excitation energy, the value of the fragment angular momentum, as well as the occupation of the magnetic sublevels could be determined. The hard projectile 16 O transfers the dissipated energy and the angular momentum transferred by the spin of the fragments nearly completely into the residue nucleus. The probability for the observation of a ground state transition in one of the heavy fragments extends to (0.85 +- 0.10) per carbon ejectile in the system 16 O + 48 Ti. The residue nucleus distribution corresponds to that expected by the statistical model from the decay of the compound-nucleus 52 Cr belonging to the ejectile 12 C, the excitation energy of which corresponds to the reaction Q-value. (orig./HSI) [de

  5. Atmospheric pressure reaction cell for operando sum frequency generation spectroscopy of ultrahigh vacuum grown model catalysts

    Science.gov (United States)

    Roiaz, Matteo; Pramhaas, Verena; Li, Xia; Rameshan, Christoph; Rupprechter, Günther

    2018-04-01

    A new custom-designed ultrahigh vacuum (UHV) chamber coupled to a UHV and atmospheric-pressure-compatible spectroscopic and catalytic reaction cell is described, which allows us to perform IR-vis sum frequency generation (SFG) vibrational spectroscopy during catalytic (kinetic) measurements. SFG spectroscopy is an exceptional tool to study vibrational properties of surface adsorbates under operando conditions, close to those of technical catalysis. This versatile setup allows performing surface science, SFG spectroscopy, catalysis, and electrochemical investigations on model systems, including single crystals, thin films, and deposited metal nanoparticles, under well-controlled conditions of gas composition, pressure, temperature, and potential. The UHV chamber enables us to prepare the model catalysts and to analyze their surface structure and composition by low energy electron diffraction and Auger electron spectroscopy, respectively. Thereafter, a sample transfer mechanism moves samples under UHV to the spectroscopic cell, avoiding air exposure. In the catalytic cell, SFG spectroscopy and catalytic tests (reactant/product analysis by mass spectrometry or gas chromatography) are performed simultaneously. A dedicated sample manipulation stage allows the model catalysts to be examined from LN2 temperature to 1273 K, with gaseous reactants in a pressure range from UHV to atmospheric. For post-reaction analysis, the SFG cell is rapidly evacuated and samples are transferred back to the UHV chamber. The capabilities of this new setup are demonstrated by benchmark results of CO adsorption on Pt and Pd(111) single crystal surfaces and of CO adsorption and oxidation on a ZrO2 supported Pt nanoparticle model catalyst grown by atomic layer deposition.

  6. Process spectroscopy in microemulsions—setup and multi-spectral approach for reaction monitoring of a homogeneous hydroformylation process

    Science.gov (United States)

    Meyer, K.; Ruiken, J.-P.; Illner, M.; Paul, A.; Müller, D.; Esche, E.; Wozny, G.; Maiwald, M.

    2017-03-01

    Reaction monitoring in disperse systems, such as emulsions, is of significant technical importance in various disciplines like biotechnological engineering, chemical industry, food science, and a growing number other technical fields. These systems pose several challenges when it comes to process analytics, such as heterogeneity of mixtures, changes in optical behavior, and low optical activity. Concerning this, online nuclear magnetic resonance (NMR) spectroscopy is a powerful technique for process monitoring in complex reaction mixtures due to its unique direct comparison abilities, while at the same time being non-invasive and independent of optical properties of the sample. In this study the applicability of online-spectroscopic methods on the homogeneously catalyzed hydroformylation system of 1-dodecene to tridecanal is investigated, which is operated in a mini-plant scale at Technische Universität Berlin. The design of a laboratory setup for process-like calibration experiments is presented, including a 500 MHz online NMR spectrometer, a benchtop NMR device with 43 MHz proton frequency as well as two Raman probes and a flow cell assembly for an ultraviolet and visible light (UV/VIS) spectrometer. Results of high-resolution online NMR spectroscopy are shown and technical as well as process-specific problems observed during the measurements are discussed.

  7. Challenge for real-time and real-space resolved spectroscopy of surface chemical reactions. Aiming at trace of irreversible and inhomogeneous reactions

    International Nuclear Information System (INIS)

    Amemiya, Kenta

    2015-01-01

    A novel experimental technique, time-resolved wavelength-dispersive soft X-ray imaging spectroscopy, is proposed in order to achieve real-time and real-space resolved spectroscopy for the observation of irreversible and inhomogeneous surface chemical reactions. By combining the wavelength-dispersed soft X rays, in which the X-ray wavelength (photon energy) changes as a function of position on the sample, with the photoelectron emission microscope, the soft X-ray absorption spectra are separately obtained at different positions on the sample without scanning the X-ray monochromator. Therefore, the real-time resolved measurement of site-selective soft X-ray absorption spectroscopy is realized in one event without repeating the chemical reaction. It is expected that the spatial distribution of different chemical species is traced during the surface chemical reaction, which is essential to understand the reaction mechanism. (author)

  8. Classical kinematic model for direct reactions of oriented reagents

    International Nuclear Information System (INIS)

    Schechter, I.; Prisant, M.G.; Levine, R.D.

    1987-01-01

    A simple kinematic model based on the concept of an orientation-dependent critical configuration for reaction is introduced and applied. The model serves two complementary purposes. In the predictive mode the model provides an easily implemented procedure for computing the reactivity of oriented reagents (including those actually amenable to measure) from a given potential energy surface. The predictions of the model are compared against classical trajectory results for the H + D 2 reaction. By use of realistic potential energy surfaces the model is applied to the Li + HF and O + HCl reactions where the HX molecules are pumped by a polarized laser. A given classical trajectory is deemed reactive or not according to whether it can surmount the barrier at that particular orientation. The essential difference with the model of Levine and Bernstein is that the averaging over initial conditions is performed by using a Monte Carlo integration. One can therefore use the correct orientation-dependent shape (and not only height) of the barrier to reaction and, furthermore, use oriented or aligned reagents. Since the only numerical step is a Monte Carlo sampling of initial conditions, very many trajectories can be run. This suffices to determine the reaction cross section for different initial conditions. To probe the products, they have employed the kinematic approach of Elsum and Gordon. The result is a model where, under varying initial conditions, examining final-state distributions or screening different potential energy surfaces can be efficiently carried out

  9. Chemical Reaction Engineering: Current Status and Future Directions.

    Science.gov (United States)

    Dudukovic, M. P.

    1987-01-01

    Describes Chemical Reaction Engineering (CRE) as the discipline that quantifies the interplay of transport phenomena and kinetics in relating reactor performance to operating conditions and input variables. Addresses the current status of CRE in both academic and industrial settings and outlines future trends. (TW)

  10. Purification of crude glycerol from transesterification reaction of palm oil using direct method and multistep method

    Science.gov (United States)

    Nasir, N. F.; Mirus, M. F.; Ismail, M.

    2017-09-01

    Crude glycerol which produced from transesterification reaction has limited usage if it does not undergo purification process. It also contains excess methanol, catalyst and soap. Conventionally, purification method of the crude glycerol involves high cost and complex processes. This study aimed to determine the effects of using different purification methods which are direct method (comprises of ion exchange and methanol removal steps) and multistep method (comprises of neutralization, filtration, ion exchange and methanol removal steps). Two crude glycerol samples were investigated; the self-produced sample through the transesterification process of palm oil and the sample obtained from biodiesel plant. Samples were analysed using Fourier Transform Infrared Spectroscopy, Gas Chromatography and High Performance Liquid Chromatography. The results of this study for both samples after purification have showed that the pure glycerol was successfully produced and fatty acid salts were eliminated. Also, the results indicated the absence of methanol in both samples after purification process. In short, the combination of 4 purification steps has contributed to a higher quality of glycerol. Multistep purification method gave a better result compared to the direct method as neutralization and filtration steps helped in removing most excess salt, fatty acid and catalyst.

  11. Molecular electronics of a single photosystem I reaction center: Studies with scanning tunneling microscopy and spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Lee, I.; Lee, J.W.; Warmack, R.J.; Allison, D.P.; Greenbaum, E. [Oak Ridge National Lab., TN (United States)

    1995-03-14

    Thylakoids and photosystem I (PSI) reaction centers were imaged by scanning tunneling microscopy. The thylakoids were isolated from spinach chloroplasts, and PSI reaction centers were extracted from thylakoid membranes. Because thylakoids are relatively thick nonconductors, they were sputter-coated with Pd/Au before imaging. PSI photosynthetic centers and chemically platinized PSI were investigated without sputter-coating. They were mounted on flat gold substrates that had been treated with mercaptoacetic acid to help bind the proteins. With tunneling spectroscopy, the PSI centers displayed a semiconductor-like response with a band gap of 1.8 eV. Lightly platinized (platinized for 1 hr) centers displayed diode-like conduction that resulted in dramatic contrast changes between images taken with opposite bias voltages. The electronic properties of this system were stable under long-term storage. 42 refs., 7 figs.

  12. Direct and quantitative photothermal absorption spectroscopy of individual particulates

    International Nuclear Information System (INIS)

    Tong, Jonathan K.; Hsu, Wei-Chun; Eon Han, Sang; Burg, Brian R.; Chen, Gang; Zheng, Ruiting; Shen, Sheng

    2013-01-01

    Photonic structures can exhibit significant absorption enhancement when an object's length scale is comparable to or smaller than the wavelength of light. This property has enabled photonic structures to be an integral component in many applications such as solar cells, light emitting diodes, and photothermal therapy. To characterize this enhancement at the single particulate level, conventional methods have consisted of indirect or qualitative approaches which are often limited to certain sample types. To overcome these limitations, we used a bilayer cantilever to directly and quantitatively measure the spectral absorption efficiency of a single silicon microwire in the visible wavelength range. We demonstrate an absorption enhancement on a per unit volume basis compared to a thin film, which shows good agreement with Mie theory calculations. This approach offers a quantitative approach for broadband absorption measurements on a wide range of photonic structures of different geometric and material compositions

  13. Direct and quantitative broadband absorptance spectroscopy with multilayer cantilever probes

    Science.gov (United States)

    Hsu, Wei-Chun; Tong, Jonathan Kien-Kwok; Liao, Bolin; Chen, Gang

    2015-04-21

    A system for measuring the absorption spectrum of a sample is provided that includes a broadband light source that produces broadband light defined within a range of an absorptance spectrum. An interferometer modulates the intensity of the broadband light source for a range of modulation frequencies. A bi-layer cantilever probe arm is thermally connected to a sample arm having at most two layers of materials. The broadband light modulated by the interferometer is directed towards the sample and absorbed by the sample and converted into heat, which causes a temperature rise and bending of the bi-layer cantilever probe arm. A detector mechanism measures and records the deflection of the probe arm so as to obtain the absorptance spectrum of the sample.

  14. Electrochemical impedance spectroscopy analysis of a thin polymer film-based micro-direct methanol fuel cell

    Science.gov (United States)

    Schulz, Tobias; Weinmüller, Christian; Nabavi, Majid; Poulikakos, Dimos

    A single cell micro-direct methanol fuel cell (micro-DMFC) was investigated using electrochemical impedance spectroscopy. The electrodes consisted of thin, flexible polymer (SU8) film microchannel structures fabricated in-house using microfabrication techniques. AC impedance spectroscopy was used to separate contributions to the overall cell polarization from the anode, cathode and membrane. A clear distinction between the different electrochemical phenomena occurring in the micro-DMFC, especially the distinction between double layer charging and Faradaic reactions was shown. The effect of fuel flow rate, temperature, and anode flow channel structure on the impedance of the electrode reactions and membrane/electrode double layer charging were investigated. Analysis of impedance data revealed that the performance of the test cell was largely limited by the presence of intermediate carbon monoxide in the anode reaction. Higher temperatures increase cell performance by enabling intermediate CO to be oxidized at much higher rates. The results also revealed that serpentine anode flow microchannels show a lower tendency to intermediate CO coverage and a more stable cell behavior than parallel microchannels.

  15. Styrene oligomerization as a molecular probe reaction for zeolite acidity: a UV-Vis spectroscopy and DFT study

    NARCIS (Netherlands)

    Buurmans, I.L.C.; Pidko, E.A.; Groot, de J.M.; Stavitski, E.; Santen, van R.A.; Weckhuysen, B.M.

    2010-01-01

    A series of H-ZSM-5 crystallites with different framework Si/Al ratios was studied by analyzing the kinetics and reaction mechanism of the oligomerization of 4-fluorostyrene as molecular probe reaction for Brønsted acidity. The formation of carbocationic species was followed by UV-Vis spectroscopy.

  16. Velocity-space observation regions of high-resolution two-step reaction gamma-ray spectroscopy

    DEFF Research Database (Denmark)

    Salewski, Mirko; Nocente, M.; Gorini, G.

    2015-01-01

    High-resolution γ-ray spectroscopy (GRS) measurements resolve spectral shapes of Dopplerbroadened γ-rays. We calculate weight functions describing velocity-space sensitivities of any two-step reaction GRS measurements in magnetized plasmas using the resonant nuclear reaction 9Be(α, nγ)12C...

  17. Hydrogen evolution reaction on electrodes with different PT/C loadings by electrochemical impedance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ortega-Chavez, L. [Inst. Tecnologico de Chihuahua 2, Chihuahua, Chih (Mexico); Ortega-Chavez, L.; Herrera-Peraza, E. [Centro de Investigacion en Materiales Avanzados, Chiuahua, Chih (Mexico); Verde, Y. [Inst. Tecnologico de Cancun, Cancun, Quintana Roo (Mexico)

    2008-04-15

    One of the most widely studied reactions in electrochemistry is the hydrogen evolution reaction (HER). HER is important for the development of water hydrolysis and fuel cell technologies. Because hydrogen-substrate interaction determines oxygen reduction efficiency, an understanding of the chemical and electronic state of hydrogen adsorbed on the electrocatalyst surface is required. Electrochemical impedance spectroscopy (EIS) is a proven highly efficient technique for interface characterization and kinetic parameter determination for different reactions carried out on interfaces. This article presented a study that utilized EIS for characterizing electrodes under HER by implementing a rotating disc electrode with different carbon supported platinum nanoparticles loadings and different potentials in acidic solutions. The results collected by EIS were analyzed in terms of equivalent circuits to calculate different parameters which were compared by statistical analysis. The study also considered the Volmer, Heyrovsky and Tafel steps in the HER reaction as well as a single electro-absorbed intermediate species. The article discussed the experimental set-up with reference to measurements, simulation and fitting. Parameters analysis using ANOVA were reviewed. It was concluded that an increase in impedance occurs when platinum loading decreases in both high and low frequencies. 22 refs., 1 tab., 5 figs.

  18. Resume and discussion of session on direct heavy ion reactions

    International Nuclear Information System (INIS)

    Hansen, O.

    1983-01-01

    A conference divides into sessions, but the physics does not always respect such divisions. I found the subject of barrier penetrabilities viewed in a coupled channels picture new, exciting and central to all heavy-ion reaction dynamics. The subject was discussed in bits and pieces over three different sessions, partly in the talks by Winther, Landowne, Braun-Munzinger and Broglia, and partly from the floor by the same people and by Smilanski, I have concentrated on that subject alone and I therefore must apologize to the speakers in my session who covered different material, that definitely merited further discussions. Also, I apologize to other session chairmen, whose territory I have invaded. (orig.)

  19. Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides

    Science.gov (United States)

    Taatjes, Craig A.

    2017-05-01

    The carbonyl oxide intermediates in the ozonolysis of alkenes, often known as Criegee intermediates, are potentially important reactants in Earth's atmosphere. For decades, careful analysis of ozonolysis systems was employed to derive an understanding of the formation and reactions of these species. Recently it has proved possible to synthesize at least some of these intermediates separately from ozonolysis, and hence to measure their reaction kinetics directly. Direct measurements have allowed new or more detailed understanding of each type of gas-phase reaction that carbonyl oxides undergo, often acting as a complement to highly detailed ozonolysis experiments. Moreover, the use of direct characterization methods to validate increasingly accurate theoretical investigations can enhance their impact well beyond the set of specific reactions that have been measured. Reactions that initiate particles or fuel their growth could be a new frontier for direct measurements of Criegee intermediate chemistry.

  20. Design of a facility for the in situ measurement of catalytic reaction by neutron scattering spectroscopy

    Science.gov (United States)

    Tan, Shuai; Cheng, Yongqiang; Daemen, Luke L.; Lutterman, Daniel A.

    2018-01-01

    Catalysis is a critical enabling science for future energy needs. The next frontier of catalysis is to evolve from catalyst discovery to catalyst design, and for this next step to be realized, we must develop new techniques to better understand reaction mechanisms. To do this, we must connect catalytic reaction rates and selectivities to the kinetics, energetics, and dynamics of individual elementary steps and relate these to the structure and dynamics of the catalytic sites involved. Neutron scattering spectroscopies offer unique capabilities that are difficult or impossible to match by other techniques. The current study presents the development of a compact and portable instrumental design that enables the in situ investigation of catalytic samples by neutron scattering techniques. The developed apparatus was tested at the Spallation Neutron Source (SNS) in Oak Ridge National Laboratory and includes a gas handling panel that allows for computer hookups to control the panel externally and online measurement equipment such as coupled GC-FID/TCD (Gas Chromatography-Flame Ionization Detector/Thermal Conductivity Detector) and MS (Mass Spectrometry) to characterize offgassing while the sample is in the neutron scattering spectrometer. This system is flexible, modular, compact, and portable enabling its use for many types of gas-solid and liquid-solid reactions at the various beamlines housed at the SNS.

  1. Experimental Guidance of ISB Corrections via Direct Nuclear Reactions

    Science.gov (United States)

    Leach, K. G.; Garrett, P. E.; Ball, G. C.; Bangay, J. C.; Bianco, L.; Demand, G. A.; Faestermann, T.; Finlay, P.; Green, K. L.; Hertenberger, R.; Kriicken, R.; Phillips, A. A.; Rand, E. T.; Sumithrarachchi, C. S.; Svensson, C. E.; Towner, I. S.; Triambak, S.; Wirth, H.-F.; Wong, J.

    2011-09-01

    The most recent isospin-symmetry-breaking corrections, δc, of Towner and Hardy for superallowed Fermi β-decay transitions, have included the opening of specific core orbitals. This change has resulted in significant deviations in some of the δc factors from their previous calculations, and an improved agreement of the individual corrected Script Ft values with the overall world average of the 13 most precise cases. While this is consistent with the conserved-vector-current (CVC) hypothesis of the Standard Model, these new calculations must be thoroughly tested, and guidance must be given for the improvement of calculations for the upper-pf shell nuclei. Using the (d,t) reaction mechanism to probe the single neutron wavefunction overlap, information regarding the relevant shell-model configurations needed in the calculation can be determined. An experiment was therefore performed with a 22 MeV polarized deuterium beam from the MP tandem Van de Graaff accelerator in Munich, Germany. Using the Q3D magnetic spectrograph, and a cathode-strip focal-plane detector, outgoing tritons were analyzed at 9 angles between 10° and 60°, up to an excitation energy of 4.8 MeV. This proceeding reports the motivational and experimental details for the 64Zn(d,t)63Zn transfer work presented.

  2. Delineating pMDI model reactions with loblolly pine via solution-state NMR spectroscopy. Part 1, Catalyzed reactions with wood models and wood polymers

    Science.gov (United States)

    Daniel J. Yelle; John Ralph; Charles R. Frihart

    2011-01-01

    To better understand adhesive interactions with wood, reactions between model compounds of wood and a model compound of polymeric methylene diphenyl diisocyanate (pMDI) were characterized by solution-state NMR spectroscopy. For comparison, finely ground loblolly pine sapwood, milled-wood lignin and holocellulose from the same wood were isolated and derivatized with...

  3. Direct estimate of cocoa powder content in cakes by colorimetry and photoacoustic spectroscopy

    NARCIS (Netherlands)

    Doka, O.; Bicanic, D.D.; Kulcsar, R.

    2014-01-01

    Cocoa is a very important ingredient in the food industry and largely consumed worldwide. In this investigation, colorimetry and photoacoustic spectroscopy were used to directly assess the content of cocoa powder in cakes; both methods provided satisfactory results. The calibration curve was

  4. A reaction cell for ambient pressure soft x-ray absorption spectroscopy

    Science.gov (United States)

    Castán-Guerrero, C.; Krizmancic, D.; Bonanni, V.; Edla, R.; Deluisa, A.; Salvador, F.; Rossi, G.; Panaccione, G.; Torelli, P.

    2018-05-01

    We present a new experimental setup for performing X-ray Absorption Spectroscopy (XAS) in the soft X-ray range at ambient pressure. The ambient pressure XAS setup is fully compatible with the ultra high vacuum environment of a synchrotron radiation spectroscopy beamline end station by means of ultrathin Si3N4 membranes acting as windows for the X-ray beam and seal of the atmospheric sample environment. The XAS detection is performed in total electron yield (TEY) mode by probing the drain current from the sample with a picoammeter. The high signal/noise ratio achievable in the TEY mode, combined with a continuous scanning of the X-ray energies, makes it possible recording XAS spectra in a few seconds. The first results show the performance of this setup to record fast XAS spectra from sample surfaces exposed at atmospheric pressure, even in the case of highly insulating samples. The use of a permanent magnet inside the reaction cell enables the measurement of X-ray magnetic circular dichroism at ambient pressure.

  5. Studies of Heterogeneously Catalyzed Liquid-Phase Alcohol Oxidation on Platinum bySum-frequency Generation Vibrational Spectroscopy and Reaction Rate Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Christopher [Univ. of California, Berkeley, CA (United States)

    2014-05-15

    Compared to many branches of chemistry, the molecular level study of catalytically active surfaces is young. Only with the invention of ultrahigh vacuum technology in the past half century has it been possible to carry out experiments that yield useful molecular information about the reactive occurrences at a surface. The reason is two-fold: low pressure is necessary to keep a surface clean for an amount of time long enough to perform an experiment, and most atomic scale techniques that are surface speci c (x-ray photoelectron spectroscopy, electron energy loss spectroscopy, Auger electron spectroscopy, etc.) cannot be used at ambient pressures, because electrons, which act as chemical probes in these techniques, are easily scattered by molecules. Sum-frequency generation (SFG) vibrational spectroscopy is one technique that can provide molecular level information from the surface without the necessity for high vacuum. Since the advent of SFG as a surface spectroscopic tool it has proved its worth in the studies of surface catalyzed reactions in the gas phase, with numerous reactions in the gas phase having been investigated on a multitude of surfaces. However, in situ SFG characterization of catalysis at the solid-liquid interface has yet to be thoroughly pursued despite the broad interest in the use of heterogeneous catalysts in the liquid phase as replacements for homogeneous counterparts. This work describes an attempt to move in that direction, applying SFG to study the solid-liquid interface under conditions of catalytic alcohol oxidation on platinum.

  6. Interference between direct and indirect modes in two-nucleon transfer reactions with heavy ions

    International Nuclear Information System (INIS)

    Scott, D.K.; Harvey, B.G.; Hendrie, D.L.; Jahnke, U.; Kraus, L.; Maguire, C.F.; Mahoney, J.; Terrien, Y.; Yagi, K.; Glendenning, N.K.

    1975-01-01

    Direct and indirect transitions to the lowest 2 + collective states are shown to interfere constructively in the pickup reaction 122 Sn( 16 O, 18 O) 120 Sn at 104 MeV, and destructively in the inverse stripping reaction 120 Sn( 18 O, 16 O) 122 Sn at 99 MeV

  7. The catalytic potency of ß-glucosidase from Pyroccus furiosus in the direct glucosylation reaction

    NARCIS (Netherlands)

    Roode, de B.M.; Meer, van der T.D.; Kaper, T.; Franssen, M.C.R.; Padt, van der A.; Oost, van der J.; Boom, R.M.

    2001-01-01

    Enzymes from extremophiles operate at conditions that are different from their `normal' counterparts, and are therefore a useful extension of the enzyme toolbox. In this paper, the direct glucosylation reaction mediated by a hyperthermophilic -glucosidase from Pyrocuccus furiosus was investigated.

  8. KAPSIES: A program for the calculation of multi-step direct reaction cross sections

    International Nuclear Information System (INIS)

    Koning, A.J.; Akkermans, J.M.

    1994-09-01

    We present a program for the calculation of continuum cross sections, sepctra, angular distributions and analyzing powers according to various quantum-mechanical theories for statistical multi-step direct nuclear reactions. (orig.)

  9. Probing the electronic structure of redox species and direct determination of intrinsic reorganization energies of electron transfer reactions

    International Nuclear Information System (INIS)

    Wang, Xue-Bin; Wang, Lai-Sheng

    2000-01-01

    An experimental technique capable of directly determining the intrinsic reorganization energies of bimolecular electron transfer reactions is described. Appropriate solution phase redox species are prepared in the gas phase using electrospray ionization and probed using photodetachment spectroscopy. Five metal complex anions involved in the Fe 2+ -Fe 3+ redox couple are investigated and the intramolecular reorganization energies are measured directly from spectral features due to removing the most loosely bound 3d electron from the Fe(II)-complexes. The photodetachment spectra also yield electronic structure information about the Fe 2+ -Fe 3+ redox couple and provide a common electronic structure origin for the reducing capability of the Fe(II)-complexes, the most common redox reagents. (c) 2000 American Institute of Physics

  10. Pd(II/HPMoV-Catalyzed Direct Oxidative Coupling Reaction of Benzenes with Olefins

    Directory of Open Access Journals (Sweden)

    Yasutaka Ishii

    2010-03-01

    Full Text Available The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc2/molybdovanadophosphoric acid (HPMoV as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation.

  11. Chirped laser dispersion spectroscopy using a directly modulated quantum cascade laser

    International Nuclear Information System (INIS)

    Hangauer, Andreas; Nikodem, Michal; Wysocki, Gerard; Spinner, Georg

    2013-01-01

    Chirped laser dispersion spectroscopy (CLaDS) utilizing direct modulation of a quantum cascade laser (QCL) is presented. By controlling the laser bias nearly single- and dual-sideband CLaDS operation can be realized in an extremely simplified optical setup with no external optical modulators. Capability of direct single-sideband modulation is a unique feature of QCLs that exhibit a low linewidth enhancement factor. The developed analytical model shows excellent agreement with the experimental, directly modulated CLaDS spectra. This method overcomes major technical limitations of mid-infrared CLaDS systems by allowing significantly higher modulation frequencies and eliminating optical fringes introduced by external modulators

  12. Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hellman, Hal

    1968-01-01

    This booklet discusses spectroscopy, the study of absorption of radiation by matter, including X-ray, gamma-ray, microwave, mass spectroscopy, as well as others. Spectroscopy has produced more fundamental information to the study of the detailed structure of matter than any other tools.

  13. Spectroscopy

    CERN Document Server

    Walker, S

    1976-01-01

    The three volumes of Spectroscopy constitute the one comprehensive text available on the principles, practice and applications of spectroscopy. By giving full accounts of those spectroscopic techniques only recently introduced into student courses - such as Mössbauer spectroscopy and photoelectron spectroscopy - in addition to those techniques long recognised as being essential in chemistry teaching - sucha as e.s.r. and infrared spectroscopy - the book caters for the complete requirements of undergraduate students and at the same time provides a sound introduction to special topics for graduate students.

  14. High-resolution spectroscopy of deeply-bound pionic atoms in heavy nuclei by pion-transfer reactions of inverse kinematics using the GSI cooler ring ESR

    International Nuclear Information System (INIS)

    Yamazaki, Toshimitsu.

    1991-02-01

    Many studies published in the past are reviewed first in relation to high-resolution spectroscopy of deeply-bound pionic atoms in heavy nuclei. The report then describes a procedure for applying the method of inverse kinematics to the case of (d, 3 He) reactions. The (d, 3 He) reaction in inverse kinematics is feasible from practical viewpoints. Thus a discussion is made of the inverse kinematics in which a heavy-ion beam ( 208 Pb for instance) with a projectile kinetic energy hits a deuteron target and ejected recoil 3 He nuclei are measured in the forward direction. The recoil momentum is calculated as a function of the Q value. Analysis shows that the recoil spectroscopy with inverse kinematics can be applied to the case of (d, 3 He) reaction, which will yield a very high mass resolution. The experimental setup for use in the first stage is then outlined, and a simple detector configuration free of magnetic field is discussed. These investigations demonstrate that the (d, 3 He) reaction in inverse kinematics provides a promising tool for obtaining high-resolution spectra of deeply-bound pionic atoms. (N.K.)

  15. Chemical kinetic studies of atmospheric reactions using tunable diode laser spectroscopy

    Science.gov (United States)

    Worsnop, Douglas R.; Nelson, David D.; Zahniser, Mark S.

    1993-01-01

    IR absorption using tunable diode laser spectroscopy provides a sensitive and quantitative detection method for laboratory kinetic studies of atmospheric trace gases. Improvements in multipass cell design, real time signal processing, and computer controlled data acquisition and analysis have extended the applicability of the technique. We have developed several optical systems using off-axis resonator mirror designs which maximize path length while minimizing both the sample volume and the interference fringes inherent in conventional 'White' cells. Computerized signal processing using rapid scan (300 kHz), sweep integration with 100 percent duty cycle allows substantial noise reduction while retaining the advantages of using direct absorption for absolute absorbance measurements and simultaneous detection of multiple species. Peak heights and areas are determined by curve fitting using nonlinear least square methods. We have applied these techniques to measurements of: (1) heterogeneous uptake chemistry of atmospheric trace gases (HCl, H2O2, and N2O5) on aqueous and sulfuric acid droplets; (2) vapor pressure measurements of nitric acid and water over prototypical stratospheric aerosol (nitric acid trihydrate) surfaces; and (3) discharge flow tube kinetic studies of the HO2 radical using isotopic labeling for product channel and mechanistic analysis. Results from each of these areas demonstrate the versatility of TDL absorption spectroscopy for atmospheric chemistry applications.

  16. Comparison between proton transfer reaction mass spectrometry and near infrared spectroscopy for the authentication of Brazilian coffee

    NARCIS (Netherlands)

    Monteiro, Pablo Inocêncio; Santos, Jânio Sousa; Alvarenga Brizola, Vitor Rafael; Pasini Deolindo, Carolina Turnes; Koot, Alex; Boerrigter-Eenling, Rita; Ruth, van Saskia; Georgouli, Konstantia; Koidis, Anastasios; Granato, Daniel

    2018-01-01

    In this study, proton-transfer reaction mass spectrometry (PTR-MS) and near-infrared spectroscopy (NIRS) were compared for the authentication of geographical and farming system origins of Brazilian coffees. For this purpose, n = 19 organic (ORG) and n = 26 conventional (CONV) coffees from

  17. Resonating group method as applied to the spectroscopy of α-transfer reactions

    Science.gov (United States)

    Subbotin, V. B.; Semjonov, V. M.; Gridnev, K. A.; Hefter, E. F.

    1983-10-01

    In the conventional approach to α-transfer reactions the finite- and/or zero-range distorted-wave Born approximation is used in liaison with a macroscopic description of the captured α particle in the residual nucleus. Here the specific example of 16O(6Li,d)20Ne reactions at different projectile energies is taken to present a microscopic resonating group method analysis of the α particle in the final nucleus (for the reaction part the simple zero-range distorted-wave Born approximation is employed). In the discussion of suitable nucleon-nucleon interactions, force number one of the effective interactions presented by Volkov is shown to be most appropriate for the system considered. Application of the continuous analog of Newton's method to the evaluation of the resonating group method equations yields an increased accuracy with respect to traditional methods. The resonating group method description induces only minor changes in the structures of the angular distributions, but it does serve its purpose in yielding reliable and consistent spectroscopic information. NUCLEAR STRUCTURE 16O(6Li,d)20Ne; E=20 to 32 MeV; calculated B(E2); reduced widths, dσdΩ extracted α-spectroscopic factors. ZRDWBA with microscope RGM description of residual α particle in 20Ne; application of continuous analog of Newton's method; tested and applied Volkov force No. 1; direct mechanism.

  18. Spectroscopy of $^{46}$Ar 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.; Kröll, T.; Krücken, T.; 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.

    2016-04-27

    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.

  19. Spectroscopy and dynamics of chemical reactions in van der Waals complexes

    International Nuclear Information System (INIS)

    Soorkia, Satchin

    2008-09-01

    Transition metal elements have d valence electrons and are characterized by a great variety of electronic configurations responsible for their specific reactivity. The elements of the second row in particular have 4d and 5s atomic orbitals of similar size and energy which can be both involved in chemical processes. We have been interested in the reactivity of a transition metal element, zirconium, combined with a simple organic functionalized molecule in a van der Waals complex formed in a supersonic molecular beam in the model reaction Zr + CH 3 F. In this context, one of the chemicals reactions that we are interested in leads to the formation of ZrF. The electronic spectroscopy of ZrF in the spectral domain 400 - 470 nm is extremely rich and surprising for a diatomic molecule. With this study, we have been able to identify the ground state of ZrF (X 2 Δ) by simulating the observed rotational structures and obtain essential information on the electronic structure. These experimental results are in agreement with ab initio calculations. The excited states of the complex Zr...F-CH 3 have been studied with a depopulation method. The spectral domain 615 - 700 nm is particularly interesting because it reveals a group of diffuse bands red-shifted and broadened with respect to the transition a 3 F → z 3 F in the metal. This transition is forbidden from the ground state a 3 F 2 of zirconium but allowed from the a 3 F 4 state. Complexation of the metal atom with a CH 3 F molecule allows coupling of these two states to occur which ensures the optical transition from the ground state of the complex. (author)

  20. Study of photo-activated electron transfer reactions in the first excited singlet state by picosecond and nanosecond laser spectroscopy

    International Nuclear Information System (INIS)

    Doizi, Denis

    1983-01-01

    Picosecond laser spectroscopy has been used to study two photo-activated electron transfer reactions: - a bimolecular electron transfer reaction between a sensitizer, DODCI, and an electron acceptor, methylviologen. The two radical ions created with an electron transfer efficiency γ ≅ 0.07 have been identified in picosecond and nanosecond laser absorption spectroscopy by adding selective solutes such as para-benzoquinone (an electron acceptor) or L(+) ascorbic acid (an electron donor). - an intramolecular electron transfer reaction in a triad molecule consisting of a tetra-aryl-porphyrin covalently linked to both a carotenoid and a quinone. The photoinduced charge separation occurs within 30 ps and leads, with a yield of 25 pc, to the formation of a zwitterion whose half-life is 2.5 μs. The experimental results obtained in these two studies show an effective decrease in the recombination rate of the two radical ions created in the encounter pair. (author) [fr

  1. Reaction pathways of photoexcited retinal in proteorhodopsin studied by pump-dump-probe spectroscopy.

    Science.gov (United States)

    Rupenyan, Alisa; van Stokkum, Ivo H M; Arents, Jos C; van Grondelle, Rienk; Hellingwerf, Klaas J; Groot, Marie Louise

    2009-12-17

    Proteorhodopsin (pR) is a membrane-embedded proton pump from the microbial rhodopsin family. Light absorption by its retinal chromophore initiates a photocycle, driven by trans/cis isomerization on the femtosecond to picosecond time scales. Here, we report a study on the photoisomerization dynamics of the retinal chromophore of pR, using dispersed ultrafast pump-dump-probe spectroscopy. The application of a pump pulse initiates the photocycle, and with an appropriately tuned dump pulse applied at a time delay after the dump, the molecules in the initial stages of the photochemical process can be de-excited and driven back to the ground state. In this way, we were able to resolve an intermediate on the electronic ground state that represents chromophores that are unsuccessful in isomerization. In particular, the fractions of molecules that undergo slow isomerization (20 ps) have a high probability to enter this state rather than the isomerized K-state. On the ground state reaction surface, return to the stable ground state conformation via a structural or vibrational relaxation occurs in 2-3 ps. Inclusion of this intermediate in the kinetic scheme led to more consistent spectra of the retinal-excited state, and to a more accurate estimation of the quantum yield of isomerization (Phi = 0.4 at pH 6).

  2. Microscopy and Cathodoluminescence Spectroscopy Characterization of Quartz Exhibiting Different Alkali-Silica Reaction Potential.

    Science.gov (United States)

    Kuchařová, Aneta; Götze, Jens; Šachlová, Šárka; Pertold, Zdeněk; Přikryl, Richard

    2016-02-01

    Different quartz types from several localities in the Czech Republic and Sweden were examined by polarizing microscopy combined with cathodoluminescence (CL) microscopy, spectroscopy, and petrographic image analysis, and tested by use of an accelerated mortar bar test (following ASTM C1260). The highest alkali-silica reaction potential was indicated by very fine-grained chert, containing significant amounts of fine-grained to cryptocrystalline matrix. The chert exhibited a dark red CL emission band at ~640 nm with a low intensity. Fine-grained orthoquartzites, as well as fine-grained metamorphic vein quartz, separated from phyllite exhibited medium expansion values. The orthoquartzites showed various CL of quartz grains, from blue through violet, red, and brown. Two CL spectral bands at ~450 and ~630 nm, with various intensities, were detected. The quartz from phyllite displayed an inhomogeneous dark red CL with two CL spectral bands of low intensities at ~460 and ~640 nm. The massive coarse-grained pegmatite quartz from pegmatite was assessed to be nonreactive and displayed a typical short-lived blue CL (~480 nm). The higher reactivity of the fine-grained hydrothermal quartz may be connected with high concentrations of defect centers, and probably with amorphized micro-regions in the quartz, respectively; indicated by a yellow CL emission (~570 nm).

  3. Methyl Radicals in Oxidative Coupling of Methane Directly Confirmed by Synchrotron VUV Photoionization Mass Spectroscopy

    Science.gov (United States)

    Luo, Liangfeng; Tang, Xiaofeng; Wang, Wendong; Wang, Yu; Sun, Shaobo; Qi, Fei; Huang, Weixin

    2013-01-01

    Gas-phase methyl radicals have been long proposed as the key intermediate in catalytic oxidative coupling of methane, but the direct experimental evidence still lacks. Here, employing synchrotron VUV photoionization mass spectroscopy, we have directly observed the formation of gas-phase methyl radicals during oxidative coupling of methane catalyzed by Li/MgO catalysts. The concentration of gas-phase methyl radicals correlates well with the yield of ethylene and ethane products. These results lead to an enhanced fundamental understanding of oxidative coupling of methane that will facilitate the exploration of new catalysts with improved performance. PMID:23567985

  4. Shedding Light on the Oxygen Reduction Reaction Mechanism in Ether-Based Electrolyte Solutions: A Study Using Operando UV-Vis Spectroscopy.

    Science.gov (United States)

    Hirshberg, Daniel; Sharon, Daniel; Afri, Michal; Lavi, Ronit; Frimer, Aryeh A; Metoki, Noa; Eliaz, Noam; Kwak, Won-Jin; Sun, Yang-Kook; Aurbach, Doron

    2018-04-04

    Using UV-vis spectroscopy in conjunction with various electrochemical techniques, we have developed a new effective operando methodology for investigating the oxygen reduction reactions (ORRs) and their mechanisms in nonaqueous solutions. We can follow the in situ formation and presence of superoxide moieties during ORR as a function of solvent, cations, anions, and additives in the solution. Thus, using operando UV-vis spectroscopy, we found evidence for the formation of superoxide radical anions during oxygen reduction in LiTFSI/diglyme electrolyte solutions. Nitro blue tetrazolium (NBT) was used to indicate the presence of superoxide moieties based on its unique spectral response. Indeed, the spectral response of NBT containing solutions undergoing ORR could provide a direct indication for the level of association of the Li cations with the electrolyte anions.

  5. Stabilization of silver nanoparticles in nonanoic acid: A temperature activated conformation reaction observed with surface enhanced Raman spectroscopy

    International Nuclear Information System (INIS)

    Henneke, Dale E.; Malyavanatham, Gokul; Kovar, Desiderio; O'Brien, D.T.; Becker, M.F.; Nichols, William T.; Keto, J.W.

    2003-01-01

    Silver nanoparticles were synthesized by ultraviolet (λ=248 nm) laser ablation of an aerosol of micron-sized source particles entrained in nitrogen. As a result of thermionic electron emission and photoionization, nanoparticles produced in this manner were highly charged. The resulting aerosol was primarily composed of nanometer sized particles. The charged nanoparticles were deflected by an electric field that was perpendicular to the aerosol flow. Deflected nanoparticles were deposited directly into n-nonanoic acid flowing along the negative collection electrode. Suspensions of nanoparticles collected in this manner were dark gray in color and were found to be flocculated. When the suspensions were heated to temperatures above 75 deg. C, a color change from gray to clear was observed. Ultraviolet/visible extinction spectroscopy was performed on each suspension following annealing at different temperatures and times. By modeling the absorption decrease as a first order reaction, a good fit for the data was found. Analysis by dynamic light scattering (DLS) showed that the initial mean flocculent size of the gray suspensions was 602 nm. DLS analysis of the suspensions taken at different annealing intervals showed that the flocculent size decreased, but maintained a narrow size distribution until the size shrank below the instrument resolution limit. The reduction in flocculent size coincided with the observed color change, and an irreversible transition to a deflocculated primary nanoparticle suspension is observed. Surface enhanced Raman scattering is used to confirm that the reaction results from a change in the orientation of the nonanoic molecule on the surface of the nanoparticle

  6. The Trojan Horse method for nuclear astrophysics: Recent results for direct reactions

    International Nuclear Information System (INIS)

    Tumino, A.; Gulino, M.; Spitaleri, C.; Cherubini, S.; Romano, S.; Cognata, M. La; Pizzone, R. G.; Rapisarda, G. G.; Lamia, L.

    2014-01-01

    The Trojan Horse method is a powerful indirect technique to determine the astrophysical factor for binary rearrangement processes A+x→b+B at astrophysical energies by measuring the cross section for the Trojan Horse (TH) reaction A+a→B+b+s in quasi free kinematics. The Trojan Horse Method has been successfully applied to many reactions of astrophysical interest, both direct and resonant. In this paper, we will focus on direct sub-processes. The theory of the THM for direct binary reactions will be shortly presented based on a few-body approach that takes into account the off-energy-shell effects and initial and final state interactions. Examples of recent results will be presented to demonstrate how THM works experimentally

  7. The Trojan Horse method for nuclear astrophysics: Recent results for direct reactions

    Energy Technology Data Exchange (ETDEWEB)

    Tumino, A.; Gulino, M. [Laboratori Nazionali del Sud, Istituto Nazionale di Fisica Nucleare, Catania, Italy and Università degli Studi di Enna Kore, Enna (Italy); Spitaleri, C.; Cherubini, S.; Romano, S. [Laboratori Nazionali del Sud, Istituto Nazionale di Fisica Nucleare, Catania, Italy and Dipartimento di Fisica e Astronomia, Università di Catania, Catania (Italy); Cognata, M. La; Pizzone, R. G.; Rapisarda, G. G. [Laboratori Nazionali del Sud, Istituto Nazionale di Fisica Nucleare, Catania (Italy); Lamia, L. [Dipartimento di Fisica e Astronomia, Università di Catania, Catania (Italy)

    2014-05-09

    The Trojan Horse method is a powerful indirect technique to determine the astrophysical factor for binary rearrangement processes A+x→b+B at astrophysical energies by measuring the cross section for the Trojan Horse (TH) reaction A+a→B+b+s in quasi free kinematics. The Trojan Horse Method has been successfully applied to many reactions of astrophysical interest, both direct and resonant. In this paper, we will focus on direct sub-processes. The theory of the THM for direct binary reactions will be shortly presented based on a few-body approach that takes into account the off-energy-shell effects and initial and final state interactions. Examples of recent results will be presented to demonstrate how THM works experimentally.

  8. Models of direct reactions and quantum pre-equilibrium for nucleon scattering on spherical nuclei

    International Nuclear Information System (INIS)

    Dupuis, M.

    2006-01-01

    When a nucleon collides with a target nucleus, several reactions may occur: elastic and inelastic scatterings, charge exchange... In order to describe these reactions, different models are involved: the direct reactions, pre-equilibrium and compound nucleus models. Our goal is to study, within a quantum framework and without any adjustable parameter, the direct and pre-equilibrium reactions for nucleons scatterings off double closed-shell nuclei. We first consider direct reactions: we are studying nucleon scattering with the Melbourne G-matrix, which represents the interaction between the projectile and one target nucleon, and with random phase approximation (RPA) wave functions which describe all target states. This is a fully microscopic approach since no adjustable parameters are involved. A second part is dedicated to the study of nucleon inelastic scattering for large energy transfer which necessarily involves the pre-equilibrium mechanism. Several models have been developed in the past to deal with pre-equilibrium. They start from the Born expansion of the transition amplitude which is associated to the inelastic process and they use several approximations which have not yet been tested. We have achieved some comparisons between second order cross sections which have been calculated with and without these approximations. Our results allow us to criticize some of these approximations and give several directions to improve the quantum pre-equilibrium models. (author)

  9. Rapid, Time-Division Multiplexed, Direct Absorption- and Wavelength Modulation-Spectroscopy

    Directory of Open Access Journals (Sweden)

    Alexander Klein

    2014-11-01

    Full Text Available We present a tunable diode laser spectrometer with a novel, rapid time multiplexed direct absorption- and wavelength modulation-spectroscopy operation mode. The new technique allows enhancing the precision and dynamic range of a tunable diode laser absorption spectrometer without sacrificing accuracy. The spectroscopic technique combines the benefits of absolute concentration measurements using calibration-free direct tunable diode laser absorption spectroscopy (dTDLAS with the enhanced noise rejection of wavelength modulation spectroscopy (WMS. In this work we demonstrate for the first time a 125 Hz time division multiplexed (TDM-dTDLAS-WMS spectroscopic scheme by alternating the modulation of a DFB-laser between a triangle-ramp (dTDLAS and an additional 20 kHz sinusoidal modulation (WMS. The absolute concentration measurement via the dTDLAS-technique allows one to simultaneously calibrate the normalized 2f/1f-signal of the WMS-technique. A dTDLAS/WMS-spectrometer at 1.37 µm for H2O detection was built for experimental validation of the multiplexing scheme over a concentration range from 50 to 3000 ppmV (0.1 MPa, 293 K. A precision of 190 ppbV was achieved with an absorption length of 12.7 cm and an averaging time of two seconds. Our results show a five-fold improvement in precision over the entire concentration range and a significantly decreased averaging time of the spectrometer.

  10. Low-dose electron energy-loss spectroscopy using electron counting direct detectors.

    Science.gov (United States)

    Maigné, Alan; Wolf, Matthias

    2018-03-01

    Since the development of parallel electron energy loss spectroscopy (EELS), charge-coupled devices (CCDs) have been the default detectors for EELS. With the recent development of electron-counting direct-detection cameras, micrographs can be acquired under very low electron doses at significantly improved signal-to-noise ratio. In spectroscopy, in particular in combination with a monochromator, the signal can be extremely weak and the detection limit is principally defined by noise introduced by the detector. Here we report the use of an electron-counting direct-detection camera for EEL spectroscopy. We studied the oxygen K edge of amorphous ice and obtained a signal noise ratio up to 10 times higher than with a conventional CCD.We report the application of electron counting to record time-resolved EEL spectra of a biological protein embedded in amorphous ice, revealing chemical changes observed in situ while exposed by the electron beam. A change in the fine structure of nitrogen K and the carbon K edges were recorded during irradiation. A concentration of 3 at% nitrogen was detected with a total electron dose of only 1.7 e-/Å2, extending the boundaries of EELS signal detection at low electron doses.

  11. Ramsey spectroscopy by direct use of resonant light on isotope atoms for single-photon detuning

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Hoon; Choi, Mi Hyun; Moon, Ye Lin; Kim, Seung Jin; Kim, Jung Bog [Korea National University of Education, Cheongwon (Korea, Republic of)

    2014-03-15

    We demonstrate Ramsey spectroscopy with cold {sup 87}Rb atoms via a two-photon Raman process. One laser beam has a cross-over resonant frequency on the {sup 85}Rb transition and the other beam has a 6.8 GHz shifted frequency. These two laser beams fulfill the two-photon Raman resonance condition, which involves a single-photon detuning of -2.6 GHz. By implementing these two lasers on cold {sup 87}Rb atoms, we demonstrate Ramsey spectroscopy with an interrogation time of the intermediate state by using π/2 Raman pulses. In our laser system, we can change the single-photon detuning to 1.2, 4.2 or -5.6 GHz by changing the {sup 85}Rb transition line used as a locking signal and an injected sideband. The laser system that directly uses resonant light on isotope atoms will be described in this paper.

  12. Solvent dependence of organic exciplex fluorescence studied by magnetic effect on reaction yield (M.A.R.Y) spectroscopy

    International Nuclear Information System (INIS)

    Pal, K.

    2011-01-01

    This work aims at understanding the various facets of one of the elementary reactions in nature, the electron transfer reaction using MARY (Magnetic effect on Reaction Yield) spectroscopy as a tool. The prime focus of study by the use this technique was the solvent dependence of organic exciplex fluorescence. Apart from that temperature dependent measurements using MARY spectroscopy have been performed to extract the activation energy parameters of electron transfer reaction. The discovery of magnetic field effect on new system was also a part of our study. The study of solvent dependence of organic exciplex fluorescence using MARY spectroscopy was carried out on the system of 9,10-dimethylanthracene (as the fluorophore) and N,N'-dimethylaniline and 4,4'-Bis(dimethylamino) diphenylmethane (as quenchers) in binary solvent mixtures of toluene/dimethylsulfoxide, benzylacetate/dimethylsulfoxide, toluene/propylenecarbonate and propylacetate/butyronitrile. The work focuses on the use of solvent mixtures rather than pure solvents. The solvent mixtures, tailored to simulate different microenvironemets, were employed to find out the effect of preferential solvation on electron transfer reaction. The contrast in the absolute field effect and linewidth values of the MARY spectra obtained in the four system as a function of dielectric constant scan suggest the imperative effect of concentration fluctuation on the electron transfer reaction. Temperature dependent measurements were performed on the system of N,N,N',N'- tetramethylparaphenylendiamin, photo-ionizing in a mixture of toluene/dimethylsulfoxide. However the sluggish response of the system to temperature changes does not really permit us to extract fruitful results. The magnetic field effect on the much studied system of Perylene/ N.N'-dimethylaniline was discovered for the first time. (author) [de

  13. Spectroscopy

    DEFF Research Database (Denmark)

    Berg, Rolf W.

    This introductory booklet covers the basics of molecular spectroscopy, infrared and Raman methods, instrumental considerations, symmetry analysis of molecules, group theory and selection rules, as well as assignments of fundamental vibrational modes in molecules.......This introductory booklet covers the basics of molecular spectroscopy, infrared and Raman methods, instrumental considerations, symmetry analysis of molecules, group theory and selection rules, as well as assignments of fundamental vibrational modes in molecules....

  14. A reaction cell with sample laser heating for in situ soft X-ray absorption spectroscopy studies under environmental conditions.

    Science.gov (United States)

    Escudero, Carlos; Jiang, Peng; Pach, Elzbieta; Borondics, Ferenc; West, Mark W; Tuxen, Anders; Chintapalli, Mahati; Carenco, Sophie; Guo, Jinghua; Salmeron, Miquel

    2013-05-01

    A miniature (1 ml volume) reaction cell with transparent X-ray windows and laser heating of the sample has been designed to conduct X-ray absorption spectroscopy studies of materials in the presence of gases at atmospheric pressures. Heating by laser solves the problems associated with the presence of reactive gases interacting with hot filaments used in resistive heating methods. It also facilitates collection of a small total electron yield signal by eliminating interference with heating current leakage and ground loops. The excellent operation of the cell is demonstrated with examples of CO and H2 Fischer-Tropsch reactions on Co nanoparticles.

  15. Use of deuterium n. m. r. spectroscopy in mechanistic studies of exchange reactions of ethers on supported metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, J.A.; Kemball, Charles; McDougall, G.S.

    1987-10-01

    Exchange reactions of diethyl ether (DEE) and tetrahydrofuran (THF) with deuterium have been studied over supported nickel, palladium, platinum, and rhodium catalysts. Products from most of the systems were analysed by deuterium n.m.r. spectroscopy (55.28 MHz) which gave quantitative results about the distribution of deuterium in the exchanged ethers. The results confirm earlier conclusions about the mechanism of the exchange of DEE and provide new evidence about the reactions of THF. Some hydrogenolysis occurred simultaneously with exchange of THF over both nickel and platinum.

  16. Expanding the enzyme universe: accessing non-natural reactions by mechanism-guided directed evolution.

    Science.gov (United States)

    Renata, Hans; Wang, Z Jane; Arnold, Frances H

    2015-03-09

    High selectivity and exquisite control over the outcome of reactions entice chemists to use biocatalysts in organic synthesis. However, many useful reactions are not accessible because they are not in nature's known repertoire. In this Review, we outline an evolutionary approach to engineering enzymes to catalyze reactions not found in nature. We begin with examples of how nature has discovered new catalytic functions and how such evolutionary progression has been recapitulated in the laboratory starting from extant enzymes. We then examine non-native enzyme activities that have been exploited for chemical synthesis, with an emphasis on reactions that do not have natural counterparts. Non-natural activities can be improved by directed evolution, thus mimicking the process used by nature to create new catalysts. Finally, we describe the discovery of non-native catalytic functions that may provide future opportunities for the expansion of the enzyme universe. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Expanding the Enzyme Universe: Accessing Non-Natural Reactions by Mechanism-Guided Directed Evolution

    Science.gov (United States)

    Renata, Hans; Wang, Z. Jane

    2015-01-01

    High selectivities and exquisite control over reaction outcomes entice chemists to use biocatalysts in organic synthesis. However, many useful reactions are not accessible because they are not in nature’s known repertoire. We will use this review to outline an evolutionary approach to engineering enzymes to catalyze reactions not found in nature. We begin with examples of how nature has discovered new catalytic functions and how such evolutionary progressions have been recapitulated in the laboratory starting from extant enzymes. We then examine non-native enzyme activities that have been discovered and exploited for chemical synthesis, emphasizing reactions that do not have natural counterparts. The new functions have mechanistic parallels to the native reaction mechanisms that often manifest as catalytic promiscuity and the ability to convert from one function to the other with minimal mutation. We present examples of how non-natural activities have been improved by directed evolution, mimicking the process used by nature to create new catalysts. Examples of new enzyme functions include epoxide opening reactions with non-natural nucleophiles catalyzed by a laboratory-evolved halohydrin dehalogenase, cyclopropanation and other carbene transfer reactions catalyzed by cytochrome P450 variants, and non-natural modes of cyclization by a modified terpene synthase. Lastly, we describe discoveries of non-native catalytic functions that may provide future opportunities for expanding the enzyme universe. PMID:25649694

  18. Direct Estimate of Cocoa Powder Content in Cakes by Colorimetry and Photoacoustic Spectroscopy

    Science.gov (United States)

    Dóka, O.; Bicanic, D.; Kulcsár, R.

    2014-12-01

    Cocoa is a very important ingredient in the food industry and largely consumed worldwide. In this investigation, colorimetry and photoacoustic spectroscopy were used to directly assess the content of cocoa powder in cakes; both methods provided satisfactory results. The calibration curve was constructed using a series of home-made cakes containing varying amount of cocoa powder. Then, at a later stage, the same calibration curve was used to quantify the cocoa content of several commercially available cakes. For self-made cakes, the relationship between the PAS signal and the content of cocoa powder was linear while a quadratic dependence was obtained for the colorimetric index (brightness) and total color difference ().

  19. Direct measurements of neutral density depletion by two-photon absorption laser-induced fluorescence spectroscopy

    International Nuclear Information System (INIS)

    Aanesland, A.; Liard, L.; Leray, G.; Jolly, J.; Chabert, P.

    2007-01-01

    The ground state density of xenon atoms has been measured by spatially resolved laser-induced fluorescence spectroscopy with two-photon excitation in the diffusion chamber of a magnetized Helicon plasma. This technique allows the authors to directly measure the relative variations of the xenon atom density without any assumptions. A significant neutral gas density depletion was measured in the core of the magnetized plasma, in agreement with previous theoretical and experimental works. It was also found that the neutral gas density was depleted near the radial walls

  20. Application of Raman spectroscopy for direct analysis of Carlina acanthifolia subsp. utzka root essential oil.

    Science.gov (United States)

    Strzemski, Maciej; Wójciak-Kosior, Magdalena; Sowa, Ireneusz; Agacka-Mołdoch, Monika; Drączkowski, Piotr; Matosiuk, Dariusz; Kurach, Łukasz; Kocjan, Ryszard; Dresler, Sławomir

    2017-11-01

    Carlina genus plants e.g. Carlina acanthifolia subsp. utzka have been still used in folk medicine of many European countries and its biological activity is mostly associated with root essential oils. In the present paper, Raman spectroscopy (RS) was applied for the first time for evaluation of essential oil distribution in root of C. acnthifolia subsp. utzka and identification of root structures containing the essential oil. Furthermore, RS technique was applied to assess chemical stability of oil during drying of plant material or distillation process. Gas chromatography-mass spectrometry was used for qualitative and quantitative analysis of the essential oil. The identity of compounds was confirmed using Raman, ATR-IR and NMR spectroscopy. Carlina oxide was found to be the main component of the oil (98.96% ± 0.15). The spectroscopic study showed the high stability of essential oil and Raman distribution analysis indicated that the oil reservoirs were localized mostly in the structures of outer layer of the root while the inner part showed nearly no signal assigned to the oil. Raman spectroscopy technique enabled rapid, non-destructive direct analysis of plant material with minimal sample preparation and allowed straightforward, unambiguous identification of the essential oil in the sample. Copyright © 2017. Published by Elsevier B.V.

  1. High-pressure synthesis of rhombohedral α-AgGaO{sub 2} via direct solid state reaction

    Energy Technology Data Exchange (ETDEWEB)

    Akhtar, Meysam [Department of Physics and Astronomy, University of Louisville, 102 Natural Science Building, Louisville, KY 40292 (United States); Menon, Madhu [Center for Computational Sciences, University of Kentucky, 325 McVey Hall, Lexington, KY 40506 (United States); Sunkara, Mahendra [Conn Center for Renewable Energy Research, University of Louisville, Ernst Hall Room 102A, Louisville, KY 40292 (United States); Sumanasekera, Gamini [Department of Physics and Astronomy, University of Louisville, 102 Natural Science Building, Louisville, KY 40292 (United States); Conn Center for Renewable Energy Research, University of Louisville, Ernst Hall Room 102A, Louisville, KY 40292 (United States); Durygin, Andriy [Center for the Study of Matter at Extreme Conditions, Florida International University, VH 140, University Park, Miami, FL 33199 (United States); Jasinski, Jacek B., E-mail: jacek.jasinski@louisville.edu [Conn Center for Renewable Energy Research, University of Louisville, Ernst Hall Room 102A, Louisville, KY 40292 (United States)

    2015-08-25

    Highlights: • Direct synthesis of α-AgGaO{sub 2} via a solid state reaction of Ag{sub 2}O and Ga{sub 2}O{sub 3} powders. • Utilizing high pressure diamond anvil cell to facilitate solid state reaction. • Experimental and theoretical study of vibrational modes for α-AgGaO{sub 2}. • Extensive characterization of synthesized α-AgGaO{sub 2} samples. • GGA + U formalism-based DFT calculations of electronic structure and band gap in α-AgGaO{sub 2}. - Abstract: In this work, we demonstrate the application of high pressure conditions to enable the direct synthesis of α-AgGaO{sub 2} via a solid state reaction of Ag{sub 2}O and Ga{sub 2}O{sub 3}. Synthesis experiments were carried out at pressures and temperatures up to ∼10 GPa and ∼600 °C, respectively, using a resistively-heated diamond anvil cell. Thus synthesized α-AgGaO{sub 2} samples were characterized and their chemical composition and crystal structure were confirmed. In particular, electron diffraction confirmed the rhombohedral delafossite crystal structure of the synthesized AgGaO{sub 2} and its corresponding lattice parameters of a = 2.99 Å and c = 18.43 Å. The vibrational modes analysis was also conducted using a combination of ab initio density functional theory (DFT) and Raman spectroscopy. This analysis yielded good agreement between the calculated Raman-active modes and experimental Raman data. Finally, the application of the GGA + U formalism-based on DFT to calculate the electronic band structure of α-AgGaO{sub 2} provided a more realistic theoretical band gap value than those reported previously.

  2. Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction

    Energy Technology Data Exchange (ETDEWEB)

    Soorkia, Satchin; Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Trevitt, Adam J.; Wilson, Kevin R.; Leone, Stephen R.

    2010-03-16

    The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and the result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.

  3. Understanding the Oxygen Evolution Reaction Mechanism on CoOx using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

    International Nuclear Information System (INIS)

    Favaro, Marco; Yang, Jinhui; Nappini, Silvia; Magnano, Elena

    2017-01-01

    Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3 O 4 /Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that the catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3 O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3 O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.

  4. Photochemical Reactions of Particulate Organic Matter: Deciphering the Role of Direct and Indirect Processes

    Science.gov (United States)

    Carrasquillo, A. J.; Gelfond, C. E.; Kocar, B. D.

    2016-12-01

    Photochemical reactions of natural organic matter (NOM) represent potentially important pathways for biologically recalcitrant material to be chemically altered in aquatic systems. Irradiation can alter the physical state of organic matter by facilitating the cycling between the particulate (POM) and dissolved (DOM) pools, however, a molecular level understanding of this chemically dynamic system is currently lacking. Photochemical reactions of a target molecule proceed by the direct absorption of a photon, or through reaction with a second photolytically generated species (i.e. the hydroxyl radical, singlet oxygen, excited triplet state NOM, hydrogen peroxide, etc.). Here, we isolate the major direct and indirect photochemical reactions of a lignocellulose-rich POM material (Phragmites australis) to determine their relative importance in changing the the chemical structure of the parent POM, and in the production of DOM. We measured POM molecular structure using a combination of NMR and FTIR for bulk analyses and scanning transmission x-ray microscopy (STXM) for spatially resolved chemistry, while the chemical composition of photo-produced DOM was measured using ultra-high resolution mass spectrometry. Results are discussed in the context of the differences in chemical composition of both NOM pools resulting from the isolated photochemical pathways. All treatments result in an increase in DOM with reaction time, indicating that the larger POM matrix is likely fragmenting into smaller more soluble species. Spectroscopic measurements, on the other hand, point to functionalization reactions which increase the abundance of alcohol, acid, and carbonyl moieties in both carbon pools. This unique dataset provides new insight into how photochemical reactions alter the chemical composition of NOM while highlighting the relative importance of indirect pathways.

  5. Recent results on fusion and direct reactions with weakly bound stable nuclei

    International Nuclear Information System (INIS)

    Shrivastava, A.

    2011-01-01

    Recent measurements of fusion and direct reactions in case of weakly bound stable nuclei at extreme sub-barrier energies using a sensitive off beam technique are presented. First section deals with deep sub-barrier fusion cross-section measurement for 67 Li + 198 Pt followed by the study of fragment capture reaction of 7 Li + 198 Pt. Deviation in the slope of the fusion excitation function, as observed in case of medium heavy systems, is absent in the present asymmetric systems at these low energies. This study shows the absence of fusion hindrance, suggesting modifications in models that explain deep sub-barrier fusion data to incorporate weakly bound asymmetric systems

  6. PTOLEMY, a program for heavy-ion direction-reaction calculations

    International Nuclear Information System (INIS)

    Gloeckner, D.H.; Macfarlane, M.H.; Pieper, S.C.

    1976-03-01

    Ptolemy is an IBM/360 program for the computation of nuclear elastic and direct-reaction cross sections. It carries out both optical-model fits to elastic-scattering data at one or more energies, and DWBA calculations for nucleon-transfer reactions. Ptolemy has been specifically designed for heavy-ion calculations. It is fast and does not require large amounts of core. The input is exceptionally flexible and easy to use. This report outlines the types of calculation that Ptolemy can carry out, summarizes the formulas used, and gives a detailed description of its input

  7. Ptolemy: a program for heavy-ion direct-reaction calculations

    International Nuclear Information System (INIS)

    Macfarlane, M.H.; Pieper, S.C.

    1978-04-01

    Ptolemy is an IBM/360 program for the computation of nuclear elastic and direct-reaction cross sections. It carries out optical-model fits to elastic-scattering data at one or more energies and for one or more combinations of projectile and target, collective model DWBA calculations of excitation processes, and finite-range DWBA calculations of nucleon-transfer reactions. It is fast and does not require large amounts of core. The input is exceptionally flexible and easy to use. The types of calculations that Ptolemy can carry out are outlined, the formulas used are summarized, and a detailed description of its input is given

  8. Wide temperature range (T = 295 K and 770-1305 K) study of the kinetics of the reactions HCO + NO and HCO + NO2 using frequency modulation spectroscopy.

    Science.gov (United States)

    Dammeier, J; Colberg, M; Friedrichs, G

    2007-08-21

    The rate constants for , HCO + NO --> HNO + CO, and , HCO + NO(2)--> products, have been measured at temperatures between 770 K modulation (FM) absorption spectroscopy. Kinetic simulations based on a comprehensive reaction mechanism showed that the rate constants for the title reactions could be sensitively extracted from the measured HCO profiles. The determined high temperature rate constants are k(1)(769-1307 K) = (7.1 +/- 2.7) x 10(12) cm(3) mol(-1) s(-1) and k(2)(804-1186 K) = (3.3 +/- 1.8) x 10(13) cm(3) mol(-1) s(-1). The room temperature values were found to be in very good agreement with existing literature data and show that both reactions are essentially temperature independent. The weak temperature dependence of can be explained by the interplay of a dominating direct abstraction pathway and a complex-forming mechanism. Both pathways yield the products HNO + CO. In contrast to , no evidence for a significant contribution of a direct high temperature abstraction channel was found for . Here, the observed temperature independent overall rate constant can be described by a complex-forming mechanism with several product channels. Detailed information on the strongly temperature dependent channel branching ratios is provided. Moreover, the high temperature rate constant of , OH + (CHO)(2), has been determined to be k(7) approximately 1.1 x 10(13) cm(3) mol(-1) s(-1).

  9. Two-pulse atomic coherent control spectroscopy of Eley-Rideal reactions: An application of an atom laser

    International Nuclear Information System (INIS)

    Joergensen, Solvejg; Kosloff, Ronnie

    2003-01-01

    A spectroscopic application of the atom laser is suggested. The spectroscopy termed 2PACC (two-pulse atomic coherent control) employs the coherent properties of matter waves from a two-pulse atom laser. These waves are employed to control a gas-surface chemical recombination reaction. The method is demonstrated for an Eley-Rideal reaction of a hydrogen or alkali atom-laser pulse where the surface target is an adsorbed hydrogen atom. The reaction yields either a hydrogen or alkali hydride molecule. The desorbed gas-phase molecular yield and its internal state is shown to be controlled by the time and phase delay between two atom-laser pulses. The calculation is based on solving the time-dependent Schroedinger equation in a diabatic framework. The probability of desorption which is the predicted 2PACC signal has been calculated as a function of the pulse parameters

  10. spectroscopy

    African Journals Online (AJOL)

    Aghomotsegin

    2015-10-14

    Oct 14, 2015 ... characterized by using phenotypic, API and Fourier transform infrared (FTIR) spectroscopy methods. One hundred and fifty-seven (157) strains were isolated from 13 cheese samples, and identification test was performed for 83 strains. At the end of the study, a total of 22 Lactococcus sp., 36 Enterecoccus ...

  11. Parental reactions to parent- and sibling-directed aggression within a domestic violence context.

    Science.gov (United States)

    Desir, Michelle P; Karatekin, Canan

    2018-02-01

    Parent- and sibling-directed aggression by minor children are two forms of family violence that often co-occur and have strong relations to prior exposure to domestic violence, yet are often overlooked in intervention efforts. In addition, current research does not examine these forms of family violence in tandem, and there is very limited research with samples exposed to domestic violence. To better understand how these forms of aggression operate within a domestic violence context, we interviewed 44 women residing in a domestic violence shelter with at least one child over 3.5 years of age who was aggressive toward them and/or siblings. Caregivers reported on their emotional reactions to children's parent-directed aggression and the types of and effectiveness of help they sought for parent- and/or sibling-directed aggression. In line with previous literature, caregivers endorsed a complex mix of emotional reactions to their children's parent-directed aggression, including anger, sadness, guilt, forgiveness, and worthlessness. In contrast to other studies, most caregivers (89%) had sought help for children's parent- and/or sibling-directed aggression and found it effective. Findings contribute to the literature on parent- and sibling-directed aggression and provide implications for how to effectively intervene.

  12. Covalent Reactions on Chemical Vapor Deposition Grown Graphene Studied by Surface-Enhanced Raman Spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Kovaříček, Petr; Bastl, Zdeněk; Valeš, Václav; Kalbáč, Martin

    2016-01-01

    Roč. 22, č. 15 (2016), s. 5404-5408 ISSN 1521-3765 R&D Projects: GA MŠk LL1301 Institutional support: RVO:61388955 Keywords : graphene * nanomaterials * Raman spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry

  13. L1{sub 0} phase transition in FePt thin films via direct interface reaction

    Energy Technology Data Exchange (ETDEWEB)

    Li Xiaohong; Sun Hongyu; Wang Fengqing; Li Wei; Zhang Xiangyi [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, 066004 Qinhuangdao (China); Liu Baoting; Guo Jianxin [College of Physics Science and Technology, Hebei University, 071002 Baoding (China)], E-mail: xyzh66@ysu.edu.cn

    2008-12-07

    Lowering the L1{sub 0} ordering temperature of FePt films is of great significance for their application as an ultrahigh density magnetic recording medium. In this study, the L1{sub 0} ordering process of FePt thin films deposited directly on Si substrates has been significantly accelerated by the interface reaction between the thin film and the Si substrate, and thus the thin films show a low L1{sub 0} ordering temperature of T = 310 deg. C as compared with those deposited on Si/SiO{sub 2} substrates. The accelerated L1{sub 0} ordering transition is predominantly dependent on the rapid growth of the ordered domains during the interface reaction. The film thickness has an important effect on the interface reaction and thus can be used to tune the L1{sub 0} ordering process of the FePt films.

  14. L10 phase transition in FePt thin films via direct interface reaction

    International Nuclear Information System (INIS)

    Li Xiaohong; Sun Hongyu; Wang Fengqing; Li Wei; Zhang Xiangyi; Liu Baoting; Guo Jianxin

    2008-01-01

    Lowering the L1 0 ordering temperature of FePt films is of great significance for their application as an ultrahigh density magnetic recording medium. In this study, the L1 0 ordering process of FePt thin films deposited directly on Si substrates has been significantly accelerated by the interface reaction between the thin film and the Si substrate, and thus the thin films show a low L1 0 ordering temperature of T = 310 deg. C as compared with those deposited on Si/SiO 2 substrates. The accelerated L1 0 ordering transition is predominantly dependent on the rapid growth of the ordered domains during the interface reaction. The film thickness has an important effect on the interface reaction and thus can be used to tune the L1 0 ordering process of the FePt films.

  15. Electrical and Dielectric Properties of Polyaniline and Polyaniline/Montmorillonite Nanocomposite Prepared by Solid Reaction Using Spectroscopy Impedance

    Directory of Open Access Journals (Sweden)

    Imene Bekri-Abbes

    2015-01-01

    Full Text Available The combination of two components with uniform distribution in nanoscale is expected to facilitate wider applications of the material. In this study, polyaniline (PAn and polyaniline/montmorillonite (Mt nanocomposite were prepared by solid reaction using persulfate of ammonium as oxidant. The phase composition and morphology of the nanocomposite were characterized by FTIR, UV-visible spectroscopy, X-ray diffractometer, thermal gravimetric analysis, and scanning electron microscopy. The electrical and dielectric properties were determined using spectroscopy impedance. The analysis of UV-visible and FTIR spectroscopy demonstrated that aniline chloride has been polymerized into PAn in its conducting emeraldine form. Thermogravimetric analysis suggested that PAn chains intercalated in the clay host are more thermally stable than those of free PAn prepared by solid-solid reaction. Electrical measurements were carried out using the complex impedance technique in the frequency range of 10−2 to 104 Hz at different temperatures. The ac conductivity data of different nanocomposites were analyzed as a function of frequency and temperature. It has been found that the incorporation of inorganic clay phase into polyaniline matrix has an effect on the electrical and dielectric properties of the nanomaterial.

  16. The quantitative monitoring of mechanochemical reaction between solid L-tartaric acid and sodium carbonate monohydrate by terahertz spectroscopy

    Science.gov (United States)

    Liu, Xiaohong; Liu, Guifeng; Zhao, Hongwei; Zhang, Zengyang; Wei, Yongbo; Liu, Min; Wen, Wen; Zhou, Xingtai

    2011-11-01

    The solid-state reaction of chiral tartaric acid and alkali carbonate was studied by terahertz time-domain spectroscopy (THz-TDS). The sodium tartrate dihydrate was synthesized with high efficiency by mechanical grinding in the solid-state without waste that is particularly sustainable and environmentally benign. Distinct THz absorptions were observed for reactants and products. It indicates that THz spectroscopy is sensitive to different materials and crystal structures. The characteristic THz absorption peak at 1.09 THz of L (+)-Tartaric acid was selected for quantitative analysis. The reaction kinetics could be expressed by the Second-order equation and the Jander equation, which is consistent with a three-dimensional diffusion mechanism. The combination of multi-techniques including synchrotron radiation X-ray powder diffraction (SRXRPD), Fourier transform infrared (FT-IR) and scanning electron microscopy (SEM) was used to investigate the grinding process and presented supporting evidences. The results demonstrate that THz spectroscopy technique has great potential applications in process monitoring and analysis in pharmaceutical and chemical synthesis industry.

  17. Amine-catalyzed direct aldol reactions of hydroxy- and dihydroxyacetone: biomimetic synthesis of carbohydrates.

    Science.gov (United States)

    Popik, Oskar; Pasternak-Suder, Monika; Leśniak, Katarzyna; Jawiczuk, Magdalena; Górecki, Marcin; Frelek, Jadwiga; Mlynarski, Jacek

    2014-06-20

    This article presents comprehensive studies on the application of primary, secondary, and tertiary amines as efficient organocatalysts for the de novo synthesis of ketoses and deoxyketoses. Mimicking the actions of aldolase enzymes, the synthesis of selected carbohydrates was accomplished in aqueous media by using proline- and serine-based organocatalysts. The presented methodology also provides direct access to unnatural L-carbohydrates from the (S)-glyceraldehyde precursor. Determination of the absolute configuration of all obtained sugars was feasible using a methodology consisting of concerted ECD and VCD spectroscopy.

  18. Direct photon production in heavy-ion reactions at SPS and RHIC

    Indian Academy of Sciences (India)

    They are considerably below the heavy-ion results which indicates that a simple scaling of prompt photons as observed in pp is not sufficient to explain the direct photons in central. Pb+Pb reactions. It is also instructive to compare the γ/π0 ratio extracted from heavy-ion data to those from pp and pC in figure 3. The value in ...

  19. Hybrid direct carbon fuel cells and their reaction mechanisms - a review

    DEFF Research Database (Denmark)

    Deleebeeck, Lisa; Kammer Hansen, Kent

    2014-01-01

    with carbon capture and storage (CCS) due to the high purity of CO2 emitted in the exhaust gas. Direct carbon (or coal) fuel cells (DCFCs) are directly fed with solid carbon to the anode chamber. The fuel cell converts the carbon at the anode and the oxygen at the cathode into electricity, heat and reaction......As coal is expected to continue to dominate power generation demands worldwide, it is advisable to pursue the development of more efficient coal power generation technologies. Fuel cells show a much higher fuel utilization efficiency, emit fewer pollutants (NOx, SOx), and are more easily combined...

  20. The direct oxidative diene cyclization and related reactions in natural product synthesis

    Directory of Open Access Journals (Sweden)

    Juliane Adrian

    2016-09-01

    Full Text Available The direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (diastereoselective preparation of substituted tetrahydrofurans. Closely related reactions start from 5,6-dihydroxy or 5-hydroxyalkenes to generate similar products in a mechanistically analogous manner. After a brief overview on the history of this group of transformations and a survey on mechanistic and stereochemical aspects, this review article provides a summary on applications in natural product synthesis. Moreover, current limitations and future directions in this area of chemistry are discussed.

  1. Murai Reaction on Furfural Derivatives Enabled by Removable N,N'-Bidentate Directing Groups.

    Science.gov (United States)

    Pezzetta, Cristofer; Veiros, Luis F; Oble, Julie; Poli, Giovanni

    2017-06-22

    Furfural and related compounds are industrially relevant building blocks obtained from lignocellulosic biomass. To enhance the added value of these renewable resources, a Ru-catalyzed hydrofurylation of alkenes, involving a directed C-H activation at C3 of the furan ring, was developed. A thorough experimental study revealed that a bidentate amino-imine directing group enabled the desired coupling. Removal of the directing group occurred during the purification step, directly releasing the C3-functionalized furfurals. Development of the reaction as well as optimization and scope of the method were described. A mechanism was proposed on the basis of DFT calculations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Directional Track Selection Technique in CR39 SSNTD for lowyield reaction experiments

    Science.gov (United States)

    Ingenito, Francesco; Andreoli, Pierluigi; Batani, Dimitri; Bonasera, Aldo; Boutoux, Guillaume; Burgy, Frederic; Cipriani, Mattia; Consoli, Fabrizio; Cristofari, Giuseppe; De Angelis, Riccardo; Di Giorgio, Giorgio; Ducret, Jean Eric; Giulietti, Danilo; Jakubowska, Katarzyna

    2018-01-01

    There is a great interest in the study of p-11B aneutronic nuclear fusion reactions, both for energy production and for determination of fusion cross-sections at low energies. In this context we performed experiments at CELIA in which energetic protons, accelerated by the laser ECLIPSE, were directed toward a solid Boron target. Because of the small cross-sections at these energies the number of expected reactions is low. CR39 Solid-State Nuclear Track Detectors (SSNTD) were used to detect the alpha particles produced. Because of the low expected yield, it is difficult to discriminate the tracks due to true fusion products from those due to natural background in the CR39. To this purpose we developed a methodology of particle recognition according to their direction with respect to the detector normal, able to determine the position of their source. We applied this to the specific experiment geometry, so to select from all the tracks those due to particles coming from the region of interaction between accelerated protons and solid boron target. This technique can be of great help on the analysis of SSNTD in experiments with low yield reactions, but can be also generally applied to any experiment where particles reach the track detector with known directions, and for example to improve the detection limit of particle spectrometers using CR39.

  3. Comparison of TiO2 photocatalysis, electrochemically assisted Fenton reaction and direct electrochemistry for simulation of phase I metabolism reactions of drugs

    NARCIS (Netherlands)

    Ruokolainen, Miina; Gül, Turan; Permentier, Hjalmar; Sikanen, Tiina; Kostiainen, Risto; Kotiaho, Tapio

    2016-01-01

    The feasibility of titanium dioxide (TiO2) photocatalysis, electrochemically assisted Fenton reaction (EC-Fenton) and direct electrochemical oxidation (EC) for simulation of phase I metabolism of drugs was studied by comparing the reaction products of buspirone, promazine, testosterone and

  4. Kinetics of the reaction F+NO+M->FNO+M studied by pulse radiolysis combined with time-resolved IR and UV spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, Palle Bjørn; Sillesen, A.; Jodkowski, J.T.

    1996-01-01

    The title reaction was initiated by pulse radiolysis of SF6/NO gas mixtures, and the formation of FNO was studied by time-resolved IR and UV spectroscopy. At SF6 pressures of 10-320 mbar at 298 K, the formation of FNO was studied by infrared diode laser spectroscopy at 1857.324 cm(-1). Comparative...

  5. Direct Detection Electron Energy-Loss Spectroscopy: A Method to Push the Limits of Resolution and Sensitivity.

    Science.gov (United States)

    Hart, James L; Lang, Andrew C; Leff, Asher C; Longo, Paolo; Trevor, Colin; Twesten, Ray D; Taheri, Mitra L

    2017-08-15

    In many cases, electron counting with direct detection sensors offers improved resolution, lower noise, and higher pixel density compared to conventional, indirect detection sensors for electron microscopy applications. Direct detection technology has previously been utilized, with great success, for imaging and diffraction, but potential advantages for spectroscopy remain unexplored. Here we compare the performance of a direct detection sensor operated in counting mode and an indirect detection sensor (scintillator/fiber-optic/CCD) for electron energy-loss spectroscopy. Clear improvements in measured detective quantum efficiency and combined energy resolution/energy field-of-view are offered by counting mode direct detection, showing promise for efficient spectrum imaging, low-dose mapping of beam-sensitive specimens, trace element analysis, and time-resolved spectroscopy. Despite the limited counting rate imposed by the readout electronics, we show that both core-loss and low-loss spectral acquisition are practical. These developments will benefit biologists, chemists, physicists, and materials scientists alike.

  6. Nuclear structure of weakly bound radioactive nuclei through elastic and and inelastic scattering on proton. Impacts of the couplings induced by these exotic nuclei on direct reactions

    International Nuclear Information System (INIS)

    Lapoux, V.

    2005-09-01

    Information on the structure, spectroscopy and target interaction potentials of exotic nuclei can be inferred by interpreting measured data from direct reactions on proton such as elastic or inelastic scattering of proton (p,p') or one-nucleon transfer reaction (p,d). A series of experimental results has been obtained at the GANIL facilities on the setting composed of the MUST telescope array used for the detection of light charged-particles and of CATS beam detectors. This setting aims at measuring reactions on light proton or deuteron targets through reverse kinematics. Particularly, results on C 10 , C 11 and on direct reactions with the He 8 beam of Spiral are presented. The first chapter is dedicated to the description of the most important theories concerning the nucleus. The experimental tools used to probe the nucleus are reported in the second chapter. The third and fourth chapters present the framework that has allowed us to analyse results from (p,p') and (p,d) reactions on weakly bound exotic nuclei. The last chapter is dedicated to the description of future experimental programs. (A.C.)

  7. Direct observation of superconducting gaps in MgB 2 by angle-resolved photoemission spectroscopy

    Science.gov (United States)

    Souma, S.; Machida, Y.; Sato, T.; Takahashi, T.; Matsui, H.; Wang, S.-C.; Ding, H.; Kaminski, A.; Campuzano, J. C.; Sasaki, S.; Kadowaki, K.

    2004-08-01

    High-resolution angle-resolved photoemission spectroscopy has been carried out to clarify the anomalous superconductivity of MgB 2. We observed three bands crossing the Fermi level, which are ascribed to B2p-σ, π and surface bands. We have succeeded for the first time in directly observing the superconducting gaps of these bands separately. We have found that the superconducting-gap sizes of σ and surface bands are 6.5 ± 0.5 and 6.0 ± 0.5 meV, respectively, while that of the π band is much smaller (1.5 ± 0.5 meV). The present experimental result unambiguously demonstrates the validity of the two-band superconductivity in MgB 2.

  8. Direct observation of superconducting gaps in MgB2 by angle-resolved photoemission spectroscopy

    International Nuclear Information System (INIS)

    Souma, S.; Machida, Y.; Sato, T.; Takahashi, T.; Matsui, H.; Wang, S.-C.; Ding, H.; Kaminski, A.; Campuzano, J.C.; Sasaki, S.; Kadowaki, K.

    2004-01-01

    High-resolution angle-resolved photoemission spectroscopy has been carried out to clarify the anomalous superconductivity of MgB 2 . We observed three bands crossing the Fermi level, which are ascribed to B2p-σ, π and surface bands. We have succeeded for the first time in directly observing the superconducting gaps of these bands separately. We have found that the superconducting-gap sizes of σ and surface bands are 6.5 ± 0.5 and 6.0 ± 0.5 meV, respectively, while that of the π band is much smaller (1.5 ± 0.5 meV). The present experimental result unambiguously demonstrates the validity of the two-band superconductivity in MgB 2

  9. Direct metabolic fingerprinting of commercial herbal tinctures by nuclear magnetic resonance spectroscopy and mass spectrometry.

    Science.gov (United States)

    Politi, Matteo; Zloh, Mire; Pintado, Manuela E; Castro, Paula M L; Heinrich, Michael; Prieto, Jose M

    2009-01-01

    Tinctures are widely used liquid pharmaceutical preparations traditionally obtained by maceration of one or more medicinal plants in ethanol-water solutions. Such a process results in the extraction of virtually hundreds of structurally diverse compounds with different polarities. Owing to the large chemical diversity of the constituents present in the herbal tinctures, the analytical tools used for the quality control of tinctures are usually optimised only for the detection of single chemical entities or specific class of compounds. In order to overcome the major limitations of the current methods used for analysis of tinctures, a new methodological approach based on NMR spectroscopy and MS spectrometry has been tested with different commercial tinctures. Diffusion-edited 1H-NMR (1D DOSY) and 1H-NMR with suppression of the ethanol and water signals have been applied here for the first time to the direct analysis of commercial herbal tinctures derived from Echinacea purpurea, Hypericum perforatum, Ginkgo biloba and Valeriana officinalis. The direct injection of the tinctures in the MS detector in order to obtain the corresponding metabolic profiles was also performed. Using both NMR and MS methods it was possible, without evaporation or separation steps, to obtain a metabolic fingerprint able to distinguish between tinctures prepared with different plants. Batch-to-batch homogeneity, as well as degradation after the expiry date of a batch, was also investigated. The techniques proposed here represent fast and convenient direct analyses of medicinal herbal tinctures.

  10. Development of time-resolved electron momentum spectroscopy. Toward real-time imaging of frontier electrons in molecular reactions

    International Nuclear Information System (INIS)

    Yamazaki, M.; Takahashi, M.

    2016-01-01

    This report will introduce a new experimental technique to readers, which we would like to propose towards advances in the field of molecular reaction dynamics. It is time-resolved electron momentum spectroscopy and aims to take in momentum space snapshots of the rapid change of molecular orbitals, which is the driving force behind any structural changes occurring in transient molecules. Following a description of the working principle of the technique, some preliminary result will be presented in order to illustrate the current performance of the apparatus. (author)

  11. High resolution X-ray photoelectron spectroscopy of styrene oxide adsorption and reaction on Ag(1 1 1)

    Science.gov (United States)

    Piao, H.; Enever, M. C. N.; Adib, K.; Hrbek, J.; Barteau, M. A.

    2004-11-01

    Synchrotron-based X-ray photoelectron spectroscopy (XPS) has been used to investigate the adsorption and reaction of styrene oxide on Ag(1 1 1). When adsorption is carried out at 250 K or above, ring opening of styrene oxide forms a stable surface oxametallacycle intermediate which eventually reacts at 485 K to regenerate styrene oxide. High resolution XPS is capable of distinguishing the oxametallacycle from molecularly adsorbed and condensed styrene oxide on the basis of different C1s peak separations. The observed separations are well accounted for by the results of DFT calculations.

  12. Yrast spectroscopy in {sup 49-51}Ti via fusion-evaporation reaction induced by a radioactive beam

    Energy Technology Data Exchange (ETDEWEB)

    Niikura, M.; Ideguchi, E.; Michimasa, S.; Ota, S.; Shimoura, S.; Wakabayashi, Y. [University of Tokyo, Center for Nuclear Study, Wako, Saitama (Japan); Aoi, N.; Baba, H.; Fukuchi, T.; Ichikawa, Y.; Kubo, T.; Kurokawa, M.; Ohnishi, T.; Suzuki, H.; Yoshida, K. [RIKEN Nishina Center, Wako, Saitama (Japan); Iwasaki, H.; Onishi, T.K.; Suzuki, D. [University of Tokyo, Department of Physics, Tokyo (Japan); Liu, M.; Zheng, Y. [Chinese Academy of Sciences, Institute of Modern Physics, Lanzhou (China)

    2009-12-15

    In-beam {gamma} -ray spectroscopy of high-spin states in {sup 49-51}Ti was performed via the fusion-evaporation reaction using a radioactive beam. By excitation function and {gamma} - {gamma} coincidence analysis, yrast high-spin levels up to I=(21/2{sup -}),(11{sup +}),(17/2{sup -}) in {sup 49-51}Ti were determined. The levels were compared with full-pf -shell model calculation. The level structure indicates the persistency of the N=28 shell gap at yrast states in {sup 49-51}Ti. (orig.)

  13. Deamidation reactions of protonated asparagine and glutamine investigated by ion spectroscopy

    NARCIS (Netherlands)

    Kempkes, L.J.M.; Martens, J.K.; Grzetic, J.; Berden, G.; Oomens, J.

    2016-01-01

    RATIONALE: Deamidation of Asn and Gln residues is a primary route for spontaneous post-translational protein modification. Several structures have been proposed for the deamidation products of the protonated amino acids. Here we verify these structures by ion spectroscopy, as well as the structures

  14. In-beam γ-ray Spectroscopy of {sup 30}P via the {sup 28}Si({sup 3}He,pγ){sup 30}P Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mcneice, E.; Setoodehnia, K. [Department of Physics and Astronomy, McMaster University, Hamilton, ON L8S 4M1 (Canada); Singh, B., E-mail: ndgroup@mcmaster.ca [Department of Physics and Astronomy, McMaster University, Hamilton, ON L8S 4M1 (Canada); Abe, Y. [Institute of Physics, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki 305-8577 (Japan); Binh, D.N. [Center for Nuclear Study (CNS), the University of Tokyo, Wako Branch at RIKEN, Wako, Saitama 351-0198 (Japan); Chen, A.A.; Chen, J. [Department of Physics and Astronomy, McMaster University, Hamilton, ON L8S 4M1 (Canada); Cherubini, S. [INFN-Laboratori Nazionali del Sud and Dipartimento di Fisica ed Astronomia, Università di Catania, 95123 Catania (Italy); Center for Nuclear Study (CNS), the University of Tokyo, Wako Branch at RIKEN, Wako, Saitama 351-0198 (Japan); Fukuoka, S. [Institute of Physics, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki 305-8577 (Japan); Hashimoto, T. [Center for Nuclear Study (CNS), the University of Tokyo, Wako Branch at RIKEN, Wako, Saitama 351-0198 (Japan); Hayakawa, T. [Japan Atomic Energy Agency (JAEA), Tokai–mura, Ibaraki 319-1195 (Japan); Ishibashi, Y.; Ito, Y. [Institute of Physics, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki 305-8577 (Japan); Kahl, D. [Center for Nuclear Study (CNS), the University of Tokyo, Wako Branch at RIKEN, Wako, Saitama 351-0198 (Japan); Komatsubara, T. [Institute of Physics, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki 305-8577 (Japan); Kubono, S. [Nishina Center, the Institute of Physical and Chemical Research (RIKEN), Wako, Saitama 351-0198 (Japan); Moriguchi, T.; Nagae, D.; Nishikiori, R.; Niwa, T. [Institute of Physics, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki 305-8577 (Japan); and others

    2014-06-15

    The level structure of {sup 30}P up to 8.25 MeV was investigated via in-beam γ-ray spectroscopy using the {sup 28}Si({sup 3}He,pγ){sup 30}P reaction at 9 MeV at the University of Tsukuba Tandem Accelerator Complex in Japan. An energy level scheme was deduced from γ-γ coincidence measurements. 47 new transitions have been observed from the previously known states (mostly resonances), thereby reducing the uncertainties in the excitation energies of 17 states from 3 to 10 keV to values of < 1 keV. Furthermore, spin assignments based on measurements of γ-ray angular distributions and γ-γ directional correlation of oriented nuclei (DCO ratios) were made for several observed levels of {sup 30}P.

  15. Analytical control of an esterification batch reaction between glycerine and fatty acids by near-infrared spectroscopy

    International Nuclear Information System (INIS)

    Blanco, Marcelo; Beneyto, Rafael; Castillo, Miguel; Porcel, Marta

    2004-01-01

    Near-infrared spectroscopy was used to control an esterification reaction between glycerine and middle- or long-chain fatty acids performed in a laboratory-scale reactor. The process involves the initial formation of monoglycerides, which is followed by that of di- and triglycerides as well as transesterification. Establishing the end point of the process is critical with a view to ensuring that the end product will have the composition required for its intended use. PLS calibration was applied to industrial and laboratory-scale batch samples, and laboratory samples were additionally used to extend calibration ranges and avoid correlation between the concentration of the batch samples. In this way, PLS calibration models for glycerine, fatty acids, water, and mono-, di- and triglycerides, were constructed. The proposed method allows the reaction to be monitored in real time, thereby avoiding long analysis times, excessive reagent consumption and the obtainment of out-of-specification products

  16. Direct reactions induced by 16O on 208Pb at high incident energy

    International Nuclear Information System (INIS)

    Mermaz, M.C.

    1978-01-01

    Direct reactions induced by 16 O mainly on 208 Pb at 20 MeV/nucleon are reviewed. The quasi-elastic transfer reaction, such as one-proton and one-neutron transfer respectively leading to 209 Bi and 209 Pb single-particle-states, is first discussed, the fragmentation of 16 O projectile on heavy targets is then envisaged. The one-nucleon transfer can be described within the framework of one-step processes using the DWBA formalism to calculate the cross sections. At high incident energy (312.6 MeV), transfer reactions involving nucleons from the deeper 1p 3/2 orbit of 16 O are kinematically favoured and well observed. At 20 MeV/A and above, a large part of the reaction cross sections seems to be due to the fragmentation of the projectile; more especially, an abrasion-ablation model have to be used in order to explain the general trend of the data (energy spectra and angular distribution)

  17. Metode Direct Polymerase Chain Reaction untuk Melacak Campylobacter sp. pada Daging Ayam (DIRECT POLYMERASE CHAIN REACTION METHOD FOR DETECTION CAMPYLOBACTER SP. OF POULTRY MEAT

    Directory of Open Access Journals (Sweden)

    Andriani .

    2013-08-01

    Full Text Available Campylobacter sp. is the most commonly reported as agent of foodborne zoonosis causing acutegastroenteritis in humans. Poultry meat is considered as a major source of C. jejuni infection in human.The conventional methods for detecting foodborne bacteria is time-consuming which rely on the of thebacteria in culture media, followed by biochemical identification. In this study polymerase chain reaction(PCR technique was used for rapid identification of the pathogenic Campylobacter sp. The samples usedwere 298 chicken carcass with sold in supermarkets and traditional markets, and were carried out inaccordance the isolation protocol ISO/ DIS 10272-1994. Identification was performed using biochemicalAPI Campy. The direct PCR (DPCR assay with two sets of primers was employed for isolation andidentification of C. jejuni and C. coli. The result of the isolation and identification both by conventional orPCR methods showed that chicken carcasses both from supermarket and traditional market werecontaminated with C. jejuni and or C. coli. Prevalence of Campylobacter sp. contamination in chicken meatwas higher by DPCR (62.6% than by conventional (19.8%, indicating that DPCR technique was moresensitive than conventional method with detection limit for C. jejuni was103 cfu/ml.

  18. Direct rate assessment of laccase catalysed radical formation in lignin by electron paramagnetic resonance spectroscopy

    DEFF Research Database (Denmark)

    Munk, Line; Andersen, Mogens Larsen; Meyer, Anne S.

    2017-01-01

    Laccases (EC 1.10.3.2) catalyse removal of an electron and a proton from phenolic hydroxyl groups, including phenolic hydroxyls in lignins, to form phenoxy radicals during reduction of O2. We employed electron paramagnetic resonance spectroscopy (EPR) for real time measurement of such catalytic...... to suspensions of the individual lignin samples produced immediate time and enzyme dose dependent increases in intensity in the EPR signal with g-values in the range 2.0047–2.0050 allowing a direct quantitative monitoring of the radical formation and thus allowed laccase enzyme kinetics assessment on lignin...... for the radical formation rate in organosolv lignin was determined by response surface methodology to pH 4.8, 33 °C and pH 5.8, 33 °C for the Tv laccase and the Mt laccase, respectively. The results verify direct radical formation action of fungal laccases on lignin without addition of mediators and the EPR...

  19. International conference: Features of nuclear excitation states and mechanisms of nuclear reactions. 51. Meeting on nuclear spectroscopy and nuclear structure. The book of abstracts

    International Nuclear Information System (INIS)

    2001-01-01

    Results of the LI Meeting on Nuclear Spectroscopy and Nuclear Structure are presented. Properties of excited states of atomic nuclei and mechanisms of nuclear reactions are considered. Studies on the theory of nucleus and fundamental interactions pertinent to experimental study of nuclei properties and mechanisms of nuclear reactions, technique and methods of experiment, application of nuclear-physical method, are provided [ru

  20. In operando observation system for electrochemical reaction by soft X-ray absorption spectroscopy with potential modulation method

    International Nuclear Information System (INIS)

    Nagasaka, Masanari; Kosugi, Nobuhiro; Yuzawa, Hayato; Horigome, Toshio

    2014-01-01

    In order to investigate local structures of electrolytes in electrochemical reactions under the same scan rate as a typical value 100 mV/s in cyclic voltammetry (CV), we have developed an in operando observation system for electrochemical reactions by soft X-ray absorption spectroscopy (XAS) with a potential modulation method. XAS spectra of electrolytes are measured by using a transmission-type liquid flow cell with built-in electrodes. The electrode potential is swept with a scan rate of 100 mV/s at a fixed photon energy, and soft X-ray absorption coefficients at different potentials are measured at the same time. By repeating the potential modulation at each fixed photon energy, it is possible to measure XAS of electrochemical reaction at the same scan rate as in CV. We have demonstrated successful measurement of the Fe L-edge XAS spectra of aqueous iron sulfate solutions and of the change in valence of Fe ions at different potentials in the Fe redox reaction. The mechanism of these Fe redox processes is discussed by correlating the XAS results with those at different scan rates

  1. Electron momentum spectroscopy of solids by the (e,2e) reaction

    International Nuclear Information System (INIS)

    Kheifets, A.S.; Vos, M.; Canney, S.A.; Guo, X.; McCarthy, I.E.

    1996-08-01

    Recent developments in (e,2e) momentum spectroscopy have resulted in the study of a diverse range of solid targets. These studies have revealed the electronic structure of solids in much more detail that was previously available using this technique. The method is now capable of producing quantitative data on energy-resolved momentum density of solids. A summary of these results is presented, in particular for aluminium, aluminium oxides and graphite. 26 refs., 9 figs

  2. Effect of surface structure on catalytic reactions: A sum frequency generation surface vibrational spectroscopy study

    International Nuclear Information System (INIS)

    McCrea, Keith R.

    2001-01-01

    In the results discussed above, it is clear that Sum Frequency Generation (SFG) is a unique tool that allows the detection of vibrational spectra of adsorbed molecules present on single crystal surfaces under catalytic reaction conditions. Not only is it possible to detect active surface intermediates, it is also possible to detect spectator species which are not responsible for the measured turnover rates. By correlating high-pressure SFG spectra under reaction conditions and gas chromatography (GC) kinetic data, it is possible to determine which species are important under reaction intermediates. Because of the flexibility of this technique for studying surface intermediates, it is possible to determine how the structures of single crystal surfaces affect the observed rates of catalytic reactions. As an example of a structure insensitive reaction, ethylene hydrogenation was explored on both Pt(111) and Pt(100). The rates were determined to be essentially the same. It was observed that both ethylidyne and di-(sigma) bonded ethylene were present on the surface under reaction conditions on both crystals, although in different concentrations. This result shows that these two species are not responsible for the measured turnover rate, as it would be expected that one of the two crystals would be more active than the other, since the concentration of the surface intermediate would be different on the two crystals. The most likely active intermediates are weakly adsorbed molecules such as(pi)-bonded ethylene and ethyl. These species are not easily detected because their concentration lies at the detection limit of SFG. The SFG spectra and GC data essentially show that ethylene hydrogenation is structure insensitive for Pt(111) and Pt(100). SFG has proven to be a unique and excellent technique for studying adsorbed species on single crystal surfaces under high-pressure catalytic reactions. Coupled with kinetic data obtained from gas chromatography measurements, it can

  3. Direct Light-up of cAMP Derivatives in Living Cells by Click Reactions

    Directory of Open Access Journals (Sweden)

    Yan Xu

    2013-10-01

    Full Text Available 8-Azidoadenosine 3′,5′-cyclic monophosphate (8-azido cAMP was directly detected in living cells, by applying Cu-free azide-alkyne cycloaddition to probe cAMP derivatives by fluorescence light-up. Fluorescence emission was generated by two non-fluorescent molecules, 8-azido cAMP as a model target and difluorinated cyclooctyne (DIFO reagent as a probe. The azide-alkyne cycloaddition reaction between 8-azido cAMP and DIFO induces fluorescence in 8-azido cAMP. The fluorescence emission serves as a way to probe 8-azido cAMP in cells.

  4. Photon Energy Threshold in Direct Photocatalysis with Metal Nanoparticles: Key Evidence from the Action Spectrum of the Reaction.

    Science.gov (United States)

    Sarina, Sarina; Jaatinen, Esa; Xiao, Qi; Huang, Yi Ming; Christopher, Philip; Zhao, Jin Cai; Zhu, Huai Yong

    2017-06-01

    By investigating the action spectra (the relationship between the irradiation wavelength and apparent quantum efficiency of reactions under constant irradiance) of a number of reactions catalyzed by nanoparticles including plasmonic metals, nonplasmonic metals, and their alloys at near-ambient temperatures, we found that a photon energy threshold exists in each photocatalytic reaction; only photons with sufficient energy (e.g., higher than the energy level of the lowest unoccupied molecular orbitals) can initiate the reactions. This energy alignment (and the photon energy threshold) is determined by various factors, including the wavelength and intensity of irradiation, molecule structure, reaction temperature, and so forth. Hence, distinct action spectra were observed in the same type of reaction catalyzed by the same catalyst due to a different substituent group, a slightly changed reaction temperature. These results indicate that photon-electron excitations, instead of the photothermal effect, play a dominant role in direct photocatalysis of metal nanoparticles for many reactions.

  5. Electrified emotions: Modulatory effects of transcranial direct stimulation on negative emotional reactions to social exclusion.

    Science.gov (United States)

    Riva, Paolo; Romero Lauro, Leonor J; Vergallito, Alessandra; DeWall, C Nathan; Bushman, Brad J

    2015-01-01

    Social exclusion, ostracism, and rejection can be emotionally painful because they thwart the need to belong. Building on studies suggesting that the right ventrolateral prefrontal cortex (rVLPFC) is associated with regulation of negative emotions, the present experiment tests the hypothesis that decreasing the cortical excitability of the rVLPFC may increase negative emotional reactions to social exclusion. Specifically, we applied cathodal transcranial direct current stimulation (tDCS) over the rVLPFC and predicted an increment of negative emotional reactions to social exclusion. In Study 1, participants were either socially excluded or included, while cathodal tDCS or sham stimulation was applied over the rVLPFC. Cathodal stimulation of rVLPFC boosted the typical negative emotional reaction caused by social exclusion. No effects emerged from participants in the inclusion condition. To test the specificity of tDCS effects over rVLPFC, in Study 2, participants were socially excluded and received cathodal tDCS or sham stimulation over a control region (i.e., the right posterior parietal cortex). No effects of tDCS stimulation were found. Our results showed that the rVLPFC is specifically involved in emotion regulation and suggest that cathodal stimulation can increase negative emotional responses to social exclusion.

  6. Direct observation of forward-scattering oscillations in the H+HD→H2+D reaction

    Science.gov (United States)

    Yuan, Daofu; Yu, Shengrui; Chen, Wentao; Sang, Jiwei; Luo, Chang; Wang, Tao; Xu, Xin; Casavecchia, Piergiorgio; Wang, Xingan; Sun, Zhigang; Zhang, Dong H.; Yang, Xueming

    2018-06-01

    Accurate measurements of product state-resolved angular distributions are central to fundamental studies of chemical reaction dynamics. Yet, fine quantum-mechanical structures in product angular distributions of a reactive scattering process, such as the fast oscillations in the forward-scattering direction, have never been observed experimentally and the nature of these oscillations has not been fully explored. Here we report the crossed-molecular-beam experimental observation of these fast forward-scattering oscillations in the product angular distribution of the benchmark chemical reaction, H + HD → H2 + D. Clear oscillatory structures are observed for the H2(v' = 0, j' = 1, 3) product states at a collision energy of 1.35 eV, in excellent agreement with the quantum-mechanical dynamics calculations. Our analysis reveals that the oscillatory forward-scattering components are mainly contributed by the total angular momentum J around 28. The partial waves and impact parameters responsible for the forward scatterings are also determined from these observed oscillations, providing crucial dynamics information on the transient reaction process.

  7. Collinear laser spectroscopy on In isotopes from heavy ion fusion reactions

    International Nuclear Information System (INIS)

    Ulm, G.

    1984-07-01

    Indium isotopes 107-111 were produced by 16 O-fusion reactions and investigated in a collinear laser geometry. The hyperfine structure and isotopic shifts are measured and the deduced magnetic dipole moments are in agreement with shell model calculations. The nuclear charge radii are determined from the isotopic shifts. (WL)

  8. Deamidation Reactions of Asparagine- and Glutamine-Containing Dipeptides Investigated by Ion Spectroscopy

    NARCIS (Netherlands)

    Kempkes, L.J.M.; Martens, J.; Grzetic, J.; Berden, G.; Oomens, J.

    2016-01-01

    Deamidation is a major fragmentation channel upon activation by collision induced dissociation (CID) for protonated peptides containing glutamine (Gln) and asparagine (Asn) residues. Here, we investigate these NH3-loss reactions for four Asn- and Gln-containing protonated peptides in terms of the

  9. Nuclear Level Densities for Modeling Nuclear Reactions: An Efficient Approach Using Statistical Spectroscopy

    International Nuclear Information System (INIS)

    Calvin W. Johnson

    2005-01-01

    The general goal of the project is to develop and implement computer codes and input files to compute nuclear densities of state. Such densities are important input into calculations of statistical neutron capture, and are difficult to access experimentally. In particular, we will focus on calculating densities for nuclides in the mass range A ∼ 50-100. We use statistical spectroscopy, a moments method based upon a microscopic framework, the interacting shell model. Second year goals and milestones: Develop two or three competing interactions (based upon surface-delta, Gogny, and NN-scattering) suitable for application to nuclei up to A = 100. Begin calculations for nuclides with A = 50-70

  10. Direct characterization of the energy level alignments and molecular components in an organic hetero-junction by integrated photoemission spectroscopy and reflection electron energy loss spectroscopy analysis.

    Science.gov (United States)

    Yun, Dong-Jin; Shin, Weon-Ho; Bulliard, Xavier; Park, Jong Hwan; Kim, Seyun; Chung, Jae Gwan; Kim, Yongsu; Heo, Sung; Kim, Seong Heon

    2016-08-26

    A novel, direct method for the characterization of the energy level alignments at bulk-heterojunction (BHJ)/electrode interfaces on the basis of electronic spectroscopy measurements is proposed. The home-made in situ photoemission system is used to perform x-ray/ultraviolet photoemission spectroscopy (XPS/UPS), reflection electron energy loss spectroscopy (REELS) and inverse photoemission spectroscopy of organic-semiconductors (OSCs) deposited onto a Au substrate. Through this analysis system, we are able to obtain the electronic structures of a boron subphthalocyanine chloride:fullerene (SubPC:C60) BHJ and those of the separate OSC/electrode structures (SubPC/Au and C60/Au). Morphology and chemical composition analyses confirm that the original SubPC and C60 electronic structures remain unchanged in the electrodes prepared. Using this technique, we ascertain that the position and area of the nearest peak to the Fermi energy (EF = 0 eV) in the UPS (REELS) spectra of SubPC:C60 BHJ provide information on the highest occupied molecular orbital level (optical band gap) and combination ratio of the materials, respectively. Thus, extracting the adjusted spectrum from the corresponding SubPC:C60 BHJ UPS (REELS) spectrum reveals its electronic structure, equivalent to that of the C60 materials. This novel analytical approach allows complete energy-level determination for each combination ratio by separating its electronic structure information from the BHJ spectrum.

  11. Laser-induced breakdown spectroscopy for lambda quantification in a direct-injection engine

    International Nuclear Information System (INIS)

    Buschbeck, M.; Büchler, F.; Halfmann, T.; Arndt, S.

    2012-01-01

    We apply laser-induced breakdown spectroscopy (LIBS) to determine local lambda values (i.e. the normalized air-fuel mass ratio) at the ignition location λ ip in a direct-injection single-cylinder optical research engine. The technique enables us to determine variations of λ ip for different fuel injection strategies, as well as correlations between variations in λ ip and the combustion dynamics. In particular we observe, that fluctuations in λ ip are not the major cause of cycle-to-cycle variations in the combustion process. Moreover, our experiments identify insufficient lean λ ip values as a source of misfires in lean combustions. In a combination of LIBS with laser-induced fluorescence (LIF), we obtain additionally information about the two-dimensional λ distribution. These results demonstrate the potential of LIBS to monitor λ values during mixture formation in gasoline engines. - Highlights: ► Determination of λ values by means of LIBS in an optical gasoline engine. ► Evaluation of λ fluctuations for different fuel injection strategies. ► Investigation of the effect of λ upon combustion dynamics. ► Combination of LIBS and LIF to obtain two-dimensional λ distributions.

  12. A flexible gas flow reaction cell for in situ x-ray absorption spectroscopy studies

    Energy Technology Data Exchange (ETDEWEB)

    Kroner, Anna B., E-mail: anna.kroner@diamond.ac.uk; Gilbert, Martin; Duller, Graham; Cahill, Leo; Leicester, Peter; Woolliscroft, Richard; Shotton, Elizabeth J. [Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Chilton, Oxfordshire, OX110DE (United Kingdom); Mohammed, Khaled M. H. [UK Catalysis Hub, Research Complex at Harwell, Rutherford Appleton Laboratory, Chilton, Oxfordshire, OX110FA (United Kingdom); School of Chemistry, University of Southampton, Southampton, SO17 1BJ (United Kingdom)

    2016-07-27

    A capillary-based sample environment with hot air blower and integrated gas system was developed at Diamond to conduct X-ray absorption spectroscopy (XAS) studies of materials under time-resolved, in situ conditions. The use of a hot air blower, operating in the temperature range of 298-1173 K, allows introduction of other techniques e.g. X-ray diffraction (XRD), Raman spectroscopy for combined techniques studies. The flexibility to use either quartz or Kapton capillaries allows users to perform XAS measurement at energies as low as 5600 eV. To demonstrate performance, time-resolved, in situ XAS results of Rh catalysts during the process of activation (Rh K-edge, Ce L{sub 3}-edge and Cr K-edge) and the study of mixed oxide membrane (La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3−δ}) under various partial oxygen pressure conditions are described.

  13. Study on in-situ electrochemical impedance spectroscopy measurement of anodic reaction in SO_2 depolarized electrolysis process

    International Nuclear Information System (INIS)

    Xue Lulu; Zhang Ping; Chen Songzhe; Wang Laijun

    2014-01-01

    SO_2 depolarized electrolysis (SDE) is the pivotal reaction in hybrid sulfur process, one of the most promising approaches for mass hydrogen production without CO_2 emission. The net result of hybrid sulfur process is to split water into hydrogen and oxygen at a relatively low voltage, which will dramatically decrease the energy consumption for the production of hydrogen. The potential loss of SDE process could be separated into four components, i.e. reversible cell potential, anode overpotential, cathode overpotential and ohmic loss. So far, it has been identified that the total cell potential for the SO_2 depolarized electrolyzer is dominantly controlled by sulfuric acid concentration of the anolyte and electrolysis temperature of the electrolysis process. In this work, an in-situ Electrochemical Impedance Spectroscopy (EIS) measurement of the anodic SDE reaction was conducted. Results show that anodic overpotential is mainly resulted from the SO_2 oxidation reaction other than ohmic resistance or mass transfer limitation. This study extends the understanding to SDE process and gives suggestions for the further improvement of the SDE performance. (author)

  14. Improvement of direct determination of trace nickel in environmental samples by diffuse reflection spectroscopy using chromaticity characteristics.

    Science.gov (United States)

    Ershova, N I; Ivanov, V M

    2000-05-01

    Cellulose and chromaton-N-super as solid supports for direct determination of the immobilized nickel complexes with dimethylglyoxime and benzyldioxime by diffuse reflection spectroscopy were compared. The advantage of chromaton-N-super with use of benzyldioxime is shown. Detection limit is 0.02 microg/mL. The proposed method was applied for the analysis of soil.

  15. Infrared photoexcitation spectroscopy of conducting polymer and C60 composites: direct evidence of photo-induced electron transfer

    NARCIS (Netherlands)

    Lee, Kwanghee; Janssen, R.A.J.; Sariciftci, N.S.; Heeger, A.J.

    1994-01-01

    We report direct spectral evidence of photoinduced electron transfer from the excited state of conducting polymer onto C60 by infrared photoexcitation spectroscopy, from 0.01 eV (100 cm-1) to 1.3 eV (11,000 cm-1). The photoinduced absorption spectra of poly(3-octylthiophene) (P30T) and

  16. Reaction between laser ablation plume and ambient gas studied by laser-induced fluorescence imaging spectroscopy

    International Nuclear Information System (INIS)

    Sasaki, K; Watarai, H

    2007-01-01

    We visualized the density distributions of C 2 (plume), NO (ambient gas), and CN (reaction product) when a graphite target was ablated by irradiating YAG laser pulses at wavelengths of 1064 and 355 nm in ambient gas mixture of NO and He. It has been shown by the density distributions of C 2 and NO that the expansion of the plume removes the ambient gas and the plume and the ambient gas locate exclusively in both the cases at 1064 and 355 nm. A high CN density was observed at the interface between the plume and the ambient gas at 1064 nm, which is reasonable since chemical reactions between the plume and the ambient gas may occur only at their interface. On the other hand, in the case at 355 nm, we observed considerable CN inside the plume, indicating that the chemical reaction processes in the laser ablation at 355 nm is different from that expected from the density distributions of the plume and the ambient gas

  17. Raman Spectroscopy of Serpentine and Reaction Products at High Pressure Using a Diamond Anvil Cell

    Science.gov (United States)

    Burgess, K.; Zinin, P.; Odake, S.; Fryer, P.; Hellebrand, E.

    2012-12-01

    Serpentine is one of the most abundant hydrous phases in the altered subducting plate, and contributes a large portion of the water flux in subduction zones. Measuring and understanding the structural changes in serpentine with pressure aids our understanding of the processes ongoing in oceanic crust and subduction zones. We have conducted high-pressure/high-temperature experiments on serpentine and its dehydration reaction products using a diamond anvil cell. We used the multifunctional in-situ measurement system equipped with a Raman device and laser heating system at the University of Hawaii. Well-characterized natural serpentinite was used in the study. Pressure was determined using the shift of the fluorescence line of a ruby placed next to the sample. Raman spectra of serpentine were obtained at higher pressures than previously published, up to 15 GPa; the peak shift with pressure fits the model determined by Auzende et al. [2004] at lower pressures. Heating was done at several different pressures up to 20 GPa, and reaction products were identified using Raman. Micro-Raman techniques allow us to determine reaction progress and heterogeneity within natural samples containing olivine and serpentine. Auzende, A-L., I. Daniel, B. Reynard, C. Lemaire, F. Guyot (2004). High-pressure behavior of serpentine minerals: a Raman spectroscopic study. Phys. Chem. Minerals 31 269-277.

  18. Application of Mössbauer spectroscopy in industrial heterogeneous catalysis: effect of oxidant on FePO{sub 4} material phase transformations in direct methanol synthesis from methane

    Energy Technology Data Exchange (ETDEWEB)

    Dasireddy, Venkata D. B. C., E-mail: dasireddy@ki.si [National Institute of Chemistry, Department of Catalysis and Chemical Reaction Engineering (Slovenia); Khan, Faiza B. [Energy Technology (South Africa); Hanzel, Darko [Jozef Stefan Institute (Slovenia); Bharuth-Ram, Krish [Durban University of Technology, Physics Department (South Africa); Likozar, Blaž [National Institute of Chemistry, Department of Catalysis and Chemical Reaction Engineering (Slovenia)

    2017-11-15

    The effect of the FePO{sub 4} material phase transformation in the direct selective oxidation of methane to methanol was studied using various oxidants, i.e. O{sub 2}, H{sub 2}O and N{sub 2}O. The phases of the heterogeneous catalyst applied, before and after the reactions, were characterized by M¨ossbauer spectroscopy. The main reaction products were methanol, carbon monoxide and carbon dioxide, whereas formaldehyde was produced in rather minute amounts. The Mössbauer spectra showed the change of the initial catalyst material, FePO{sub 4} (tridymite-like phase (tdm)), to the reduced metal form, iron(II) pyrophosphate, Fe{sub 2}P{sub 2}O{sub 7}, and thereafter, the material phase change was governed by the oxidation with individual oxidizing species.Mössbauer spectroscopy measurements applied along with X-ray diffraction (XRD) studies on fresh, reduced and spent catalytic materials demonstrated a transformation of the catalyst to a mixture of phases which depended on operating process conditions. Generally, activity was low and should be a subject of further material optimization and engineering, while the selectivity towards methanol at low temperatures applied was adequate. The proceeding redox mechanism should thus play a key role in catalytic material design, while the advantage of iron-based heterogeneous catalysts primarily lies in them being comparably inexpensive and comprising non-critical raw materials only.

  19. X-ray photoelectron spectroscopy study of CO2 reaction with polycrystalline uranium surface

    International Nuclear Information System (INIS)

    Liu Kezhao; Yu Yong; Zhou Juesheng; Wu Sheng; Wang Xiaolin; Fu Yibei

    1999-10-01

    The adsorption of CO 2 on 'clean' depleted polycrystalline uranium metal surface has been studied by X-ray photoelectron spectroscopy (XPS) at 300 K. The 'clean' surface were prepared by Ar + ion sputtering under ultra-high vacuum (UHV) condition with a base pressure 6.7 x 10 -8 Pa. The result s shows that adsorption of CO 2 on 'clean' uranium metal took place in total dissociation, and leads to the formation of uranium dioxide, uranium carbides and free carbon. The total dissociation of CO 2 produced carbon, oxygen species, CO 2 2- and CO 3 2- species. The diffusion tendency of carbon was much stronger than that of oxygen, and led to form a carbide in oxide-metal interface while the oxygen remained on their surface as an oxide

  20. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

    Science.gov (United States)

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

    2016-10-24

    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. In-situ, real-time, studies of film growth processes using ion scattering and direct recoil spectroscopy techniques.

    Energy Technology Data Exchange (ETDEWEB)

    Smentkowski, V. S.

    1999-04-22

    Time-of-flight ion scattering and recoil spectroscopy (TOF-ISARS) enables the characterization of the composition and structure of surfaces with 1-2 monolayer specificity. It will be shown that surface analysis is possible at ambient pressures greater than 3 mTorr using TOF-ISARS techniques; allowing for real-time, in situ studies of film growth processes. TOF-ISARS comprises three analytical techniques: ion scattering spectroscopy (ISS), which detects the backscattered primary ion beam; direct recoil spectroscopy (DRS), which detects the surface species recoiled into the forward scattering direction; and mass spectroscopy of recoiled ions (MSRI), which is 3 variant of DRS capable of isotopic resolution for all surface species--including H and He. The advantages and limitations of each of these techniques will be discussed. The use of the three TOF-ISARS methods for real-time, in situ film growth studies at high ambient pressures will be illustrated. It will be shown that MSRI analysis is possible during sputter deposition. It will be also be demonstrated that the analyzer used for MSRI can also be used for time of flight secondary ion mass spectroscopy (TOF-SIMS) under high vacuum conditions. The use of a single analyzer to perform the complimentary surface analytical techniques of MSRI and SIMS is unique. The dwd functionality of the MSRI analyzer provides surface information not obtained when either MSRI or SIMS is used independently.

  2. Contactless, probeless and non-titrimetric determination of acid-base reactions using broadband acoustic resonance dissolution spectroscopy (BARDS).

    Science.gov (United States)

    Ahmed, M Rizwan; McSweeney, Sean; Krüse, Jacob; Vos, Bastiaan; Fitzpatrick, Dara

    2018-02-12

    pH determination is a routine measurement in scientific laboratories worldwide. Most major advances in pH measurement were made in the 19th and early 20th century. pH measurements are critical for the determination of acid base reactions. This study demonstrates how an acid-base reaction can be monitored without the use of a pH probe, indicator and titres of reagent. The stoichiometric reaction between carbonate and HCl acid yields specific quantities of CO 2 , which causes reproducible changes to the compressibility of the solvent. This in turn slows down the speed of sound in solution which is induced by a magnetic follower gently tapping the inner wall of the vessel. As a consequence the frequencies of the acoustic resonances in the vessel are reduced. This approach is called Broadband Acoustic Resonance Dissolution Spectroscopy (BARDS) which harnesses this phenomenon for many applications. The acid-carbonate experiments have also been validated using H 2 SO 4 acid and using both potassium and sodium counterions for the carbonate. This method can be used to interrogate strong acid-base reactions in a rapid and non-invasive manner using carbonate as the base. The data demonstrate the first example of a reactant also acting as an indicator. The applicability of the method to weak acids has yet to be determined. A novel conclusion from the study is that a person with a well-trained ear is capable of determining the concentration and pH of a strong acid just by listening. This brings pH measurement into the realm of human perception.

  3. Dilepton spectroscopy at intermediate energies; the carbon - carbon reaction at 1 GeV/A

    International Nuclear Information System (INIS)

    Prunet, M.

    1995-01-01

    The Physics context of this work is heavy ion collisions at relativistic energies where di-electron provide informations on the produced hot and dense nuclear matter. The experiment is performed by the DiLepton Spectrometer (DLS) Collaboration at the Lawrence Berkeley's Bevalac. After a description of the apparatus, we review the whole program and the main results so far obtained: first evidence of a significant di-electron signal at energies above 1 GeV/A; improvement of the understanding of di-electron production (electromagnetic decays of hadrons, π + π - annihilation and hadronic Bremsstrahlung). The results of p-p, p-d reactions from 1 to 4.9 GeV/A show that hadronic Bremsstrahlung (pp, pn) should be reformulated. Our analysis, optimized on the reaction Carbon-Carbon at 1 GeV/A, has been applied to α-Ca and d-Ca. We have developed two main aspects: improvement of the time resolution (500 ps) in order to eliminate all of the protons. Improvement of the space resolution (300 μ) for better mass resolution, in particular in the ρ region. We obtain the cross section of di-electron production as a function of mass, transverse momentum and rapidity from the C-C, α-Ca and d-Ca reactions at 1 GeV/A. We also compare the cross section for all of the measured systems at 1 GeV/A, including Ca-Ca, and we show a (ApAt) α dependence with α ≅ 1.1. A study of the associated multiplicity has also been performed. Nevertheless, the limited acceptance of the DLS and its poor mass resolution to identify the ρ, ω vector mesons, do not allow to conclude on hadron behaviour in nuclear matter. This point is one of the main goal of the HADES project at GSI (Darmstadt), which we give a brief description of the main features. (authors). 60 refs

  4. Radiative capture reactions and spectroscopy of multipolar anions in the framework of Gamow Shell Model

    International Nuclear Information System (INIS)

    Fossez, Kevin

    2014-01-01

    Small open quantum systems, whose properties are profoundly affected by the environment of continuum states, are intensely studied in various fields of Physics: nuclear physics, atomic and molecular physics, quantum optics, etc. These different many-body systems, in spite of their specific features, have generic properties which are common to all weakly bound or unbound systems close to the threshold. Coupling to the continuum is essential to describe the low-energy nuclear reactions of astrophysical interest, the formation of halo states in nuclei, atomic clusters and dipolar anions, or the near-threshold two neutron and alpha particle correlations (clustering). Recently, the open quantum system extension of the nuclear shell model, the Gamow shell model (GSM), based on the Berggren ensemble, has been applied successfully for the description of resonant states spectra in atomic nuclei. The coupled-channel formulation of the GSM (GSM-CC) allows to describe various low-energy nuclear reactions. In this work, the GSM-CC is formulated and applied for the description of proton/neutron radiative capture reactions of astrophysical interest, such as: 17 F(p, γ) 18 Ne, 7 Be(p, γ) 8 B and 7 Li(n, γ) 8 Li. Moreover, for the first time, the GSM has been applied in atomic physics for the description of spectra of dipolar anions. Systematic investigation of the hydrogen cyanide dipolar anion (HCN - ) allowed to identify the collective bands of states both in the strong coupling regime, for weakly bound halo states, and in the weak coupling regime above the dissociation threshold. In the strong coupling regime, K J = 0 anion a rotational band has been found. Above the threshold, K J quantum number is not conserved. Resonances in this regime form rotational bands according to the angular momentum of the rotating molecule, whereas the band head energies and the lifetimes depend predominantly on the external electron wave function. (author) [fr

  5. Localizing internal friction along the reaction coordinate of protein folding by combining ensemble and single-molecule fluorescence spectroscopy

    Science.gov (United States)

    Borgia, Alessandro; Wensley, Beth G.; Soranno, Andrea; Nettels, Daniel; Borgia, Madeleine B.; Hoffmann, Armin; Pfeil, Shawn H.; Lipman, Everett A.; Clarke, Jane; Schuler, Benjamin

    2012-01-01

    Theory, simulations and experimental results have suggested an important role of internal friction in the kinetics of protein folding. Recent experiments on spectrin domains provided the first evidence for a pronounced contribution of internal friction in proteins that fold on the millisecond timescale. However, it has remained unclear how this contribution is distributed along the reaction and what influence it has on the folding dynamics. Here we use a combination of single-molecule Förster resonance energy transfer, nanosecond fluorescence correlation spectroscopy, microfluidic mixing and denaturant- and viscosity-dependent protein-folding kinetics to probe internal friction in the unfolded state and at the early and late transition states of slow- and fast-folding spectrin domains. We find that the internal friction affecting the folding rates of spectrin domains is highly localized to the early transition state, suggesting an important role of rather specific interactions in the rate-limiting conformational changes. PMID:23149740

  6. High resolution spectroscopy of the 12Lambda B hypernucleus produced by the (e,e'K+) reaction.

    Science.gov (United States)

    Miyoshi, T; Sarsour, M; Yuan, L; Zhu, X; Ahmidouch, A; Ambrozewicz, P; Androic, D; Angelescu, T; Asaturyan, R; Avery, S; Baker, O K; Bertovic, I; Breuer, H; Carlini, R; Cha, J; Chrien, R; Christy, M; Cole, L; Danagoulian, S; Dehnhard, D; Elaasar, M; Empl, A; Ent, R; Fenker, H; Fujii, Y; Furic, M; Gan, L; Garrow, K; Gasparian, A; Gueye, P; Harvey, M; Hashimoto, O; Hinton, W; Hu, B; Hungerford, E; Jackson, C; Johnston, K; Juengst, H; Keppel, C; Lan, K; Liang, Y; Likhachev, V P; Liu, J H; Mack, D; Margaryan, A; Markowitz, P; Martoff, J; Mkrtchyan, H; Nakamura, S N; Petkovic, T; Reinhold, J; Roche, J; Sato, Y; Sawafta, R; Simicevic, N; Smith, G; Stepanyan, S; Tadevosyan, V; Takahashi, T; Tanida, K; Tang, L; Ukai, M; Uzzle, A; Vulcan, W; Wells, S; Wood, S; Xu, G; Yamaguchi, H; Yan, C

    2003-06-13

    High-energy, cw electron beams at new accelerator facilities allow electromagnetic production and precision study of hypernuclear structure, and we report here on the first experiment demonstrating the potential of the (e,e'K+) reaction for hypernuclear spectroscopy. This experiment is also the first to take advantage of the enhanced virtual photon flux available when electrons are scattered at approximately zero degrees. The observed energy resolution was found to be approximately 900 keV for the (12)(Lambda)B spectrum, and is substantially better than any previous hypernuclear experiment using magnetic spectrometers. The positions of the major excitations are found to be in agreement with a theoretical prediction and with a previous binding energy measurement, but additional structure is also observed in the core excited region, underlining the future promise of this technique.

  7. Spectroscopy of #Lambda#28Al, #Lambda#12B and #Lambda#7He by the (e,e(prime)K+) Reaction

    International Nuclear Information System (INIS)

    Matsumura, Akihiko

    2010-01-01

    Hypernuclear spectroscopy by the (e,e(prime)K + ) reaction is one of the powerful tools to investigate precise structures of hypernuclei and to study ΛN interaction. The second generation hypernuclear experiment at JLab Hall C(E01-011) was successfully performed in 2005, introducing the two novel experimental configurations, High resolution and large acceptance Kaon Spectrometer(HKS) and Tilt method. Thanks to these new configurations, various hypernuclei such as # Lambda# 28 Al, # Lambda# 12 B and # Lambda# 7 He were measured with precise energy resolution of 500 keV (FWHM). Obtained absolute binding energies and cross sections were compared with other experimental data and recent theoretical calculations based on shell model and cluster model. The results of this study provided new information on ΛN interaction.

  8. Radical Rearrangement Chemistry in Ultraviolet Photodissociation of Iodotyrosine Systems: Insights from Metastable Dissociation, Infrared Ion Spectroscopy, and Reaction Pathway Calculations.

    Science.gov (United States)

    Ranka, Karnamohit; Zhao, Ning; Yu, Long; Stanton, John F; Polfer, Nicolas C

    2018-05-29

    We report on the ultraviolet photodissociation (UVPD) chemistry of protonated tyrosine, iodotyrosine, and diiodotyrosine. Distonic loss of the iodine creates a high-energy radical at the aromatic ring that engages in hydrogen/proton rearrangement chemistry. Based on UVPD kinetics measurements, the appearance of this radical is coincident with the UV irradiation pulse (8 ns). Conversely, sequential UVPD product ions exhibit metastable decay on ca. 100 ns timescales. Infrared ion spectroscopy is capable of confirming putative structures of the rearrangement products as proton transfers from the imine and β-carbon hydrogens. Potential energy surfaces for the various reaction pathways indicate that the rearrangement chemistry is highly complex, compatible with a cascade of rearrangements, and that there is no preferred rearrangement pathway even in small molecular systems like these. Graphical Abstract.

  9. In situ Spectroscopy of Solid-State Chemical Reaction in PbBr2-Deposited CsBr Crystals

    Science.gov (United States)

    Kondo, Shin-ichi; Matsunaga, Toshihiro; Saito, Tadaaki; Asada, Hiroshi

    2003-09-01

    It is possible to measure the fundamental optical absorption spectra of CsPbBr3 and Cs4PbBr6, whose stability is predicted by the study of phase diagram in the binary system CsBr-PbBr2, by means of in situ optical absorption and reflection spectroscopy of thermally induced solid-state chemical reaction in PbBr2-deposited CsBr crystals. On heavy annealing of the crystals, the Pb2+ ions are uniformly dispersed in the crystal matrix. The present experiment provides a novel method for measuring intrinsic optical absorption of ternary metal halides and also for in situ monitoring of doping metal halide crystal with impurities (metal ions or halogen ions).

  10. High-resolution γ-ray spectroscopy of hyperfragments produced by stopped K- reactions

    International Nuclear Information System (INIS)

    Miwa, K.; Tanida, K.; Akikawa, H.; Fukao, Y.; Hiyama, E.; Hotchi, H.; Imai, K.; Miura, Y.; Mizunuma, K.; Nakamura, S.N.; Niiyama, M.; Ota, S.; Saha, P.K.; Takahashi, H.; Takahashi, T.; Tamura, H.; Terashima, S.; Togawa, M.; Ukai, M.

    2005-01-01

    We performed an experiment to measure γ rays of hyperfragments produced by stopped K- reactions on light (A= 1/2+) in 7 Λ Li with 10 B, 11 B and 12 C targets and obtained the γ-ray intensity to be (7.5+/-1.6)x10-4 per stopped K- for 10 B target. In addition, a candidate for a new hypernuclear γ ray was observed. These results show that this method is quite suitable for the systematic study of hypernuclei

  11. Nuclear structure of weakly bound radioactive nuclei through elastic and and inelastic scattering on proton. Impacts of the couplings induced by these exotic nuclei on direct reactions; Structure de noyaux radioactifs faiblement lies par diffusions elastiques et inelastiques sur proton. Effets des couplages induits par ces noyaux exotiques sur les reactions directes

    Energy Technology Data Exchange (ETDEWEB)

    Lapoux, V

    2005-09-15

    Information on the structure, spectroscopy and target interaction potentials of exotic nuclei can be inferred by interpreting measured data from direct reactions on proton such as elastic or inelastic scattering of proton (p,p') or one-nucleon transfer reaction (p,d). A series of experimental results has been obtained at the GANIL facilities on the setting composed of the MUST telescope array used for the detection of light charged-particles and of CATS beam detectors. This setting aims at measuring reactions on light proton or deuteron targets through reverse kinematics. Particularly, results on C{sup 10}, C{sup 11} and on direct reactions with the He{sup 8} beam of Spiral are presented. The first chapter is dedicated to the description of the most important theories concerning the nucleus. The experimental tools used to probe the nucleus are reported in the second chapter. The third and fourth chapters present the framework that has allowed us to analyse results from (p,p') and (p,d) reactions on weakly bound exotic nuclei. The last chapter is dedicated to the description of future experimental programs. (A.C.)

  12. Detecting paraprotein interference on a direct bilirubin assay by reviewing the photometric reaction data.

    Science.gov (United States)

    García-González, Elena; Aramendía, Maite; González-Tarancón, Ricardo; Romero-Sánchez, Naiara; Rello, Luis

    2017-07-26

    The direct bilirubin (D-Bil) assay on the AU Beckman Coulter instrumentation can be interfered by paraproteins, which may result in spurious D-Bil results. In a previous work, we took advantage of this fact to detect this interference, thus helping with the identification of patients with unsuspected monoclonal gammopathies. In this work, we investigate the possibility to detect interference based on the review of the photometric reactions, regardless of the D-Bil result. The D-Bil assay was carried out in a set of 2164 samples. It included a group of 164 samples with paraproteins (67 of which caused interference on the assay), as well as different groups of samples for which high absorbance background readings could also be expected (i.e. hemolyzed, lipemic, or icteric samples). Photometric reaction data were reviewed and receiver operating characteristics (ROC) curves were used to establish a cut-off for absorbance that best discriminates interference. The best cut-off was 0.0100 for the absorbance at the first photometric point of the complementary wavelength in the blank cuvette. Once the optimal cut-off for probable interference was selected, all samples analyzed in our laboratory that provided absorbance values above this cut-off were further investigated to try to discover paraproteins. During a period of 6 months, we detected 44 samples containing paraproteins, five of which belonged to patients with non-diagnosed monoclonal gammopathies. Review of the photometric reaction data permits the systematic detection of paraprotein interference on the D-Bil AU assay, even for samples for which reasonable results are obtained.

  13. Monitoring transcranial direct current stimulation induced changes in cortical excitability during the serial reaction time task.

    Science.gov (United States)

    Ambrus, Géza Gergely; Chaieb, Leila; Stilling, Roman; Rothkegel, Holger; Antal, Andrea; Paulus, Walter

    2016-03-11

    The measurement of the motor evoked potential (MEP) amplitudes using single pulse transcranial magnetic stimulation (TMS) is a common method to observe changes in motor cortical excitability. The level of cortical excitability has been shown to change during motor learning. Conversely, motor learning can be improved by using anodal transcranial direct current stimulation (tDCS). In the present study, we aimed to monitor cortical excitability changes during an implicit motor learning paradigm, a version of the serial reaction time task (SRTT). Responses from the first dorsal interosseous (FDI) and forearm flexor (FLEX) muscles were recorded before, during and after the performance of the SRTT. Online measurements were combined with anodal, cathodal or sham tDCS for the duration of the SRTT. Negative correlations between the amplitude of online FDI MEPs and SRTT reaction times (RTs) were observed across the learning blocks in the cathodal condition (higher average MEP amplitudes associated with lower RTs) but no significant differences in the anodal and sham conditions. tDCS did not have an impact on SRTT performance, as would be predicted based on previous studies. The offline before-after SRTT MEP amplitudes showed an increase after anodal and a tendency to decrease after cathodal stimulation, but these changes were not significant. The combination of different interventions during tDCS might result in reduced efficacy of the stimulation that in future studies need further attention. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  14. Direct reactions in inverse kinematics for nuclear structure studies far off stability at low incident energies

    International Nuclear Information System (INIS)

    Egelhof, P.

    1997-02-01

    The investigation of light-ion induced direct reactions with exotic beams in inverse kinematics gives access to a wide field of nuclear structure studies in the region far off stability. The present contribution will focus on the investigation of few-nucleon transfer reactions, which turn out to be most favourably studied with good-quality low-energy radioactive beams, as provided by the new generation of radioactive beam facilities presently planned or under construction at Caen, Grenoble, Munich, and elsewhere. An overview on the physics motivation, basically concerning nuclear structure and nuclear astrophysics questions, is given. Of particular interest are the nuclear shell model in the region far off stability, the two-body residual interaction in nuclei, the structure of halo nuclei, as well as the understanding of the r-process scenario. The experimental conditions, along with the experimental concept, for such measurements are discussed with particular emphasis on the kinematical conditions, the observables, as well as the appropriate detection schemes. The concept of a large solid angle TPC ionization chamber as an active target for experiments with low-energy radioactive beams is presented. It turns out to be a highly effective detection scheme, well suited for the present experimental conditions, at least for light exotic beams up to Z∼20. (orig.)

  15. On the theory of direct reactions with many particle final states

    International Nuclear Information System (INIS)

    Trautmann, D.; Baur, G.

    1977-01-01

    We study the theory of direct reactions with many particle final states. First, we concentrate on the DWBA formulation of the break-up of deuterons on heavy nuclei below the Coulomb barrier. Because there are no free parameters, this permits a clean test of the theory by comparing it to the experimental data. The agreement is very good. The theory is applied to the break-up of antideuteronic atoms. Then the effect of virtual deuteron break-up on Rutherford scattering is studied. It is small, but it seems to be measurable. Also the deuteron break-up above the Coulomb barrier can be well explained theoretically. In this context, small effects are studied briefly. A semiclassical theory of the break-up process is given, which results in an intuitive picture and a fast computational method. Our theory lends itself in a natural way to the study of stripping reactions to unbound states. The relation of stripping into the continuum to elastic scattering of the transferred particle on the same target nucleus is explained. Then the connection of stripping to bound and unbound states is established. Finally various examples of stripping of uncharged and charged particles into the continuum are given to illustrate the theory. Resonance wave functions describing the transferred particle are discussed. In a conclusion an outlook for possible future developments of experiment and theory is given. (author)

  16. Computational comparison of quantum-mechanical models for multistep direct reactions

    International Nuclear Information System (INIS)

    Koning, A.J.; Akkermans, J.M.

    1993-01-01

    We have carried out a computational comparison of all existing quantum-mechanical models for multistep direct (MSD) reactions. The various MSD models, including the so-called Feshbach-Kerman-Koonin, Tamura-Udagawa-Lenske and Nishioka-Yoshida-Weidenmueller models, have been implemented in a single computer system. All model calculations thus use the same set of parameters and the same numerical techniques; only one adjustable parameter is employed. The computational results have been compared with experimental energy spectra and angular distributions for several nuclear reactions, namely, 90 Zr(p,p') at 80 MeV, 209 Bi(p,p') at 62 MeV, and 93 Nb(n,n') at 25.7 MeV. In addition, the results have been compared with the Kalbach systematics and with semiclassical exciton model calculations. All quantum MSD models provide a good fit to the experimental data. In addition, they reproduce the systematics very well and are clearly better than semiclassical model calculations. We furthermore show that the calculated predictions do not differ very strongly between the various quantum MSD models, leading to the conclusion that the simplest MSD model (the Feshbach-Kerman-Koonin model) is adequate for the analysis of experimental data

  17. Action Video Games Improve Direction Discrimination of Parafoveal Translational Global Motion but Not Reaction Times.

    Science.gov (United States)

    Pavan, Andrea; Boyce, Matthew; Ghin, Filippo

    2016-10-01

    Playing action video games enhances visual motion perception. However, there is psychophysical evidence that action video games do not improve motion sensitivity for translational global moving patterns presented in fovea. This study investigates global motion perception in action video game players and compares their performance to that of non-action video game players and non-video game players. Stimuli were random dot kinematograms presented in the parafovea. Observers discriminated the motion direction of a target random dot kinematogram presented in one of the four visual quadrants. Action video game players showed lower motion coherence thresholds than the other groups. However, when the task was performed at threshold, we did not find differences between groups in terms of distributions of reaction times. These results suggest that action video games improve visual motion sensitivity in the near periphery of the visual field, rather than speed response. © The Author(s) 2016.

  18. Serial MR Spectroscopy Reveals a Direct Metabolic Effect of Cediranib in Glioblastoma

    Science.gov (United States)

    Kim, Heisoog; Catana, Ciprian; Ratai, Eva-Maria; Andronesi, Ovidiu C.; Jennings, D.; Batchelor, Tracy T.; Jain, Rakesh K.; Sorensen, A. Gregory

    2011-01-01

    Proton magnetic resonance spectroscopy (1H-MRS) is increasingly used in clinical studies of brain tumor to provide information about tissue metabolic profiles. In this study, we evaluated changes in the levels of metabolites predominant in recurrent glioblastoma (rGBM), to characterize the response of rGBM to anti-angiogenic therapy. We examined thirty-one rGBM patients treated with daily doses of cediranib, acquiring serial chemical shift imaging data at specific time points during the treatment regimen. We defined spectra from three regions of interest (ROIs)—enhancing tumor (ET), peritumoral tissue (PT), and normal tissue on the contralateral side (cNT)—in post-contrast T1-weighted images, and normalized the concentrations of N-acetylaspartate (NAA) and choline (Cho) in each ROI to the concentration of creatine in cNT (norCre). We analyzed the ratios of these normalized metabolites (i.e., NAA/Cho, NAA/norCre, and Cho/norCre) by averaging all patients and categorizing two different survival groups. Relative to pre-treatment values, NAA/Cho in ET was unchanged through day 28. However, after day 28, NAA/Cho significantly increased in relation to a significant increase in NAA/norCre and a decrease in Cho/norCre; interestingly, the observed trend was reversed after day 56, consistent with the clinical course of GBM recurrence. Notably, ROC analysis indicated that NAA/Cho in tumor shows a high prediction to 6-month overall survival. These metabolic changes in these rGBM patients strongly suggest a direct metabolic effect of cediranib, and might also reflect an anti-tumor response to anti-angiogenic treatment during the first two months of treatment. Further study is needed to confirm these findings. PMID:21507932

  19. Optical emission spectroscopy diagnostics of an atmospheric pressure direct current microplasma jet

    Energy Technology Data Exchange (ETDEWEB)

    Sismanoglu, B.N., E-mail: bogos@ita.b [Departamento de Fisica, Instituto Tecnologico de Aeronautica, Comando-Geral de Tecnologia Aeroespacial, Pca Marechal Eduardo Gomes 50, 12 228-900, Sao Jose dos Campos, SP (Brazil); Amorim, J., E-mail: jayr.amorim@bioetanol.org.b [Centro de Ciencia e Tecnologia do Bioetanol - CTBE, Caixa Postal 6170, 13083-970 Campinas, Sao Paulo (Brazil); Souza-Correa, J.A., E-mail: jorge.correa@bioetanol.org.b [Centro de Ciencia e Tecnologia do Bioetanol - CTBE, Caixa Postal 6170, 13083-970 Campinas, Sao Paulo (Brazil); Oliveira, C., E-mail: carlosf@ita.b [Departamento de Fisica, Instituto Tecnologico de Aeronautica, Comando-Geral de Tecnologia Aeroespacial, Pca Marechal Eduardo Gomes 50, 12 228-900, Sao Jose dos Campos, SP (Brazil); Gomes, M.P., E-mail: gomesmp@ita.b [Departamento de Fisica, Instituto Tecnologico de Aeronautica, Comando-Geral de Tecnologia Aeroespacial, Pca Marechal Eduardo Gomes 50, 12 228-900, Sao Jose dos Campos, SP (Brazil)

    2009-11-15

    This paper is about the use of optical emission spectroscopy as a diagnostic tool to determine the gas discharge parameters of a direct current (98% Ar-2% H{sub 2}) non-thermal microplasma jet, operated at atmospheric pressure. The electrical and optical behaviors were studied to characterize this glow discharge. The microplasma jet was investigated in the normal and abnormal glow regimes, for current ranging from 10 to 130 mA, at approx 220 V of applied voltage for copper cathode. OH (A {sup 2}SIGMA{sup +}, nu = 0 -> X {sup 2}PI, nu' = 0) rotational bands at 306.357 nm and also the 603.213 nm Ar I line, which is sensitive to van der Waals broadening, were used to determine the gas temperature, which ranges from 550 to 800 K. The electron number densities, ranging from 6.0 x 10{sup 14} to 1.4 x 10{sup 15} cm{sup -3}, were determined through a careful analysis of the main broadening mechanisms of the H{sub beta} line. From both 603.213 nm and 565.070 nm Ar I line broadenings, it was possible to obtain simultaneously electron number density and temperature (approx 8000 K). Excitation temperatures were also measured from two methods: from two Cu I lines and from Boltzmann-plot of 4p-4s and 5p-4s Ar I transitions. By employing H{sub alpha} line, the hydrogen atoms' H temperature was estimated (approx 18,000 K) and found to be surprisingly hotter than the excitation temperature.

  20. pH-dependent electron transfer reaction and direct bioelectrocatalysis of the quinohemoprotein pyranose dehydrogenase

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, Kouta [Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan); Matsumura, Hirotoshi; Ishida, Takuya [Department of Biomaterial Sciences, Graduate School of Agriculture and Life Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-8657 (Japan); Yoshida, Makoto [Department of Environmental and Natural Resource Science, Tokyo University of Agriculture and Technology, Fuchu, Tokyo 183-8509 (Japan); Igarashi, Kiyohiko; Samejima, Masahiro [Department of Biomaterial Sciences, Graduate School of Agriculture and Life Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-8657 (Japan); Ohno, Hiroyuki [Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan); Nakamura, Nobuhumi, E-mail: nobu1@cc.tuat.ac.jp [Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)

    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. - Highlights: • pH dependencies of activity were different for the reduction of cyt c and DCPIP. • DET-based bioelectrocatalysis of CcPDH was observed. • The similar pH-dependent profile was found with cyt c and electrode. • The present results suggested that IET reaction of CcPDH shows pH dependence.

  1. Dynamic structural change of the self-assembled lanthanum complex induced by lithium triflate for direct catalytic asymmetric aldol-Tishchenko reaction.

    Science.gov (United States)

    Horiuchi, Yoshihiro; Gnanadesikan, Vijay; Ohshima, Takashi; Masu, Hyuma; Katagiri, Kosuke; Sei, Yoshihisa; Yamaguchi, Kentaro; Shibasaki, Masakatsu

    2005-09-05

    The development of a direct catalytic asymmetric aldol-Tishchenko reaction and the nature of its catalyst are described. An aldol-Tishchenko reaction of various propiophenone derivatives with aromatic aldehydes was promoted by [LaLi3(binol)3] (LLB), and reactivity and enantioselectivity were dramatically enhanced by the addition of lithium trifluoromethanesulfonate (LiOTf). First, we observed a dynamic structural change of LLB by the addition of LiOTf using 13C NMR spectroscopy, electronspray ionization mass spectrometry (ESI-MS), and cold-spray ionization mass spectrometry (CSI-MS). X-ray crystallography revealed that the structure of the newly generated self-assembled complex was a binuclear [La2Li4(binaphthoxide)5] complex 6. A reverse structural change of complex 6 to LLB by the addition of one equivalent of Li2(binol) was also confirmed by ESI-MS and experimental results. The drastic concentration effects on the direct catalytic asymmetric aldol-Tishchenko reaction suggested that the addition of LiOTf to LLB generated an active oligomeric catalyst species.

  2. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  3. Capturing Structural Snapshots during Photochemical Reactions with Ultrafast Raman Spectroscopy: From Materials Transformation to Biosensor Responses.

    Science.gov (United States)

    Fang, Chong; Tang, Longteng; Oscar, Breland G; Chen, Cheng

    2018-06-21

    Chemistry studies the composition, structure, properties, and transformation of matter. A mechanistic understanding of the pertinent processes is required to translate fundamental knowledge into practical applications. The current development of ultrafast Raman as a powerful time-resolved vibrational technique, particularly femtosecond stimulated Raman spectroscopy (FSRS), has shed light on the structure-energy-function relationships of various photosensitive systems. This Perspective reviews recent work incorporating optical innovations, including the broad-band up-converted multicolor array (BUMA) into a tunable FSRS setup, and demonstrates its resolving power to watch metal speciation and photolysis, leading to high-quality thin films, and fluorescence modulation of chimeric protein biosensors for calcium ion imaging. We discuss advantages of performing FSRS in the mixed time-frequency domain and present strategies to delineate mechanisms by tracking low-frequency modes and systematically modifying chemical structures with specific functional groups. These unique insights at the chemical-bond level have started to enable the rational design and precise control of functional molecular machines in optical, materials, energy, and life sciences.

  4. Structures and reaction pathways of the molybdenum centres of sulfite-oxidizing enzymes by pulsed EPR spectroscopy.

    Science.gov (United States)

    Enemark, John H; Astashkin, Andrei V; Raitsimring, Arnold M

    2008-12-01

    SOEs (sulfite-oxidizing enzymes) are physiologically vital and occur in all forms of life. During the catalytic cycle, the five-co-ordinate square pyramidal oxo-molybdenum active site passes through the Mo(V) state, and intimate details of the structure can be obtained from variable frequency pulsed EPR spectroscopy through the hyperfine and nuclear quadrupole interactions of nearby magnetic nuclei. By employing variable spectrometer operational frequencies, it is possible to optimize the measurement conditions for difficult quadrupolar nuclei of interest (e.g. (17)O, (33)S, (35)Cl and (37)Cl) and to simplify the interpretation of the spectra. Isotopically labelled model Mo(V) compounds provide further insight into the electronic and geometric structures and chemical reactions of the enzymes. Recently, blocked forms of SOEs having co-ordinated sulfate, the reaction product, were detected using (33)S (I=3/2) labelling. This blocking of product release is a possible contributor to fatal human sulfite oxidase deficiency in young children.

  5. Solid-state reaction in Ti/Ni multilayered films studied by using magneto-optical spectroscopy

    CERN Document Server

    Lee, Y P; Kim, K W; Kim, C G; Kudryavtsev, Y V; Nemoshkalenko, V V; Szymanski, B

    2000-01-01

    A comparative study of the solid-state reaction (SSR) in a series of Ti/Ni multilayered films (MLDs) with bilayer periods of 0.65-22.2 nm and a constant Ti to Ni sublayer thickness ratio was performed by using experimental and computer-simulated magneto-optical (MO) spectroscopy based on different models of MLFs, as well as x-ray diffraction (XRD). The spectral and sublayer thickness dependences of the MO properties of the Ti/Ni MLFs were explained on the basis of the electromagnetic theory. The existence of a threshold nominal Ni-sublayer thickness of about 3 nm for the as-deposited Ti/Ni MLF to observe of the equatorial Kerr effect was explained by a solid-state reaction which formed nonmagnetic alloyed regions between pure components during the MLF deposition. The SSR in the Ti/Ni MLFs, which was caused by the low temperature annealing, led to the formation of an amorphous Ti-Ni alloy and took place mainly in the Ti/Ni MLFs with ''thick'' sublayers. For the caes of Ti/Ni MLFs, the MO approach turned out to...

  6. Combined operando X-ray diffraction–electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries

    Science.gov (United States)

    Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

    2015-01-01

    Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ∼20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4. PMID:26345306

  7. Combined operando X-ray diffraction-electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries.

    Science.gov (United States)

    Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

    2015-09-08

    Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ∼20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4.

  8. Direct determination of enthalpies of solid phase reactions by immersion method; Determination directe des enthalpies de reaction en phase solide par une methode de plongee

    Energy Technology Data Exchange (ETDEWEB)

    Roux, A; Richard, M; Eyraud, L; Stevanovic, M; Elston, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-07-01

    It is not generally possible to measure the enthalpy change corresponding to solid phase reactions using the dynamic differential thermal analysis method because these reactions are usually too slow at the temperature of operation of present equipment. A ballistic differential thermal analysis apparatus has been developed which is based on an immersion-compensation method; it overcomes the difficulties previously encountered. This apparatus has been used after calibration for determining the enthalpies of formation of calcium and cadmium titanates. and also the Wigner energies of BeO, MgO and Al{sub 2}O{sub 3} samples irradiated at variable dose at a temperature of under 100 deg. C. (authors) [French] Il n'est generalement pas possible de mesurer la variation d'enthalpie correspondant aux reactions en phase solide par la methode d'analyse thermique differentielle dynamique. En effet, ces reactions sont le plus souvent trop lentes aux temperatures d'utilisation des dispositifs actuels. Un appareil d'analyse thermique differentielle balistique, base sur une methode de plongee avec compensation, a ete mis au point et permet de surmonter les difficultes precedentes. Apres etalonnages, cet appareil a ete utilise pour la determination des enthalpies de formation du titanate de calcium et du titanate de cadmium ainsi que pour celle des energies Wigner emmagasinees dans des echantillons de BeO, MgO et Al{sub 2}O{sub 3} irradies a une temperature inferieure a 100 deg. C et a differentes doses. (auteurs)

  9. Investigation of direct photon production in 200 A GeV S + Au reactions

    International Nuclear Information System (INIS)

    1994-01-01

    Direct thermal photons in the p T range of 0--5 GeV/c are expected to provide a sensitive probe of the early conditions of the Quark Gluon Plasma which may be formed in relativistic heavy ion collisions. The production of single photons in 200 A GeV S + Au reactions has been investigated using the 3,800 element Pbglass calorimeter of CERN experiment WA80. Neutral π 0 and η cross sections have been measured via their two-photon decay branch yields. The measured π 0 and η cross sections have been used to calculate the expected inclusive yield of decay photons. Excess photon yield, beyond that attributed to radiative decays and background sources, may be associated with thermal photon emission. Excess, ''direct'' photon yields have been extracted from high-statistics S + Au photon data for different event centrality classes. A slight excess photon yield above that which may be accounted for by hadronic decays was observed for central events

  10. Transformation of meta-stable calcium silicate hydrates to tobermorite: reaction kinetics and molecular structure from XRD and NMR spectroscopy

    Science.gov (United States)

    2009-01-01

    Understanding the integrity of well-bore systems that are lined with Portland-based cements is critical to the successful storage of sequestered CO2 in gas and oil reservoirs. As a first step, we investigate reaction rates and mechanistic pathways for cement mineral growth in the absence of CO2 by coupling water chemistry with XRD and NMR spectroscopic data. We find that semi-crystalline calcium (alumino-)silicate hydrate (Al-CSH) forms as a precursor solid to the cement mineral tobermorite. Rate constants for tobermorite growth were found to be k = 0.6 (± 0.1) × 10-5 s-1 for a solution:solid of 10:1 and 1.6 (± 0.8) × 10-4 s-1 for a solution:solid of 5:1 (batch mode; T = 150°C). This data indicates that reaction rates for tobermorite growth are faster when the solution volume is reduced by half, suggesting that rates are dependent on solution saturation and that the Gibbs free energy is the reaction driver. However, calculated solution saturation indexes for Al-CSH and tobermorite differ by less than one log unit, which is within the measured uncertainty. Based on this data, we consider both heterogeneous nucleation as the thermodynamic driver and internal restructuring as possible mechanistic pathways for growth. We also use NMR spectroscopy to characterize the site symmetry and bonding environment of Al and Si in a reacted tobermorite sample. We find two [4]Al coordination structures at δiso = 59.9 ppm and 66.3 ppm with quadrupolar product parameters (PQ) of 0.21 MHz and 0.10 MHz (± 0.08) from 27Al 3Q-MAS NMR and speculate on the Al occupancy of framework sites by probing the protonation environment of Al metal centers using 27Al{1H}CP-MAS NMR. PMID:19144195

  11. Equilibrium constants in aqueous lanthanide and actinide chemistry from time-resolved fluorescence spectroscopy: The role of ground and excited state reactions

    International Nuclear Information System (INIS)

    Billard, I.; Luetzenkirchen, K.

    2003-01-01

    Equilibrium constants for aqueous reactions between lanthanide or actinide ions and (in-) organic ligands contain important information for various radiochemical problems, such as nuclear reprocessing or the migration of radioelements in the geosphere. We study the conditions required to determine equilibrium constants by time-resolved fluorescence spectroscopy measurements. Based on a simulation study it is shown that the possibility to determine equilibrium constants depends upon the reaction rates in the photoexcited states of the lanthanide or actinide ions. (orig.)

  12. The ({sup 18}O, {sup 16}O) reaction as a probe for nuclear spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cappuzzello, F.; Bondì, M.; Nicolosi, D.; Tropea, S. [INFN - Laboratori Nazionali del Sud, Via S. Sofia 62, I-95125 Catania, Italy and Dipartimento di Fisica e Astronomia, Università di Catania, Via S. Sofia 64, I-95125 Catania (Italy); Agodi, A.; Carbone, D.; Cavallaro, M.; Cunsolo, A. [INFN - Laboratori Nazionali del Sud, Via S. Sofia 62, I-95125 Catania (Italy); Borello-Lewin, T.; Rodrigues, M. R. D. [Instituto de Física - Universidade de São Paulo, Rua do Matão Travessa R Nr.187, 05508-090 Cidade Universitária, São Paulo (Brazil); De Napoli, M. [INFN - Sezione di Catania, Via S. Sofia 64, I-95125 Catania (Italy); Linares, R. [Instituto de Física, Universidade Federal Fluminense, Avenida Litoranea s/n, Gragoata, 24210-340, Niteroi, RJ (Brazil); Foti, A. [Dipartimento di Fisica e Astronomia, Università di Catania, Via S. Sofia 64, I-95125 Catania, Italy and INFN - Sezione di Catania, Via S. Sofia 64, I-95125 Catania (Italy)

    2014-11-11

    The response of nuclei to the ({sup 18}O, {sup 16}O) two-neutron transfer reaction at 84 MeV incident energy has been systematically studied at the Catania INFN-LNS laboratory. The experiments were performed using several solid targets from light ({sup 9}Be, {sup 11}B, {sup 12,13}C, {sup 16}O, {sup 28}Si) to heavy ones ({sup 58,64}Ni, {sup 120}Sn, {sup 208}Pb). The {sup 16}O ejectiles were detected at forward angles by the MAGNEX magnetic spectrometer. Exploiting the large momentum acceptance (−10%, +14%) and solid angle (50 msr) of the spectrometer, energy spectra were obtained with a relevant yield up to about 20 MeV excitation energy. The application of the powerful trajectory reconstruction technique did allow to get energy spectra with energy resolution of about 150 keV and angular distributions with angular resolution better than 0.3°. A common feature observed with light nuclei is the appearance of unknown resonant structures at high excitation energy. The strong population of these latter together with the measured width can reveal the excitation of a collective mode connected with the transfer of a pair.

  13. Imaging the electron transfer reaction of Ne2+ with Ar using position-sensitive coincidence spectroscopy

    International Nuclear Information System (INIS)

    Harper, Sarah M; Hu Wanping; Price, Stephen D

    2002-01-01

    A new experiment, employing position-sensitive detection coupled with time-of-flight mass spectrometry, has been used to investigate the single-electron transfer reaction between Ne 2+ and Ar by detecting the resulting pairs of singly charged ions in coincidence. The experimental technique allows the determination of the individual velocity vectors of the ionic products, in the centre-of-mass frame, for each reactive event detected. The experiments show that forward scattering dominates the reactivity, although a bimodal angular distribution is apparent. In addition, the spectra show that at laboratory frame collision energies from 4-14 eV the reactivity is dominated by Ne 2+ (2p 4 , 3 P) accepting an electron from an argon atom to form the ground state of Ne + together with an Ar + ion in an excited electronic level, predominantly arising from the Ar + (3s 2 3p 4 3d) configuration. The form of this reactivity, and the differences between the reactivity observed in these experiments and those performed at higher collision energies, are well reproduced by Landau-Zener theory

  14. Quantitative assessment of the ion-beam irradiation induced direct damage of nucleic acid bases through FTIR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Qing, E-mail: huangq@ipp.ac.cn [Key Laboratory of Ion Beam Bio-engineering, Institute of Technical Biology and Agriculture Engineering, Hefei Institutes of Physical Science, Chinese Academy of Sciences (China); University of Science and Technology of China, Hefei 230029, Anhui (China); Su, Xi; Yao, Guohua; Lu, Yilin; Ke, Zhigang; Liu, Jinghua; Wu, Yuejin; Yu, Zengliang [Key Laboratory of Ion Beam Bio-engineering, Institute of Technical Biology and Agriculture Engineering, Hefei Institutes of Physical Science, Chinese Academy of Sciences (China)

    2014-07-01

    Energetic particles exist ubiquitously in nature, and when they hit DNA molecules in organisms, they may induce critical biological effects such as mutation. It is however still a challenge to measure directly and quantitatively the damage imposed by the energetic ions on target DNA molecules. In this work we attempted to employ Fourier transformation infrared (FTIR) spectroscopy to assess the ion-induced direct damage of four nucleic acid bases, namely, thymine (T), cytosine (C), guanine (G), and adenine (A), which are the building blocks of DNA molecules. The samples were prepared as thin films, irradiated by argon ion-beams at raised ion fluences, and in the meantime measured by FTIR spectroscopy for the damage in a quasi-in-situ manner. It was found that the low-energy ion-beam induced radiosensitivity of the four bases shows the sequence G > T > C > A, wherein the possible mechanism was also discussed.

  15. Crystalline state photoreactions direct observation of reaction processes and metastable intermediates

    CERN Document Server

    Ohashi, Yuji

    2014-01-01

    Offering some 300 references, this book focuses on chemical reactions in the crystalline state. The reactions span many fields in inorganic and organic chemistry, making this a useful resource for inorganic, organic and physical chemists and graduate students.

  16. New directions in point-contact spectroscopy based on scanning tunneling microscopy techniques (Review Article)

    International Nuclear Information System (INIS)

    Tartaglini, E.; Verhagen, T.G.A.; Galli, F.; Trouwborst, M.L.; Aarts, J.; Van-Ruitebbeek, J.M.; Muller, R.; Shiota, T.

    2013-01-01

    Igor Yanson showed 38 years ago for the first time a point-contact measurement where he probed the energy resolved spectroscopy of the electronic scattering inside the metal. Since this first measurement, the pointcontact spectroscopy (PCS) technique improved enormously. The application of the scanning probe microscopy (SPM) techniques in the late 1980s allowed achieving contacts with a diameter of a single atom. With the introduction of the mechanically controlled break junction technique, even spectroscopy on freely suspended chains of atoms could be performed. In this paper, we briefly review the current developments of PCS and show recent experiments in advanced scanning PCS based on SPM techniques. We describe some results obtained with both needle-anvil type of point contacts and scanning tunneling microscopy (STM). We also show our first attempt to lift up with a STM a chain of single gold atoms from a Au(110) surface.

  17. Pigment organization and their interactions in reaction centers of photosystem II: optical spectroscopy at 6 K of reaction centers with modified pheophytin composition.

    Science.gov (United States)

    Germano, M; Shkuropatov, A Y; Permentier, H; de Wijn, R; Hoff, A J; Shuvalov, V A; van Gorkom, H J

    2001-09-25

    Photosystem II reaction centers (RC) with selectively exchanged pheophytin (Pheo) molecules as described in [Germano, M., Shkuropatov, A. Ya., Permentier, H., Khatypov, R. A., Shuvalov, V. A., Hoff, A. J., and van Gorkom, H. J. (2000) Photosynth. Res. 64, 189-198] were studied by low-temperature absorption, linear and circular dichroism, and triplet-minus-singlet absorption-difference spectroscopy. The ratio of extinction coefficients epsilon(Pheo)/epsilon(Chl) for Q(Y) absorption in the RC is approximately 0.40 at 6 K and approximately 0.45 at room temperature. The presence of 2 beta-carotenes, one parallel and one perpendicular to the membrane plane, is confirmed. Absorption at 670 nm is due to the perpendicular Q(Y) transitions of the two peripheral chlorophylls (Chl) and not to either Pheo. The "core" pigments, two Pheo and four Chl absorb in the 676-685 nm range. Delocalized excited states as predicted by the "multimer model" are seen in the active branch. The inactive Pheo and the nearby Chl, however, mainly contribute localized transitions at 676 and 680 nm, respectively, although large CD changes indicate that exciton interactions are present on both branches. Replacement of the active Pheo prevents triplet formation, causes an LD increase at 676 and 681 nm, a blue-shift of 680 nm absorbance, and a bleach of the 685 nm exciton band. The triplet state is mainly localized on the Chl corresponding to B(A) in purple bacteria. Both Pheo Q(Y) transitions are oriented out of the membrane plane. Their Q(X) transitions are parallel to that plane, so that the Pheos in PSII are structurally similar to their homologues in purple bacteria.

  18. Evidence of multiband superconductivity in the quaternary borocarbide superconductor YNi2B2C using directional point-contact spectroscopy

    International Nuclear Information System (INIS)

    Raychaudhuri, Pratap; Sheet, Goutam; Mukhopadhyay, Sourin; Takeya, H.

    2007-01-01

    In this paper, we review our recent investigations on the gap anisotropy of the quaternary borocarbide superconductor YNi 2 B 2 C using directional point-contact spectroscopy. Through a detailed study of the temperature and magnetic field dependence of the superconducting energy gaps we show that the gap anisotropy in this material originates from electrons on different Fermi sheets having very different Fermi velocities. The gap anisotropy in this material is therefore well explained through a multiband scenario where electrons in different k-directions have very different electron-phonon coupling strength

  19. Intrinsic reaction kinetics of coal char combustion by direct measurement of ignition temperature

    International Nuclear Information System (INIS)

    Kim, Ryang-Gyoon; Jeon, Chung-Hwan

    2014-01-01

    A wire heating reactor that can use a synchronized experimental method was developed to obtain the intrinsic kinetics of large coal char particles ranging in size from 0.4 to 1 mm. This synchronization system consists of three parts: a thermocouple wire for both heating and direct measurement of the particle temperature, a photodetector sensor for determining ignition/burnout points by measuring the intensity of luminous emission from burning particles, and a high-speed camera–long-distance microscope for observing and recording the movement of luminous zone directly. Coal char ignition was found to begin at a spot on the particle's external surface and then moved across the entire particle. Moreover, the ignition point determined according to the minimum of dT/dt is a spot point and not a full growth point. The ignition temperature of the spot point rises as the particle diameter increases. A spot ignition model, which describes the ignition in terms of the internal conduction and external/internal oxygen diffusion, was then developed to evaluate the intrinsic kinetics and predict the ignition temperature of the coal char. Internal conduction was found to be important in large coal char particles because its effect becomes greater than that of oxygen diffusion as the particle diameter increases. In addition, the intrinsic kinetics of coal char obtained from the spot ignition model for two types of coal does not differ significantly from the results of previous investigators. -- Highlights: • A novel technique was used to measure the coal char particle temperature. • The ignition point determined from a dT/dt minimum is a spot ignition point. • A spot ignition model was suggested to analyze the intrinsic reaction kinetics of coal char. • Internal conduction has to be considered in order to evaluate the intrinsic kinetics for larger particle (above 1 mm)

  20. Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

    Science.gov (United States)

    Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

    2018-04-01

    The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

  1. Acetate self-mixing and direct thermal reaction for preparation of LiCoO2

    International Nuclear Information System (INIS)

    Jung, Bum-Young; Kang, Hyun-Koo; Jeong, In-Seong; Han, Kyoo-Seung; Lee, Youngil; Choo, Jaebum; Ryu, Kwang Sun

    2004-01-01

    Layered LiCoO 2 as a cathode material for rechargeable lithium battery is prepared using the acetate self-mixing method. Using this method, the preparation procedure consists of just two steps: spontaneous and homogeneous mixing of molten acetates at 80 deg. C, as well as direct thermal reaction at high temperature without any pulverization, grinding, agglomeration, particle morphology controlling, particle size controlling, and even artificial stirring of reactants. When lithium and cobalt acetates are exposed to the temperature of 80 deg. C, they can be fluidized substances by themselves without any solvents and spontaneously mixed together. In this way, layered LiCoO 2 phase is prepared by just simple heat treatment. The heating at 350 deg. C is interposed to accomplish steady intermediate phase translation without any intermittent cooling. The 7 Li MAS NMR and Raman spectra upon the thermal exposure of the reactants demonstrate the feature of the spontaneous mixing process of the molten reactants. The LiCoO 2 prepared by the acetate self-mixing method show quite prospective properties as a cathode material for lithium rechargeable battery, an initial discharge capacity of 149.5 mAh/g and the discharge capacity retention of 98.9% and 97.5% after 10 and 20 cycles, respectively

  2. Description of heavy-ion fusion in terms of direct reaction theory

    International Nuclear Information System (INIS)

    Hong, S.W.

    1987-01-01

    A direct reaction description of the heavy-ion fusion, proposed by Udagawa, Kim and Tamura, has been successfully used in calculating the fusion cross sections and the spin distributions for a number of systems in the energy regions from the sub-barrier to the above-barrier region. A fusion potential is introduced in this theory and the radius of the fusion potential is treated as an adjustable parameter. The theory is thus a one-parameter theory. The results obtained by Udagawa, Kim and Tamura showed that the radius parameter ranges from 1.4 to 1.5 fm, which is much larger than the radius (1.0 fm) used in other models. A hard evidence is shown to demonstrate the necessity of the long-ranged fusion potential radius in the near-barrier region. In the above-barrier region, the use of the energy-dependent optical potential and the energy-dependent fusion potential radius is proved to be essential in reproducing the measured fusion cross sections. As a further application of the theory, the double folded potential model is utilized to provide the real part of the optical potential. The imaginary part of the optical potential is determined so that not only the elastic scattering but also the fusion cross sections can be reproduced

  3. Colorimetry and photoacoustic spectroscopy as suitable tools for direct determination of cocoa powder in confectionary products

    NARCIS (Netherlands)

    Doka, O.; Pragai, E.; Bicanic, D.D.; Kulcsar, R.

    2013-01-01

    Laser photoacoustic spectroscopy (PAS) and colorimetry have been used to rapidly and accurately determine the content of fat-free cocoa solids in dark chocolates. Both techniques are inexpensive and require only a one-time calibration step versus a method capable of absolute concentration

  4. Bright trions in direct-bandgap silicon nanocrystals revealed bylow-temperature single-nanocrystal spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Kůsová, Kateřina; Pelant, Ivan; Valenta, J.

    2015-01-01

    Roč. 4, Oct (2015), e336 ISSN 2047-7538 R&D Projects: GA ČR(CZ) GBP108/12/G108; GA ČR GPP204/12/P235 Institutional support: RVO:68378271 Keywords : silicon nanocrystals * single-nanocrystal spectroscopy * luminescing trions Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 13.600, year: 2015

  5. Comparison of TiO2 photocatalysis, electrochemically assisted Fenton reaction and direct electrochemistry for simulation of phase I metabolism reactions of drugs.

    Science.gov (United States)

    Ruokolainen, Miina; Gul, Turan; Permentier, Hjalmar; Sikanen, Tiina; Kostiainen, Risto; Kotiaho, Tapio

    2016-02-15

    The feasibility of titanium dioxide (TiO2) photocatalysis, electrochemically assisted Fenton reaction (EC-Fenton) and direct electrochemical oxidation (EC) for simulation of phase I metabolism of drugs was studied by comparing the reaction products of buspirone, promazine, testosterone and 7-ethoxycoumarin with phase I metabolites of the same compounds produced in vitro by human liver microsomes (HLM). Reaction products were analysed by UHPLC-MS. TiO2 photocatalysis simulated the in vitro phase I metabolism in HLM more comprehensively than did EC-Fenton or EC. Even though TiO2 photocatalysis, EC-Fenton and EC do not allow comprehensive prediction of phase I metabolism, all three methods produce several important metabolites without the need for demanding purification steps to remove the biological matrix. Importantly, TiO2 photocatalysis produces aliphatic and aromatic hydroxylation products where direct EC fails. Furthermore, TiO2 photocatalysis is an extremely rapid, simple and inexpensive way to generate oxidation products in a clean matrix and the reaction can be simply initiated and quenched by switching the UV lamp on/off. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Electrochemical kinetics and X-ray absorption spectroscopy investigations of select chalcogenide electrocatalysts for oxygen reduction reaction applications

    International Nuclear Information System (INIS)

    Ziegelbauer, Joseph M.; Murthi, Vivek S.; O'Laoire, Cormac; Gulla, Andrea F.; Mukerjee, Sanjeev

    2008-01-01

    Transition metal-based chalcogenide electrocatalysts exhibit a promising level of performance for oxygen reduction reaction applications while offering significant economic benefits over the state of the art Pt/C systems. The most active materials are based on Ru x Se y clusters, but the toxicity of selenium will most likely limit their embrace by the marketplace. Sulfur-based analogues do not suffer from toxicity issues, but suffer from substantially less activity and stability than their selenium brethren. The structure/property relationships that result in these properties are not understood due to ambiguities regarding the specific morphologies of Ru x S y -based chalcogenides. To clarify these properties, an electrochemical kinetics study was interpreted in light of extensive X-ray diffraction, scanning electron microscopy, and in situ X-ray absorption spectroscopy evaluations. The performance characteristics of ternary M x Ru y S z /C (M = Mo, Rh, or Re) chalcogenide electrocatalysts synthesized by the now-standard low-temperature nonaqueous (NA) route are compared to commercially available (De Nora) Rh- and Ru-based systems. Interpretation of performance differences is made in regards to bulk and surface properties of these systems. In particular, the overall trends of the measured activation energies in respect to increasing overpotential and the gross energy values can be explained in regards to these differences

  7. F/Cl + C2H2 reactions: Are the addition and hydrogen abstraction direct processes?

    International Nuclear Information System (INIS)

    Li Jilai; Geng Caiyun; Huang Xuri; Zhan Jinhui; Sun Chiachung

    2006-01-01

    The reactions of atomic radical F and Cl with acetylene have been studied theoretically using ab initio quantum chemistry methods and transition state theory. The doublet potential energy surfaces were calculated at the CCSD(T)/aug-cc-pVDZ//CCSD/6-31G(d,p), CCSD(T)/aug-cc-pVDZ//UMP2/6-311++G(d,p) and compound method Gaussian-3 levels. Two reaction mechanisms including the addition-elimination and the hydrogen abstraction reaction mechanisms are considered. In the addition-elimination reactions, the halogen atoms approach C 2 H 2 , perpendicular to the C≡C triple bond, forming the pre-reactive complex C1 at the reaction entrance. C1 transforms to intermediate isomer I1 via transition state TSC1/1 with a negative/small barrier for C 2 H 2 F/C 2 H 2 Cl system, which can proceed by further eliminating H atom endothermally. While the hydrogen abstraction reactions also involve C1 for the fluorine atom abstraction of hydrogen, yet the hydrogen abstraction by chlorine atom first forms a collinear hydrogen-bonded complex C2. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. According to our results, the presence of pre-reactive complexes indicates that the simple hydrogen abstraction and addition in the halogen atoms reaction with unsaturated hydrocarbon should be more complex. Furthermore, based on the analysis of the kinetics of all channels through which the addition and abstraction reactions proceed, we expect that the actual feasibility of the reaction channels may depend on the reaction conditions in the experiment. The present study may be helpful for probing the mechanisms of the title reactions and understanding the halogen chemistry

  8. Characterization of TiAlN thin film annealed under O2 by in situ time of flight direct recoil spectroscopy/mass spectroscopy of recoiled ions and ex situ x-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Tempez, A.; Bensaoula, A.; Schultz, A.

    2002-01-01

    The oxidation of an amorphous TiAlN coating has been studied by in situ direct recoil spectroscopy (DRS) and mass spectroscopy of recoiled ions (MSRI) and ex situ x-ray photoelectron spectroscopy (XPS). DRS and MSRI monitored the changes in surface composition as the sample was heated to 460 deg. C under an 18 O 2 pressure of 10 -6 Torr. Angular resolved XPS data were acquired for thickness-dependence information. The initial surface was partially oxidized from air exposure. Both DRS and XPS showed the Al-rich near surface and the presence of N in the subsurface. As shown by DRS and MSRI, oxidation at elevated temperatures yielded surface nitrogen loss and Ti enrichment. XPS confirmed the preferential formation of TiO 2 on the surface. This study also provides a comparison between the direct recoil (neutrals and ions) and the ionic recoil signals. In our conditions, the negative ionic fraction of all elements except H tracks their true surface content variations given by DRS. The results were compared with early work performed on identical samples. In this case the TiAlN film was oxidized with an O 2 pressure in the mTorr range and the surface changes are followed in situ by positive MSRI and XPS. This experiment also indicates that Al and N are buried under TiO 2 but from 600 deg. C

  9. Direct correlation of charge transfer absorption with molecular donor:acceptor interfacial area via photothermal deflection spectroscopy

    KAUST Repository

    Domingo, Ester

    2015-04-09

    We show that the Charge Transfer (CT) absorption signal in bulk-heterojunction (BHJ) solar cell blends, measured by photothermal deflection spectroscopy (PDS), is directly proportional to the density of molecular donor/acceptor interfaces. Since the optical transitions from ground state to the interfacial CT state are weakly allowed at photon energies below the optical gap of both donor and acceptor, we can exploit the use of this sensitive linear absorption spectroscopy for such quantification. Moreover, we determine the absolute molar extinction coefficient of the CT transition for an archetypical polymer-fullerene interface. The latter is ~100 times lower than the extinction coefficient of the donor chromophore involved, allowing us to experimentally estimate the transition dipole moment (0.3 D) and the electronic coupling between ground state and CT state to be on the order of 30 meV.

  10. Fabrication of a Schottky junction diode with direct growth graphene on silicon by a solid phase reaction

    International Nuclear Information System (INIS)

    Kalita, Golap; Hirano, Ryo; Ayhan, Muhammed E; Tanemura, Masaki

    2013-01-01

    We demonstrate fabrication of a Schottky junction diode with direct growth graphene on n-Si by the solid phase reaction approach. Metal-assisted crystallization of a-C thin film was performed to synthesize transfer-free graphene directly on a SiO 2 patterned n-Si substrate. Graphene formation at the substrate and catalyst layer interface is achieved in presence of a Co catalytic and CoO carbon diffusion barrier layer. The as-synthesized material shows a linear current–voltage characteristic confirming the metallic behaviour of the graphene structure. The direct grown graphene on n-Si substrate creates a Schottky junction with a potential barrier of 0.44 eV and rectification diode characteristic. Our finding shows that the directly synthesized graphene on Si substrate by a solid phase reaction process can be a promising technique to fabricate an efficient Schottky junction device. (paper)

  11. Magnesium stearine production via direct reaction of palm stearine and magnesium hydroxide

    Science.gov (United States)

    Pratiwi, M.; Ylitervo, P.; Pettersson, A.; Prakoso, T.; Soerawidjaja, T. H.

    2017-06-01

    The fossil oil production could not compensate with the increase of its consumption, because of this reason the renewable alternative energy source is needed to meet this requirement of this fuel. One of the methods to produce hydrocarbon is by decarboxylation of fatty acids. Vegetable oil and fats are the greatest source of fatty acids, so these can be used as raw material for biohydrocarbon production. From other researchers on their past researchs, by heating base soap from divalent metal, those metal salts will decarboxylate and produce hydrocarbon. This study investigate the process and characterization of magnesium soaps from palm stearine by Blachford method. The metal soaps are synthesized by direct reaction of palm stearine and magnesium hydroxide to produce magnesium stearine and magnesium stearine base soaps at 140-180°C and 6-10 bar for 3-6 hours. The operation process which succeed to gain metal soaps is 180°C, 10 bar, for 3-6 hours. These metal soaps are then compared with commercial magnesium stearate. Based on Thermogravimetry Analysis (TGA) results, the decomposition temperature of all the metal soaps were 250°C. Scanning Electron Microscope with Energy Dispersive X-ray (SEM-EDX) analysis have shown the traces of sodium sulphate for magnesium stearate commercial and magnesium hydroxide for both type of magnesium stearine soaps. The analysis results from Microwave Plasma-Atomic Emission Spectrometry (MP-AES) have shown that the magnesium content of magnesium stearine approximate with magnesium stearate commercial and lower compare with magnesium stearine base soaps. These experiments suggest that the presented saponification process method could produced metal soaps comparable with the commercial metal soaps.

  12. Direct Measurements of Half-Cycle Reaction Heats during Atomic Layer Deposition by Calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Lownsbury, James M. [Department; Gladden, James A. [Department; Campbell, Charles T. [Department; Department; Kim, In Soo [Materials; Martinson, Alex B. F. [Materials

    2017-10-05

    We introduce a new high-temperature adsorption calorimeter that approaches the ideal limit of a heat detector whereby the signal at any time is proportional to the heat power being delivered to the sample and prove its sensitivity for measuring pulse-to-pulse heats of half-reactions during atomic layer deposition (ALD) at 400 K. The heat dynamics of amorphous Al2O3 growth via sequential self-limiting surface reaction of trimethylaluminum (TMA) and H2O is clearly resolved. Calibration enables quantitation of the exothermic TMA and H2O half-reactions with high precision, -343 kJ/mol TMA and -251 kJ/mol H2O, respectively. A time resolution better than 1 ms is demonstrated, allowing for the deconvolution of at least two distinct surface reactions during TMA microdosing. It is further demonstrated that this method can provide the heat of reaction versus extent of reaction during each precursors half-reaction, thus providing even richer mechanistic information on the surface processes involved. The broad applicability of this novel calorimeter is demonstrated through excellent signal-to-noise ratios of less exothermic ALD half-reactions to produce TiO2 and MnO.

  13. Determination of metal impurities in MOX powder by direct current arc atomic emission spectroscopy. Application of standard addition method for direct analysis of powder sample

    International Nuclear Information System (INIS)

    Furuse, Takahiro; Taguchi, Shigeo; Kuno, Takehiko; Surugaya, Naoki

    2016-12-01

    Metal impurities in MOX powder obtained from uranium and plutonium recovered from reprocessing process of spent nuclear fuel have to be determined for its characterization. Direct current arc atomic emission spectroscopy (DCA-AES) is one of the useful methods for direct analysis of powder sample without dissolving the analyte into aqueous solution. However, the selection of standard material, which can overcome concerns such as matrix matching, is quite important to create adequate calibration curves for DCA-AES. In this study, we apply standard addition method using the certified U_3O_8 containing known amounts of metal impurities to avoid the matrix problems. The proposed method provides good results for determination of Fe, Cr and Ni contained in MOX samples at a significant quantity level. (author)

  14. Insight into organic reactions from the direct random phase approximation and its corrections

    Energy Technology Data Exchange (ETDEWEB)

    Ruzsinszky, Adrienn [Department of Physics, Temple University, Philadelphia, Pennsylvania 19122 (United States); Zhang, Igor Ying; Scheffler, Matthias [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany)

    2015-10-14

    The performance of the random phase approximation (RPA) and beyond-RPA approximations for the treatment of electron correlation is benchmarked on three different molecular test sets. The test sets are chosen to represent three typical sources of error which can contribute to the failure of most density functional approximations in chemical reactions. The first test set (atomization and n-homodesmotic reactions) offers a gradually increasing balance of error from the chemical environment. The second test set (Diels-Alder reaction cycloaddition = DARC) reflects more the effect of weak dispersion interactions in chemical reactions. Finally, the third test set (self-interaction error 11 = SIE11) represents reactions which are exposed to noticeable self-interaction errors. This work seeks to answer whether any one of the many-body approximations considered here successfully addresses all these challenges.

  15. Insight into organic reactions from the direct random phase approximation and its corrections

    International Nuclear Information System (INIS)

    Ruzsinszky, Adrienn; Zhang, Igor Ying; Scheffler, Matthias

    2015-01-01

    The performance of the random phase approximation (RPA) and beyond-RPA approximations for the treatment of electron correlation is benchmarked on three different molecular test sets. The test sets are chosen to represent three typical sources of error which can contribute to the failure of most density functional approximations in chemical reactions. The first test set (atomization and n-homodesmotic reactions) offers a gradually increasing balance of error from the chemical environment. The second test set (Diels-Alder reaction cycloaddition = DARC) reflects more the effect of weak dispersion interactions in chemical reactions. Finally, the third test set (self-interaction error 11 = SIE11) represents reactions which are exposed to noticeable self-interaction errors. This work seeks to answer whether any one of the many-body approximations considered here successfully addresses all these challenges

  16. Optical spectroscopy of an atomic nucleus: Progress toward direct observation of the {sup 229}Th isomer transition

    Energy Technology Data Exchange (ETDEWEB)

    Hehlen, Markus P., E-mail: hehlen@lanl.gov [Los Alamos National Laboratory, Mailstop E549, Los Alamos, NM 87545 (United States); Greco, Richard R. [Los Alamos National Laboratory, Mailstop E549, Los Alamos, NM 87545 (United States); Rellergert, Wade G.; Sullivan, Scott T. [Department of Physics and Astronomy, University of California, Los Angeles, CA 90095 (United States); DeMille, David [Department of Physics, Yale University, New Haven, CT 06511 (United States); Jackson, Robert A. [School of Physical and Geographical Sciences, Keele University, Keele, Staffordshire ST5 5BG (United Kingdom); Hudson, Eric R. [Department of Physics and Astronomy, University of California, Los Angeles, CA 90095 (United States); Torgerson, Justin R. [Los Alamos National Laboratory, Mailstop E549, Los Alamos, NM 87545 (United States)

    2013-01-15

    The nucleus of the thorium-229 isotope possesses a first excited nuclear state ({sup 229m}Th) at an exceptionally low energy of 7.8{+-}0.5 eV above the nuclear ground state ({sup 229g}Th), as determined by earlier indirect measurements. This is the only nuclear excited state known that is within the range of optical spectroscopy. This paper reports progress toward detecting the {sup 229m}Th state directly by luminescence spectroscopy in the vacuum ultraviolet spectral region. The estimated natural linewidth of the {sup 229g}Th{r_reversible}{sup 229m}Th isomer transition of 2{pi} Multiplication-Sign 0.1 to 2{pi} Multiplication-Sign 10 mHz is expected to broaden to {approx}10 kHz for {sup 229}Th{sup 4+} doped into a suitable crystal. The factors governing the choice of crystal system and the substantial challenges in acquiring a sufficiently large quantity of {sup 229}Th are discussed. We show that the {sup 229g}Th{r_reversible}{sup 229m}Th transition energy can be identified to within 0.1 nm by luminescence excitation and luminescence spectroscopy using the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory. This would open the door for subsequent laser-based measurements of the isomer transition and future applications of {sup 229}Th in nuclear clocks. We also show that {sup 233}U-doped materials should produce an intrinsic, continuous, and sufficiently high rate of {sup 229m}Th{yields}{sup 229g}Th luminescence and could be a useful aid in the initial direct search of the isomer transition. - Highlights: Black-Right-Pointing-Pointer Thorium-229 has a long-lived nuclear excited state. Black-Right-Pointing-Pointer It is the only known nuclear isomer within the reach of optical spectroscopy. Black-Right-Pointing-Pointer Thorium-229 doped fluoride crystals may offer sufficiently high luminescence rates. Black-Right-Pointing-Pointer Luminescence excitation spectroscopy in the vacuum ultraviolet spectral region may enable the first direct observation of

  17. Study of some direct reactions at 00 in 18O+26Mg and 18O+12C systems

    International Nuclear Information System (INIS)

    Payet, J.

    1984-01-01

    Direct transfer reactions induced by a 18 O beam on 12 C and 26 Mg targets, have been studied at the MP tandem (Orsay) with an experimental set up giving the possibility to have angular distributions up to 0 0 . Transfer reactions to discrete levels were analysed in the D.W.B.A. framework. This analysis confirms the interest as a spectroscopic tool of this 0 0 measurements. The ( 18 O, 16 O) and ( 18 O, 20 Ne) reactions were observed up to 40 MeV excitation energy. A diffractionnal model, including the one step direct transfer hypothesis, gives a qualitative agreement with the angular distributions and the energy spectra. A parametrization of a specific small angles development of the transfer amplitudes does not give good results with physical values for the parameters. 32 refs [fr

  18. From waste to value - direct utilization of limonene from orange peel in a biocatalytic cascade reaction towards chiral carvolactone

    NARCIS (Netherlands)

    Oberleitner, N.; Ressmann, A. K.; Bica, K.; Gaertner, P.; Fraaije, M. W.; Bornscheuer, U. T.; Rudroff, F.; Mihovilovic, M. D.

    2017-01-01

    In this proof of concept study we demonstrate direct utilization of limonene containing waste product orange peel as starting material for a biocatalytic cascade reaction. The product of this cascade is chiral carvolactone, a promising building block for thermoplastic polymers. Four different

  19. Direct Imaging and Spectroscopy of a Young Extrasolar Kuiper Belt in the Nearest OB Association

    OpenAIRE

    Currie, Thayne; Lisse, Carey M.; Kuchner, Marc J.; Madhusudhan, Nikku; Kenyon, Scott J.; Thalmann, Christian; Carson, Joseph; Debes, John H.

    2015-01-01

    We describe the discovery of a bright, young Kuiper belt-like debris disk around HD 115600, a $\\sim$ 1.4--1.5 M$_\\mathrm{\\odot}$, $\\sim$ 15 Myr old member of the Sco-Cen OB Association. Our H-band coronagraphy/integral field spectroscopy from the \\textit{Gemini Planet Imager} shows the ring has a (luminosity scaled) semi major axis of ($\\sim$ 22 AU) $\\sim$ 48 AU, similar to the current Kuiper belt. The disk appears to have neutral scattering dust, is eccentric (e $\\sim$ 0.1--0.2), and could b...

  20. Magnitude and direction of the change in dipole moment associated with excitation of the primary electron donor in Rhodopseudomonas sphaeroides reaction centers

    Energy Technology Data Exchange (ETDEWEB)

    Lockhart, D.J.; Boxer, S.G.

    1987-02-10

    The magnitude and direction of the change in dipole moment, ..delta mu.., associated with the Q/sub y/ transition of the dimeric primary electron donor (special pair or P870) in Rhodopseudomonas sphaeroides reaction centers have been measured by Stark spectroscopy at 20 /sup 0/C. The magnitude of ..delta mu.. is found to be f/sup -1/ (10.3 +/- 0.7) D, where f is a correction factor for the local dielectric properties of the protein matrix. With the spherical cavity approximation and an effective local dielectric constant of 2, f = 1.2, and absolute value of ..delta mu.. is 8.6 +/- 0.6 D. Absolute value of ..delta mu.. for the Q/sub y/ transition of the special pair is approximately a factor of 3.4 and 2 greater than for the monomeric bacteriochlorophylls and bacteriopheophytins, respectively, in the reaction center. The angle between ..delta mu.. and the transition dipole moment for excitation of the first singlet electron state of the special pair was found to be 24 +/- 2/sup 0/. The measured values are combined to suggest a physical model in which the lowest excited singlet state of the special pair has substantial charge-transfer character and where charge is separated between the two monomers comprising the dimeric special pair. This leads to the hypothesis that the first charge-separated state in bacterial photosynthesis is formed directly upon photoexcitation. These data provide stringent values for comparison with theoretical calculations of the electronic structure of the chromophores in the reaction center.

  1. In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

    Science.gov (United States)

    Zhang, Kaige; Li, Gongke; Hu, Yuling

    2015-10-28

    The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

  2. Direct solid surface fluorescence spectroscopy of standard chemicals and humic acid in ternary system.

    Science.gov (United States)

    Mounier, S; Nicolodelli, G; Redon, R; Milori, D M B P

    2017-04-15

    The front face fluorescence spectroscopy is often used to quantify chemicals in well-known matrices as it is a rapid and powerful technique, with no sample preparation. However it was not used to investigate extracted organic matter like humic substances. This work aims to fully investigate for the first time front face fluorescence spectroscopy response of a ternary system including boric acid, tryptophan and humic substances, and two binaries system containing quinine sulfate or humic substance in boric acid. Pure chemicals, boric acid, tryptophan, quinine sulfate and humic acid were mixed together in solid pellet at different contents from 0 to 100% in mass. The measurement of excitation emission matrix of fluorescence (3D fluorescence) and laser induced fluorescence were then done in the front face mode. Fluorescence matrices were decomposed using the CP/PARAFAC tools after scattering treatments. Results show that for 3D fluorescence there is no specific component for tryptophan and quinine sulfate, and that humic substances lead to a strong extinction effect for mixture containing quinine sulfate. Laser induced fluorescence gives a very good but non-specific related response for both quinine sulfate and tryptophan. No humic substances fluorescence response was found, but extinction effect is observed as for 3D fluorescence. This effect is stronger for quinine sulfate than for tryptophan. These responses were modeled using a simple absorbance versus emission model. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. DIRECT IMAGING AND SPECTROSCOPY OF A YOUNG EXTRASOLAR KUIPER BELT IN THE NEAREST OB ASSOCIATION

    International Nuclear Information System (INIS)

    Currie, Thayne; Lisse, Carey M.; Kuchner, Marc; Madhusudhan, Nikku; Kenyon, Scott J.; Thalmann, Christian; Carson, Joseph; Debes, John

    2015-01-01

    We describe the discovery of a bright, young Kuiper belt–like debris disk around HD 115600, a ∼1.4–1.5 M ⊙ , ∼15 Myr old member of the Sco–Cen OB Association. Our H-band coronagraphy/integral field spectroscopy from the Gemini Planet Imager shows the ring has a (luminosity-scaled) semimajor axis of (∼22 AU) ∼ 48 AU, similar to the current Kuiper belt. The disk appears to have neutral-scattering dust, is eccentric (e ∼ 0.1–0.2), and could be sculpted by analogs to the outer solar system planets. Spectroscopy of the disk ansae reveal a slightly blue to gray disk color, consistent with major Kuiper belt chemical constituents, where water ice is a very plausible dominant constituent. Besides being the first object discovered with the next generation of extreme adaptive optics systems (i.e., SCExAO, GPI, SPHERE), HD 115600's debris ring and planetary system provide a key reference point for the early evolution of the solar system, the structure, and composition of the Kuiper belt and the interaction between debris disks and planets

  4. DIRECT IMAGING AND SPECTROSCOPY OF A YOUNG EXTRASOLAR KUIPER BELT IN THE NEAREST OB ASSOCIATION

    Energy Technology Data Exchange (ETDEWEB)

    Currie, Thayne [National Astronomical Observatory of Japan, Subaru Telescope, Hilo, HI (United States); Lisse, Carey M. [Applied Physics Laboratory, The Johns Hopkins University, Laurel, MD (United States); Kuchner, Marc [NASA Goddard Space Flight Center, Greenbelt, MD (United States); Madhusudhan, Nikku [Institute for Astronomy, University of Cambridge, Cambridge (United Kingdom); Kenyon, Scott J. [Harvard-Smithsonian Center for Astrophysics, Cambridge, MA (United States); Thalmann, Christian [ETH-Zurich, Zurich (Switzerland); Carson, Joseph [Department of Physics and Astronomy, The College of Charleston, Charleston, SC (United States); Debes, John [Space Telescope Science Institute, Baltimore, MD (United States)

    2015-07-01

    We describe the discovery of a bright, young Kuiper belt–like debris disk around HD 115600, a ∼1.4–1.5 M{sub ⊙}, ∼15 Myr old member of the Sco–Cen OB Association. Our H-band coronagraphy/integral field spectroscopy from the Gemini Planet Imager shows the ring has a (luminosity-scaled) semimajor axis of (∼22 AU) ∼ 48 AU, similar to the current Kuiper belt. The disk appears to have neutral-scattering dust, is eccentric (e ∼ 0.1–0.2), and could be sculpted by analogs to the outer solar system planets. Spectroscopy of the disk ansae reveal a slightly blue to gray disk color, consistent with major Kuiper belt chemical constituents, where water ice is a very plausible dominant constituent. Besides being the first object discovered with the next generation of extreme adaptive optics systems (i.e., SCExAO, GPI, SPHERE), HD 115600's debris ring and planetary system provide a key reference point for the early evolution of the solar system, the structure, and composition of the Kuiper belt and the interaction between debris disks and planets.

  5. Nuclear spectroscopy with lithium ions

    International Nuclear Information System (INIS)

    Heiser, C.

    1977-02-01

    A survey of the state of nuclear spectroscopy with lithium ions is given. Proceeding from the physical and nuclear properties the specific topics arising by the acceleration of these ions are discussed. The results obtained from measurements of excitation functions of different lithium reactions, particularly of compound reactions, with several target nuclei are summarized. Besides compound reactions direct reactions are important, especially transfer reactions, elastic and inelastic scattering and exchange reactions. The results on high spin states obtained by in-beam gamma-spectroscopy are discussed in detail. Finally the possibilities are considered for accelerating lithium ions in the cyclotron U-120 and in the tandem generator EGP-10 of the ZfK. (author)

  6. The use of deuterium n.m.r. spectroscopy in mechanistic studies of exchange reactions of ethers on supported metal catalysts

    International Nuclear Information System (INIS)

    Campbell, J.A.; Kemball, Charles; McDougall, G.S.

    1987-01-01

    Exchange reactions of diethyl ether (DEE) and tetrahydrofuran (THF) with deuterium have been studied over supported nickel, palladium, platinum, and rhodium catalysts. Products from most of the systems were analysed by deuterium n.m.r. spectroscopy (55.28 MHz) which gave quantitative results about the distribution of deuterium in the exchanged ethers. The results confirm earlier conclusions about the mechanism of the exchange of DEE and provide new evidence about the reactions of THF. Some hydrogenolysis occurred simultaneously with exchange of THF over both nickel and platinum. (author)

  7. Direct Energy Supply to the Reaction Mixture during Microwave-Assisted Hydrothermal and Combustion Synthesis of Inorganic Materials

    Directory of Open Access Journals (Sweden)

    Roberto Rosa

    2014-05-01

    Full Text Available The use of microwaves to perform inorganic synthesis allows the direct transfer of electromagnetic energy inside the reaction mixture, independently of the temperature manifested therein. The conversion of microwave (MW radiation into heat is useful in overcoming the activation energy barriers associated with chemical transformations, but the use of microwaves can be further extended to higher temperatures, thus creating unusual high-energy environments. In devising synthetic methodologies to engineered nanomaterials, hydrothermal synthesis and solution combustion synthesis can be used as reference systems to illustrate effects related to microwave irradiation. In the first case, energy is transferred to the entire reaction volume, causing a homogeneous temperature rise within a closed vessel in a few minutes, hence assuring uniform crystal growth at the nanometer scale. In the second case, strong exothermic combustion syntheses can benefit from the application of microwaves to convey energy to the reaction not only during the ignition step, but also while it is occurring and even after its completion. In both approaches, however, the direct interaction of microwaves with the reaction mixture can lead to practically gradient-less heating profiles, on the basis of which the main observed characteristics and properties of the aforementioned reactions and products can be explained.

  8. Direct Enantioselective Reaction between Hemiacetals and Phosphorus Ylides: Important Role of a By-Product in the Asymmetric Transformation.

    Science.gov (United States)

    Wang, Rui; Wang, Linqing; Yang, Dongxu; Li, Dan; Liu, Xihong; Wang, Pengxin; Wang, Kezhou; Zhu, Haiyong; Bai, Lutao

    2018-05-16

    By employing a simple in-situ generated magnesium catalyst, the direct asymmetric reaction between hemiacetals and P-ylides is achieved via a tandem Wittig-oxa-Michael reaction sequence. Enantioenriched chromans, isochromans and tetrahydropyrans can be obtained in good chemical yields. (-)-Erythrococcamide B can be asymmetrically synthesized through this synthetic technique. In this work, the by-product, TPO, was identified as a necessary additive in this asymmetric synthetic method. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Status on Establishing the Feasibility of Lead Slowing Down Spectroscopy for Direct Measurement of Plutonium in Used Fuel

    Energy Technology Data Exchange (ETDEWEB)

    Kulisek, Jonathan A.; Anderson, Kevin K.; Casella, Andrew M.; Gesh, Christopher J.; Warren, Glen A.; Gavron, Victor A.; Devlin, M.; Haight, R. C.; O' Donnell, J. M.; Danon, Yaron; Weltz, Adam; Bonebrake, Eric; Imel, G. R.; Harris, Jason; Beller, Dennis; Hatchett, D.; Droessler, J.

    2012-08-30

    Developing a method for the accurate, direct, and independent assay of the fissile isotopes in bulk materials (such as used fuel) from next-generation domestic nuclear fuel cycles is a goal of the Office of Nuclear Energy, Fuel Cycle R&D, Material Protection and Control Technology (MPACT) Campaign. To meet this goal, MPACT supports a multi-institutional collaboration to study the feasibility of Lead Slowing Down Spectroscopy. This technique is an active nondestructive assay method that has the potential to provide independent, direct measurement of Pu and U isotopic masses in used fuel with an uncertainty considerably lower than the approximately 10% typical of today’s confirmatory assay methods. This paper will present efforts on the development of time-spectral analysis algorithms, fast neutron detector advances, and validation and testing measurements.

  10. Direct conversion from Jerusalem artichoke to hydroxymethylfurfural (HMF) using the Fenton reaction.

    Science.gov (United States)

    Seo, Yeong Hwan; Han, Jong-In

    2014-05-15

    A simple method for hydroxymethylfurfural (HMF) production from non-crop biomass of the Jerusalem artichoke was developed using the Fenton reaction, in a mixture of 2-butanol and water. Four parameters (temperature, reaction time, Fe(2+) concentration, and H2O2 concentration) were identified as experimental factors, and HMF yield was selected as the response parameter. The experimental factors were optimised by employing Response Surface Methodology (RSM). The maximum HMF yield, of 46%, was obtained with a reaction time of 90 min, Fe(2+) concentration of 1.3 mM, and 0.47 M of H2O2 at 180 °C. Copyright © 2014. Published by Elsevier Ltd.

  11. Directing Reaction Pathways through Controlled Reactant Binding at Pd-TiO2 Interfaces.

    Science.gov (United States)

    Zhang, Jing; Wang, Bingwen; Nikolla, Eranda; Medlin, J Will

    2017-06-01

    Recent efforts to design selective catalysts for multi-step reactions, such as hydrodeoxygenation (HDO), have emphasized the preparation of active sites at the interface between two materials having different properties. However, achieving precise control over interfacial properties, and thus reaction selectivity, has remained a challenge. Here, we encapsulated Pd nanoparticles (NPs) with TiO 2 films of regulated porosity to gain a new level of control over catalyst performance, resulting in essentially 100 % HDO selectivity for two biomass-derived alcohols. This catalyst also showed exceptional reaction specificity in HDO of furfural and m-cresol. In addition to improving HDO activity by maximizing the interfacial contact between the metal and metal oxide sites, encapsulation by the nanoporous oxide film provided a significant selectivity boost by restricting the accessible conformations of aromatics on the surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Directing reaction pathways by catalyst active-site selection using self-assembled monolayers.

    Science.gov (United States)

    Pang, Simon H; Schoenbaum, Carolyn A; Schwartz, Daniel K; Medlin, J Will

    2013-01-01

    One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism.

  13. Hantzsch Reaction Starting Directly from Alcohols through a Tandem Oxidation Process

    Directory of Open Access Journals (Sweden)

    Xiaobing Liu

    2017-01-01

    Full Text Available A Brønsted acidic ionic liquid, 3-(N,N-dimethyldodecylammonium propanesulfonic acid hydrogen sulphate ([DDPA][HSO4], has been successfully applied to catalyze sequential oxidation of aromatic alcohols with NaNO3 followed by their condensation with dicarbonyl compound and ammonium acetate. The corresponding pyridine analogues of Hantzsch 1,4-dihydropyridines could be obtained as a major product with high yields by the multicomponent reaction. The present work utilizing alcohols instead of aldehyde in Hantzsch reaction is a valid and green alternative to the classical synthesis of the corresponding pyridine analogues of Hantzsch 1,4-dihydropyridines.

  14. Soft x-ray spectroscopy optimisation for the direct determination of valence

    International Nuclear Information System (INIS)

    Wison, N.C.; MacRae, C.M.; Nelson, S.

    2002-01-01

    Full text: Measuring the valence of elements and mapping their occurrence throughout a sample can give important insights into the chemistry of complex systems. The toxic nature of Cr 6+ gives great concern over its disposal in the environment. Being able to resolve Cr 6+ from Cr 3+ allows us to tackle these important problems. The electron probe micro-analyser (EPMA) is routinely used to provide micron resolution chemical analysis. However it is often possible to resolve changes in soft X-ray peak shape and position that reflect changes in the chemical state and crystal structure. A soft x-rays is usually considered to be one of less than 1.5 keV in energy In this study we have compared a range of Cr containing compounds, and measured the differences in the Cr Lα line. In some samples, the Cr L line can be 'relatively weak, so to maximise its excitation probability, a set of Monte Carlo simulations were performed using the CASINO V2.0 package and the most efficient excitation voltage was determined. We also investigate the soft x-ray spectroscopy using electronic structure calculations to produce theoretical Density of States (DOS) for comparison with the measured spectra. The theoretical calculations can aid in understanding spectrum shape and polarisation of the soft x-ray signal in unknown samples, when a full range of standards is not available. Copyright (2002) Australian Society for Electron Microscopy Inc

  15. Future directions of positron annihilation spectroscopy in low-k dielectric films

    International Nuclear Information System (INIS)

    Gidley, D.W.; Vallery, R.S.; Liu, M.; Peng, H.G.

    2007-01-01

    Positronium Annihilation Lifetime Spectroscopy (PALS) has become recognized in the microelectronics industry as one of only several methods capable of quantitatively characterizing engineered nanopores in next-generation (k < 2.2) interlayer dielectric (ILD) thin films. Successes and shortcomings of PALS to date will be assessed and compared with other methods of porosimetry such as ellipsometric and X-ray porosimetries (EP and XRP). A major theme in future low-k research focuses on the ability to integrate porous ILD's into chip fabrication; the vulnerability of porous dielectrics to etching, ashing, and chemical-mechanical polishing in process integration is delaying the introduction of ultra-low-k films. As device size approaches 45 nm the need to probe very small (sub-nanometer), semi-isolated pores beneath thin diffusion barriers is even more challenging. Depth-profiled PALS with its ability to determine a quantitative pore interconnection length and easily resolve 0.3 nm pores beneath diffusion barriers or in trench-patterned dielectrics should have a bright future in porous ILD research. The ability of PALS (and PAS in general) to deduce evolution and growth of pores with porosity should find broad applicability in the emerging field of high performance materials with strategically engineered nanopores. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  16. Constraining the 19Ne(p,γ)20Na Reaction Rate Using a Direct Measurement at DRAGON

    Science.gov (United States)

    Wilkinson, R.; Lotay, G.; Lennarz, A.; Ruiz, C.; Christian, G.; Akers, C.; Catford, W. N.; Chen, A. A.; Connolly, D.; Davids, B.; Hutcheon, D. A.; Jedrejcic, D.; Laird, A. M.; Martin, L.; McNeice, E.; Riley, J.; Williams, M.

    2018-01-01

    A direct measurement of the 19Ne(p, γ)20 Na reaction has been performed in inverse kinematics at the DRAGON recoil separator, at an energy ˜ 10 keV higher than previous measurements. The key resonance in the 19 Ne + p system relevant for ONe novae and Type-I X-ray burst temperatures have been successfully measured for the first time. Preliminary estimates of the resonance energy and strength are reported as Ec.m. ≈ 458 keV and ωγ ≈ 18 meV. These results are consistent with previous direct measurements, but disagree with the most recent study of the 19Ne(p, γ)20 Na reaction rate. These preliminary results will be finalised after a forthcoming negative log-likelihood analysis.

  17. Direct mapping of the angle-dependent barrier to reaction for Cl + CHD3 using polarized scattering data

    Science.gov (United States)

    Pan, Huilin; Wang, Fengyan; Czakó, Gábor; Liu, Kopin

    2017-12-01

    The transition state, which gates and modulates reactive flux, serves as the central concept in our understanding of activated reactions. The barrier height of the transition state can be estimated from the activation energy taken from thermal kinetics data or from the energetic threshold in the measured excitation function (the dependence of reaction cross-sections on initial collision energies). However, another critical and equally important property, the angle-dependent barrier to reaction, has not yet been amenable to experimental determination until now. Here, using the benchmark reaction of Cl + CHD3(v1 = 1) as an example, we show how to map this anisotropic property of the transition state as a function of collision energy from the preferred reactant bond alignment of the backward-scattered products—the imprints of small impact-parameter collisions. The deduced bend potential at the transition state agrees with ab initio calculations. We expect that the method should be applicable to many other direct reactions with a collinear barrier.

  18. Modelling and simulation of a direct ethanol fuel cell considering multistep electrochemical reactions, transport processes and mixed potentials

    International Nuclear Information System (INIS)

    Meyer, Marco; Melke, Julia; Gerteisen, Dietmar

    2011-01-01

    Highlights: → A DEFC model considering the mixed potential formation at cathode and anode. → The low cell voltage at open circuit is due to the parasitic reaction of ethanol and oxygen. → Under load, only the parasitic oxidation of ethanol is significant. → Inhibiting the parasitic reactions can approximately double the current density. - Abstract: In this work a one-dimensional mathematical model of a direct ethanol fuel cell (DEFC) is presented. The electrochemical oxidation of ethanol in the catalyst layers is described by several reaction steps leading to surface coverage with adsorbed intermediates (CH 3 CO, CO, CH 3 and OH) and to the final products acetaldehyde, acetic acid and CO 2 . A bifunctional reaction mechanism is assumed for the activation of water on a binary catalyst favouring the further oxidation of adsorbates blocking active catalyst sites. The chemical reactions are highly coupled with the charge and reactant transport. The model accounts for crossover of the reactants through the membrane leading to the phenomenon of cathode and anode mixed potentials due to the parasitic oxidation and reduction of ethanol and oxygen, respectively. Polarisation curves of a DEFC were recorded for various ethanol feed concentrations and were used as reference data for the simulation. Based on one set of model parameters the characteristic of electronic and protonic potential, the relative surface coverage and the parasitic current densities in the catalyst layers were studied.

  19. Direct synthesis of acid-base bifunctionalized hexagonal mesoporous silica and its catalytic activity in cascade reactions.

    Science.gov (United States)

    Shang, Fanpeng; Sun, Jianrui; Wu, Shujie; Liu, Heng; Guan, Jingqi; Kan, Qiubin

    2011-03-01

    A series of efficient acid-base bifunctionalized hexagonal mesoporous silica (HMS) catalysts contained aminopropyl and propanesulfonic acid have been synthesized through a simple co-condensation by protection of amino group. The results of small-angle XRD, TEM, and N(2) adsorption-desorption measurements show that the resultant materials have mesoscopic structures. X-ray photoelectron spectroscopies, elemental analysis (EA), back titration, (29)Si NMR and (13)C NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The resultant catalysts exhibit excellent acid-basic properties, which make them possess high activity for one-pot deacetalization-Knoevenagel and deacetalization-nitroaldol (Henry) reactions. Copyright © 2010 Elsevier Inc. All rights reserved.

  20. Characterization of a direct dc-excited discharge in water by optical emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Bruggeman, Peter; Leys, Christophe [Department of Applied Physics, Ghent University, Jozef Plateaustraat 22, B-9000 Ghent (Belgium); Schram, Daan [Department of Applied Physics, Technische Universiteit Eindhoven, PO Box 513, 5600 MB Eindhoven (Netherlands); Gonzalez, Manuel A [Departamento de Fisica Aplicada, Universidad de Valladolid, 47011 Valladolid (Spain); Rego, Robby [Flemish Institute of Technological Research, VITO Materials, Boeretang 200, B-2400 Mol (Belgium); Kong, Michael G [Department of Electronic and Electrical Engineering, Loughborough University, Loughborough, Leicestershire LE11 3TU (United Kingdom)], E-mail: peter.bruggeman@ugent.be

    2009-05-01

    Dc-excited discharges generated in water at the tip of a tungsten wire which is located at the orifice of a quartz capillary are investigated by time-averaged optical emission spectroscopy. Two distinctive discharge modes are observed. For small conductivities of the liquid the discharge is a streamer-like discharge in the liquid itself (liquid mode). For conductivities above typically 45 {mu}S cm{sup -1} a large vapour bubble is formed and a streamer discharge in this vapour bubble is observed (bubble mode). Plasma temperatures and electron densities are investigated for both modes. The gas temperature is estimated from the rotational temperature of N{sub 2}(C-B) and is 1600 {+-} 200 K for the bubble mode and 1900 {+-} 200 K for the liquid mode. The rotational temperature of OH(A-X) is up to 2 times larger and cannot be used as an estimate for the gas temperature. The rotational population distribution of OH(A), {nu} = 0 is also non-Boltzmann with a large overpopulation of high rotational states. This discrepancy in rotational temperatures is discussed in detail. Electron densities are obtained from the Stark broadening of the hydrogen Balmer beta line. The electron densities in the liquid mode are of the order of 10{sup 21} m{sup -3}. In the bubble mode electron densities are significantly smaller: (3-4) x 10{sup 20} m{sup -3}. These values are compared with the Stark broadening of the hydrogen alpha and gamma lines and with electron densities obtained from current density measurements. The chemical reactivities of the bubble and liquid modes are compared by means of the hydrogen peroxide production rate.

  1. Characterization of a direct dc-excited discharge in water by optical emission spectroscopy

    International Nuclear Information System (INIS)

    Bruggeman, Peter; Leys, Christophe; Schram, Daan; Gonzalez, Manuel A; Rego, Robby; Kong, Michael G

    2009-01-01

    Dc-excited discharges generated in water at the tip of a tungsten wire which is located at the orifice of a quartz capillary are investigated by time-averaged optical emission spectroscopy. Two distinctive discharge modes are observed. For small conductivities of the liquid the discharge is a streamer-like discharge in the liquid itself (liquid mode). For conductivities above typically 45 μS cm -1 a large vapour bubble is formed and a streamer discharge in this vapour bubble is observed (bubble mode). Plasma temperatures and electron densities are investigated for both modes. The gas temperature is estimated from the rotational temperature of N 2 (C-B) and is 1600 ± 200 K for the bubble mode and 1900 ± 200 K for the liquid mode. The rotational temperature of OH(A-X) is up to 2 times larger and cannot be used as an estimate for the gas temperature. The rotational population distribution of OH(A), ν = 0 is also non-Boltzmann with a large overpopulation of high rotational states. This discrepancy in rotational temperatures is discussed in detail. Electron densities are obtained from the Stark broadening of the hydrogen Balmer beta line. The electron densities in the liquid mode are of the order of 10 21 m -3 . In the bubble mode electron densities are significantly smaller: (3-4) x 10 20 m -3 . These values are compared with the Stark broadening of the hydrogen alpha and gamma lines and with electron densities obtained from current density measurements. The chemical reactivities of the bubble and liquid modes are compared by means of the hydrogen peroxide production rate.

  2. Allergic reactions in red tattoos: Raman spectroscopy for 'fingerprint' detection of chemical risk spectra in tattooed skin and culprit tattoo inks.

    Science.gov (United States)

    Hutton Carlsen, K; Køcks, M; Sepehri, M; Serup, J

    2016-11-01

    The aim of this study was to assess the feasibility of Raman spectroscopy as a screening technique for chemical characterisation of tattoo pigments in pathologic reacting tattoos and tattoo ink stock products to depict unsafe pigments and metabolites of pigments. Twelve dermatome shave biopsies from allergic reactions in red tattoos were analysed with Raman spectroscopy (A 785-nm 300 mW diode laser). These were referenced to samples of 10 different standard tattoo ink stock products, three of these identified as the culprit inks used by the tattooist and thus by history the source of the allergy. Three primary aromatic amine (PAA) laboratory standards (aniline, o-anisidine and 3,3'-dichlorobenzidine) were also studied. Application of Raman spectroscopy to the shave biopsies was technically feasible. In addition, all ten inks and the three PAA standards could be discriminated. 10/12 shave biopsies provided clear fingerprint Raman signals which differed significantly from background skin, and Raman spectra from 8/12 biopsies perfectly matched spectra from the three culprit ink products. The spectrum of one red ink (a low cost product named 'Tattoo', claimed to originate from Taiwan, no other info on label) was identified in 5/12 biopsies. Strong indications of the inks 'Bright Red' and 'Crimson Red' were seen in three biopsies. The three PAA's could not be unambiguously identified. This study, although on a small-scale, demonstrated Raman spectroscopy to be feasible for chemical analysis of red pigments in allergic reactions. Raman spectroscopy has a major potential for fingerprint screening of problematic tattoo pigments in situ in skin, ex vivo in skin biopsies and in tattoo ink stock products, thus, to eliminate unsafe ink products from markets. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  3. Exploiting Synergistic Effects in Organozinc Chemistry for Direct Stereoselective C-Glycosylation Reactions at Room Temperature.

    Science.gov (United States)

    Hernan-Gomez, Alberto; Orr, Samantha; Uzelac, Marina; Kennedy, Alan; Barroso, Santiago; Jusseau, Xavier; Lemaire, Sebastien; Farina, Vittorio; Hevia, Eva

    2018-06-01

    Pairing a range of bis(aryl) zinc reagents ZnAr2 with the stronger Lewis acidic [(ZnArF2)] (ArF = C6F5), enables highly stereoselective cross-coupling between glycosyl bromides and ZnAr2 without the use of a transition metal. Reactions occur at room temperature with excellent levels of stereoselectivity, where ZnArF2 acts as a non-coupling partner although its presence is crucial for the execution of the C(sp2)-C(sp3) bond formation process. Mechanistic studies have uncovered a unique synergistic partnership between the two zinc reagents, which circumvents the need for transition-metal catalysis or forcing reaction conditions. Key to the success of the coupling is the avoidance of solvents that act as Lewis bases vs. diarylzinc compounds (e.g. THF. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Highly enantio- and diastereoselective reactions of γ-substituted butenolides through direct vinylogous conjugate additions

    KAUST Repository

    Zhang, Wen; Tan, Davin; Lee, Richmond; Tong, Guanghu; Chen, Wenchao; Qi, Baojian; Huang, Kuo-Wei; Tan, Choonhong; Jiang, Zhiyong

    2012-01-01

    The strength of the weak: An L-tert-leucine-derived amine-thiourea catalyst (see scheme, green box) promotes the asymmetric vinylogous conjugate addition reaction between γ-aryl- and alkyl-substituted butenolides with the butenamides and enoates shown. Computational studies show the preference for the observed stereochemistry is a result of favourable weak non-bonding interactions, which stabilize the transition state. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Highly enantio- and diastereoselective reactions of γ-substituted butenolides through direct vinylogous conjugate additions

    KAUST Repository

    Zhang, Wen

    2012-09-05

    The strength of the weak: An L-tert-leucine-derived amine-thiourea catalyst (see scheme, green box) promotes the asymmetric vinylogous conjugate addition reaction between γ-aryl- and alkyl-substituted butenolides with the butenamides and enoates shown. Computational studies show the preference for the observed stereochemistry is a result of favourable weak non-bonding interactions, which stabilize the transition state. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Recent developments in fusion and direct reactions with weakly bound nuclei

    International Nuclear Information System (INIS)

    Canto, L.F.; Gomes, P.R.S.; Donangelo, R.; Lubian, J.; Hussein, M.S.

    2015-01-01

    In this Report we give a balanced account of the experimental and theoretical advances acquired over the last decade in the field of near-barrier fusion reactions induced by weakly bound stable and unstable nuclei. The elastic scattering and breakup reactions of these systems are also extensively reviewed as they play an important role in the fusion process. We review several theoretical tools used in the description of the data. The concepts of Complete Fusion (CF), Incomplete Fusion (ICF) and Total Fusion (TF), which is the sum of CF and ICF, are discussed and recent work on the calculation of these quantities is reviewed. The Continuum Discretized Coupled Channels (CDCC) method and its semiclassical version are described in detail and their limitations are pointed out. More importantly, we describe the salient features of the conclusions reached from the more than 40 measurements made, over a decade, of near-barrier fusion, elastic scattering and breakup reactions, and confront these data with the CDCC or other methods appropriate for these processes at the energy regime in question.

  7. Children's direct fright and worry reactions to violence in fiction and news television programs.

    Science.gov (United States)

    van der Molen, Juliette H Walma; Bushman, Brad J

    2008-09-01

    To examine whether violence in fictional and news television content frightens and worries children. Mixed factorial. Type of reaction (fright, worry) and television programming (violent news, violent fiction) were within-subjects factors, whereas age, sex, and television viewing frequency were between-subjects factors. Participants included 572 children (47% boys), aged 8 to 12 years, from 9 urban and rural primary schools in the Netherlands. The main exposure was to descriptions of 8 threats frequently depicted in fictional and news programs (eg, murder, war, house fires). Children reported whether they were frightened or worried by these threats. Violent threats increased both fright and worry. These 2 reactions could be distinguished from one another in a factor analysis. When violent content was described as news, it produced more fear reactions than when it was described as fiction. Fright and worry were greater in girls than in boys, in younger children than in older children, and in light television viewers than in heavy television viewers. Pediatricians should inform parents, educators, policy makers, and broadcasters about the potentially harmful effect of violent programming on children's emotions, especially in the case of news programming.

  8. Study of In-Cylinder Reactions of High Power-Density Direct Injection Diesel Engines

    National Research Council Canada - National Science Library

    Jansons, M

    2004-01-01

    Direct-injection (DI) Diesel or compression-ignition (CI) engine combustion process is investigated when new design and operational strategies are employed in order to achieve a high power-density (HPD) engine...

  9. Direct Determination of Contaminants and Major and Minor Nutrients in Solid Fertilizers Using Laser-Induced Breakdown Spectroscopy (LIBS).

    Science.gov (United States)

    Andrade, Daniel F; Pereira-Filho, Edenir Rodrigues

    2016-10-11

    Contaminants (Cd, Cr, and Pb) as well as minor (B, Cu, Mn, Na, and Zn) and major (Ca and Mg) elements were directly determined in solid fertilizer samples using laser-induced breakdown spectroscopy (LIBS). Factorial designs were used to define the most appropriate LIBS parameters and pellet pressure on solid fertilizers. Emission lines for all of the analytes were collected and employed 12 signal normalization modes. The best results were obtained using a laser energy of 75 mJ, a spot size of 50 μm, a pressure of 10 t/in., and a delay of 2.0 μs. Good correlation was obtained between the calibration model's prediction using the proposed LIBS method and the reference values obtained with ICP-OES. The limits of detection (LOD) for the proposed method varied from 2 mg/kg (for Cd) to 1% (for Zn).

  10. Direct Structural and Chemical Characterization of the Photolytic Intermediates of Methylcobalamin Using Time-Resolved X-ray Absorption Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Subramanian, Ganesh; Zhang, Xiaoyi; Kodis, Gerdenis; Kong, Qingyu; Liu, Cunming; Chizmeshya, Andrew; Weierstall, Uwe; Spence, John

    2018-04-05

    Cobalt−carbon bond cleavage is crucial to most natural and synthetic applications of the cobalamin class of compounds, and here we present the first direct electronic and geometric structural characteristics of intermediates formed following photoexcitation of methylcobalamin (MeCbl) using time-resolved X-ray absorption spectroscopy (XAS). We catch transients corresponding to two intermediates, in the hundreds of picoseconds and a few microseconds. Highlights of the picosecond intermediate, which is reduced in comparison to the ground state, are elongation of the upper axial Co−C bond and relaxation of the corrin ring. This is not so with the recombining photocleaved products captured at a few microseconds, where the Co−C bond almost (yet not entirely) reverts to its ground state configuration and a substantially elongated lower axial Co−NIm bond is observed. The reduced cobalt site here confirms formation of methyl radical as the photoproduct.

  11. Direct detection of ligand binding to Sepharose-immobilised protein using saturation transfer double difference (STDD) NMR spectroscopy

    International Nuclear Information System (INIS)

    Haselhorst, Thomas; Muenster-Kuehnel, Anja K.; Oschlies, Melanie; Tiralongo, Joe; Gerardy-Schahn, Rita; Itzstein, Mark von

    2007-01-01

    We report an easy and direct application of 'Saturation Transfer Double Difference' (STDD) NMR spectroscopy to identify ligands that bind to a Sepharose-immobilised target protein. The model protein, cytidine 5'-monophosphate sialic acid (CMP-Sia) synthetase, was expressed as a Strep-Tag II fusion protein and immobilised on Strep-Tactin Sepharose. STD NMR experiments of the protein-enriched Sepharose matrix in the presence of a binding ligand (cytidine 5'-triphosphate, CTP) and a non-binding ligand (α/β-glucose) clearly show that CTP binds to the immobilised enzyme, whereas glucose has no affinity. This approach has three major advantages: (a) only low quantities of protein are required, (b) no specialised NMR technology or the application of additional data analysis by non-routine methods is required, and (c) easy multiple use of the immobilised protein is available

  12. Direct observation of superconducting gaps in MgB{sub 2} by angle-resolved photoemission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Souma, S.; Machida, Y.; Sato, T.; Takahashi, T.; Matsui, H.; Wang, S.-C.; Ding, H.; Kaminski, A.; Campuzano, J.C.; Sasaki, S.; Kadowaki, K

    2004-08-01

    High-resolution angle-resolved photoemission spectroscopy has been carried out to clarify the anomalous superconductivity of MgB{sub 2}. We observed three bands crossing the Fermi level, which are ascribed to B2p-{sigma}, {pi} and surface bands. We have succeeded for the first time in directly observing the superconducting gaps of these bands separately. We have found that the superconducting-gap sizes of {sigma} and surface bands are 6.5 {+-} 0.5 and 6.0 {+-} 0.5 meV, respectively, while that of the {pi} band is much smaller (1.5 {+-} 0.5 meV). The present experimental result unambiguously demonstrates the validity of the two-band superconductivity in MgB{sub 2}.

  13. Model-independent spectroscopic information and the peripheral direct capture A(a,γ)B reaction at stellar energies

    International Nuclear Information System (INIS)

    Igamov, S.B.; Yarmukhamedov, R.

    2004-01-01

    Full text: Despite the impressive progress in our understanding of these processes has been made in the last decades, there are still many problems connected with obtaining precise data on the A(p,γ )B and A(α,γ )B reactions cross sections at stellar energies to be solved. One of the possibilities of solving these problems is based on the principally peripheral character of charged particles interaction at low energy and the possibility of using the information on asymptotic normalization coefficients (ANC) (or respective nuclear vertex constants (NVC) for the virtual decay B→A+a ) of the overlap functions for the A(p,γ )B and A(α,γ)B reactions. This review is devoted to critical analysis of traditional methods of obtaining ANC information from DWBA - method calculation of proton transfer reactions and two - body potential model calculation of the direct capture reactions. Moreover in this review modified two - body potential approach allowing to determine both the ANC for virtual decays B→p+A and B→α+A and astrophysical S-factor, S(E), for the A(p,γ)B and A(α,γ)B at stellar energies E (∼ 25 keV) is discussed. This method involves two additional conditions that allow to verify the peripheral character of the considered reactions. New information about rates of t( α ,γ ) 7 Li, 3 He(α ,γ ) 7 Be, 7 Be(p,γ ) 8 B and 12 C(p,γ ) 13 N reactions and estimation of the values of the ANC's for 7 Li →α+t, 7 Be→α+ 3 He, and 8 B→ 7 Be+p has also been presented

  14. Direct Dynamics Simulation of the Thermal 3CH2 + 3O2 Reaction. Rate Constant and Product Branching Ratios.

    Science.gov (United States)

    Lakshmanan, Sandhiya; Pratihar, Subha; Machado, Francisco Bolivar Correto; Hase, William Louis

    2018-04-26

    The reaction of 3CH2 with 3O2 is of fundamental importance in combustion and the reaction is complex as a result of multiple extremely exothermic product channels. In the present study, direct dynamics simulations were performed to study the reaction on both the singlet and triplet potential energy surfaces (PESs). The simulations were performed at the UM06/6-311++G(d,p) level of theory. Trajectories were calculated at a temperature of 300 K and all reactive trajectories proceeded through the carbonyl oxide Criegee intermediate, CH2OO, on both the singlet and triplet PESs. The triplet surface leads to only one product channel, H2CO + O(3P), while the singlet surface leads to 8 product channels with their relative importance as: CO + H2O > CO + OH + H ~ H2CO + O(1D) > HCO + OH ~ CO2 + H2 ~ CO + H2 + O(1D) > CO2 + H + H > HCO + O(1D) + H. Reaction on the singlet PES is barrierless, consistent with experiment and the total rate constant on the singlet surface is 0.93 ± 0.22 x 10-12 cm3molecule-1s-1 in comparison to the recommended experimental rate constant of 3.3 x 10-12 cm3molecule-1s-1. The simulation product yields for the singlet PES are compared with experiment and the most significant differences are for H, CO2, and H2O. Reaction on the triplet surface is also barrierless, inconsistent with experiment. A discussion is given of the need for future calculations to address the: (1) barrier on the triplet PES for 3CH2 + 3O2 → 3CH2OO; (2) temperature dependence of the 3CH2 + 3O2 reaction rate constant and product branching ratios; and (3) possible non-RRKM dynamics of the 1CH2OO Criegee intermediate.

  15. [Direct costs and clinical aspects of adverse drug reactions in patients admitted to a level 3 hospital internal medicine ward].

    Science.gov (United States)

    Tribiño, Gabriel; Maldonado, Carlos; Segura, Omar; Díaz, Jorge

    2006-03-01

    Adverse drug reactions (ADRs) occur frequently in hospitals and increase costs of health care; however, few studies have quantified the clinical and economic impact of ADRs in Colombia. These impacts were evaluated by calculating costs associated with ADRs in patients hospitalized in the internal medicine ward of a Level 3 hospital located in Bogotá, Colombia. In addition, salient clinical features of ADRs were identified and characterized. Intensive follow-ups for a cohort of patients were conducted for a five month period in order to detect ADRs; different ways to classify them, according to literature, were considered as well. Information was collected using the INVIMA reporting format, and causal probability was evaluated with the Naranjo algorithm. Direct costs were calculated from the perspective of payer, based on the following costs: additional hospital stay, medications, paraclinical tests, additional procedures, patient displacement to intermediate or intensive care units, and other costs. Of 836 patients admitted to the service, 268 adverse drug reactions were detected in 208 patients (incidence proportion 25.1%, occurence rate 0.32). About the ADRs found, 74.3% were classified as probable, 92.5% were type A, and 81.3% were moderate. The body system most often affected was the circulatory system (33.9%). Drugs acting on the blood were most frequently those ones associated with adverse reactions (37.6%). The costs resulting from medical care of adverse drug reactions varied from COL dollar 93,633,422 (USD dollar 35,014.92) to COL dollar 122,155,406 (USD dollar 45,680.94), according to insurance type, during the study period. Adverse drug reactions have a significant negative health and financial impact on patient welfare. Because of the substantial resources required for their medical care and the significant proportion of preventable adverse reactions, active programs of institutional pharmacovigilance are highly recommended.

  16. Direct Observation of Ultrafast Hole Injection from Lead Halide Perovskite by Differential Transient Transmission Spectroscopy.

    Science.gov (United States)

    Ishioka, Kunie; Barker, Bobby G; Yanagida, Masatoshi; Shirai, Yasuhiro; Miyano, Kenjiro

    2017-08-17

    Efficient charge separation at the interfaces of the perovskite with the carrier transport layers is crucial for perovskite solar cells to achieve high power conversion efficiency. We present a systematic experimental study on the hole injection dynamics from MAPbI 3 perovskite to three typical hole transport materials (HTMs). We extract the carrier dynamics directly related to the hole injection by employing a pump light with short absorption depth and comparing the transient transmission signals excited on the two sides of the sample. The differential transmission signals reveal the hole injections to PTAA and PEDOT:PSS to be complete within 1 and 2 ps, respectively, and that to NiO x to exhibit an additional slow process on a 40 ps time scale. The obtained injection dynamics are discussed in comparison with the device performance of the solar cells containing the same MAPbI 3 /HTM interfaces.

  17. Direct projectile break up its relation to the astrophysically revelant fusion reactions

    International Nuclear Information System (INIS)

    Bertulani, C.A.; Hussein, M.S.

    1990-05-01

    The break-up into two pieces of weakly bound nuclei passing by the Coulomb field of a large Z nucleus can provide useful information on the inverse fusion reactions which are important for the elemental formation in the stars. However, the nuclear interaction complicates considerably the extraction of such information. A study is made of the contributions of the Coulomb and nuclear interaction to the process, showing when the Coulomb break-up prevails and how a reliable separation of multipolarities can be done. (author)

  18. Direct gas-phase epoxidation of propylene to propylene oxide through radical reactions: A theoretical study

    Science.gov (United States)

    Kizilkaya, Ali Can; Fellah, Mehmet Ferdi; Onal, Isik

    2010-03-01

    The gas-phase radical chain reactions which utilize O 2 as the oxidant to produce propylene oxide (PO) are investigated through theoretical calculations. The transition states and energy profiles were obtained for each path. The rate constants were also calculated. The energetics for the competing pathways indicate that PO can be formed selectively due to its relatively low activation barrier (9.3 kcal/mol) which is in a good agreement with the experimental value (11 kcal/mol) of gas-phase propylene epoxidation. The formation of the acrolein and combustion products have relatively high activation barriers and are not favored. These results also support the recent experimental findings.

  19. Discovery of a Significant Acetone•Hydroperoxy Adduct Chaperone Effect and Its Impact on the Determination of Room Temperature Rate Constants for Acetonylperoxy/Hydroperoxy Self-Reactions and Cross Reaction Via Infrared Kinetic Spectroscopy.

    Science.gov (United States)

    Grieman, F. J.; Hui, A. O.; Okumura, M.; Sander, S. P.

    2017-12-01

    In order to model the upper troposphere/lower stratosphere in regions containing acetone properly, the kinetics of the acetonylperoxy/hydroperoxy self-reactions and cross reaction have been studied over a wide temperature range using Infrared Kinetic Spectroscopy. We report here the determination of different rate constants for the acetonylperoxy chemistry that we obtained at 298 K compared to currently accepted values. A considerable increase in the observed HO2 self-reaction rate constant due to rate enhancement via the chaperone effect from the reaction between HO2 and the (CH3)2CO•HO2 hydrogen-bonded adduct, even at room temperature, was discovered that was previously ignored. Correct determination of the acetonylperoxy and hydroperoxy kinetics must include this dependence of the HO2 self-reaction rate on acetone concentration. Via excimer laser flash photolysis to create the radical reactants, HO2 absorption was monitored in the infrared by diode laser wavelength modulation detection simultaneously with CH3C(O)CH2O2absorption monitored in the ultraviolet at 300 nm as a function of time. Resulting decay curves were fit concurrently first over a short time scale to obtain the rate constants minimizing subsequent product reactions. Modeling/fitting with a complete reaction scheme was then performed to refine the rate constants and test their veracity. Experiments were carried out over a variety of concentrations of acetone and methanol. Although no effect due to methanol concentration was found at room temperature, the rate constant for the hydroperoxy self-reaction was found to increase linearly with acetone concentration which is interpreted as the adduct being formed and resulting in a chaperone mechanism that enhances the self-reaction rate: (CH3)2CO·HO2 + HO2 → H2O2 + O2 + (CH3)2CO Including this effect, the resulting room temperature rate constants for the cross reaction and the acetonylperoxy self-reaction were found to be 2-3 times smaller than

  20. Adverse reactions from community directed treatment with ivermectin (CDTI for onchocerciasis and loiasis in Ondo State, Nigeria

    Directory of Open Access Journals (Sweden)

    O.A Otubanjo

    2008-12-01

    Full Text Available Onchocerciasis is an endemic disease in Ondo state, Nigeria. Community directed distribution of ivermectin is currently on-going in some local government areas of the state. Randomly selected persons (2 331 males and 2 469 females were interviewed using a modified rapid assessment procedure for Loa loa (RAPLOA to assess community directed treatment with ivermectin. The retrospective study evaluated the coverage, impacts and adverse reactions to the drug treatment. A questionnaire was administered by house-to-house visit in six local government areas, implementing community directed treatment with ivermectin (CDTI in this bioclimatic zone. A total of 2,398 respondents were reported to have participated in the treatment. The overall ivermectin coverage of 49.96% was recorded (range 0 - 52% in different communities. Adverse reactions from ivermectin administration were experienced in 38% of individuals. Diverse adverse reactions experienced included predominantly itching (18.50%; oedema, especially of the face and the limbs (8.2%; rashes (3.4% and body weakness (2.4%. Expulsion of intestinal worms occurred in 0.96% of the respondents. The occurrence of adverse reactions in relation to age categories was statistically significant. Neither fatal nor severe adverse reactions were reported by respondents. Significantly, despite experienced adverse reactions, continued participation, acceptability and compliance to ivermectin treatment was expressed by the various communities. This attitude is in consonance with the African Programme for Onchocerciasis Control (APOC objectives. Rev. Biol. Trop. 56 (4: 1635-1643. Epub 2008 December 12.La oncocercosis es endémica en el estado Ondo, Nigeria. Se seleccionaron 4 800 personas al azar para evaluar con encuesta retrospectiva la cobertura, efectos y reacciones al tratamiento farmacológico con ivermectina administrado por la misma comunidad. La cobertura global de ivermectina fue 50 % con reacciones adversas en

  1. Investigations of structure, bonding, and reactions of radiation-induced free radicals in the solid state using electron spin resonance spectroscopy

    International Nuclear Information System (INIS)

    Hudson, R.L.

    1978-01-01

    Electron spin resonance spectroscopy (ESR) has been used to study the structure, bonding, and reactions of several types of free radicals produced by γ irradiation of solids at 77K. Well-defined spectral patterns and the use of photolysis and annealing treatments assisted the analyses and interpretations. The radical anion BF 3 - was generated and identified unequivocally in a matrix of tetramethylsilane at 77K. Both the ESR data and theoretical calculations support a pyramidal structure with a bond angle of about 110 0 . The present experiments showed that BF 3 - has ESR parameters consistent with those of the isoelectronic radicals CF 3 , NF 3 + , and F 2 NO. γ irradiation of polycrystalline trimethyl borate at 77K gave an ESR spectrum which was assigned to the dimer radical anion [(MeO) 3 B.B(OMe) 3 ] - . Radical anions of dialkyl carbonates were observed for the first time and found to undergo a β-scission reaction to produce alkyl radicals. This free radical reaction is unusual in that it proceeds both thermally and photochemically. For the dimethyl carbonate radical anion, 13 C parameters were obtained from a 13 C enriched sample. The photolysis of trapped radicals in γ irradiated carboxylic esters, RC(O)OR', was studied by ESR spectroscopy and two different reactions were characterized. Two hypervalent silicon radical anions were prepared and examined in SI(OCH 3 ) 4 . The results of the present work thus represent the first complete sets of data on the silicon 3s and 3p spin densities for such species. The first PL 3 - radical anion was prepared by the γ irradiation of crystalline trimethylphosphite, and identified through its photolysis reactions and from the results of radiation chemical experiments

  2. Dual-level direct dynamics studies for the hydrogen abstraction reaction of 1,1-difluoroethane with O( 3P)

    Science.gov (United States)

    Liu, Jing-yao; Li, Ze-sheng; Dai, Zhen-wen; Zhang, Gang; Sun, Chia-chung

    2004-01-01

    We present dual-level direct dynamics calculations for the CH 3CHF 2 + O( 3P) hydrogen abstraction reaction in a wide temperature range, based on canonical variational transition-state theory including small curvature tunneling corrections. For this reaction, three distinct transition states, one for α-abstraction and two for β-abstraction, have been located. The potential energy surface information is obtained at the MP2(full)/6-311G(d,p) level of theory, and higher-level single-point calculations for the stationary points are preformed at several levels, namely QCISD(T)/6-311+G(3df,3pd), G2, and G3 using the MP2 geometries, as well as at the G3//MP4SDQ/6-311G(d,p) level. The energy profiles are further refined with the interpolated single-point energies method at the G3//MP2(full)/6-311G(d,p) level. The total rate constants match the experimental data reasonable well in the measured temperature range 1110-1340 K. It is shown that at low temperature α-abstraction may be the major reaction channel, while β-abstraction will have more contribution to the whole reaction rate as the temperature increases.

  3. Low-lying states and structure of the exotic 8He via direct reactions on the proton

    International Nuclear Information System (INIS)

    Skaza, F.; Lapoux, V.; Keeley, N.; Alamanos, N.; Auger, F.; Beaumel, D.; Becheva, E.; Blumenfeld, Y.; Delaunay, F.; Drouart, A.; Gillibert, A.; Giot, L.; Khan, E.; Nalpas, L.; Pakou, A.; Pollacco, E.; Raabe, R.; Roussel-Chomaz, P.; Rusek, K.; Scarpaci, J.-A.; Sida, J.-L.; Stepantsov, S.; Wolski, R.

    2007-01-01

    The structure of the light exotic nucleus 8 He was investigated using direct reactions of the 8 He SPIRAL beam on a proton-rich target. The (p,p') scattering to the 2 1 + state, the (p,d) 7 He and (p,t) 6 He transfer reactions, were measured at the energy E lab =15.7 A.MeV. The light charged particles (p,d,t) were detected in the MUST Si-strip telescope array. The excitation spectrum of 8 He was extracted from the (p,p') reaction. Above the known 2 1 + excited state at 3.6 MeV, a second resonance was found around 5.4 MeV. The cross sections were analyzed within the coupled-reaction channels framework, using microscopic potentials. It is inferred that the 8 He ground state has a more complex neutron-skin structure than suggested by previous α+4n models assuming a pure (1p 3/2 ) 4 configuration

  4. Direct Test of the Brown Dwarf Evolutionary Models Through Secondary Eclipse Spectroscopy of LHS 6343

    Science.gov (United States)

    Albert, Loic

    2015-10-01

    As the number of field Brown Dwarfs counts in the thousands, interpreting their physical parameters (mass, temperature, radius, luminosity, age, metallicity) relies as heavily as ever on atmosphere and evolutionary models. Fortunately, models are largely successful in explaining observations (colors, spectral types, luminosity), so they appear well calibrated in a relative sense. However, an absolute model-independent calibration is still lacking. Eclipsing BDs systems are a unique laboratory in this respect but until recently only one such system was known, 2M0535-05 - a very young (1 Gyr) - was identified (62.1+/-1.2 MJup, 0.783+/-0.011 RJup) transiting LHS6343 with a 12.7-day period. We propose to use WFC3 in drift scan mode and 5 HST orbits to determine the spectral type (a proxy for temperature) as well as the near-infrared luminosity of this brown dwarf. We conducted simulations that predict a signal-to-noise ratio ranging between 10 and 30 per resolution element in the peaks of the spectrum. These measurements, coupled with existing luminosity measurements with Spitzer at 3.6 and 4.5 microns, will allow us to trace the spectral energy distribution of the Brown Dwarf and directly calculate its blackbody temperature. It will be the first field Brown Dwarfs with simultaneous measurements of its radius, mass, luminosity and temperature all measured independently of models.

  5. Atomic emission and atomic fluorescence spectroscopy in the direct current plasma

    International Nuclear Information System (INIS)

    Hendrick, M.S.

    1985-01-01

    The Direct Current Plasma (DCP) was investigated as a source for Atomic Emission (AE) and Atomic Fluorescence Spectrometry (AFS). The DCP was optimized for AE analyses using simplex optimization and Box-Behnken partial factorial experimental design, varying argon flows, and plasma position. Results were compared with a univariate search carried out in the region of the simplex optimum. Canonical analysis demonstrated that no true optimum exists for sensitivity, precision, or drift. A stationary ridge, where combinations of conditions gave comparable instrumental responses, was found. The DCP as an excitation source for AFS in a flame was used for diagnostic studies of the DCP. Moving the aerosol introduction tube behind the DCP with respect to the flame improved the characteristics of the DCP as a narrow line source, although self-absorption was observed at high concentrations of metal salt solutions in the DCP. Detection limits for Cd, Co, Cr, Cu, Fe, Mg, Mn, Zn, and Ni were in the low ng/mL region. Theoretical expressions for scatter correction with a two-line technique were derived, although no correction was necessary to achieve accurate results for standard reference materials

  6. Fluctuation effects on average cross sections in compound, direct and doorway state resonance reactions

    International Nuclear Information System (INIS)

    Moldauer, P.A.

    1979-01-01

    The main features of the effects of S-matrix flucturations on average cross sections are reviewed with emphasis on recent developments on the enhancement of small cross sections and cross sections between directly coupled channels. Examples are given in which the effect can distort the shape of a doorway state resonance so as to reduce its observed width. 4 figures

  7. Direct photon production in heavy-ion reactions at SPS and RHIC

    Indian Academy of Sciences (India)

    An outlook on the perspective of photon measurements at ... QCD, the theory of strong interaction, enters the perturbative regime and is calculable. ... While photon production may be less difficult to treat than some other processes ... the context of both prompt and thermal direct photons, as they are dominated by the lowest.

  8. Direct formation of LiAlH4 by a mechanochemical reaction

    International Nuclear Information System (INIS)

    Kojima, Yoshitsugu; Kawai, Yasuaki; Haga, Tetsuya; Matsumoto, Mitsuru; Koiwai, Akihiko

    2007-01-01

    A small amount of lithium tetrahydridoaluminate (LiAlH 4 ) was directly synthesized by ball-milling of lithium hydride LiH and aluminum Al in a H 2 atmosphere (1 MPa) at room temperature. Concomitant formation of lithium hexahydridoaluminate Li 3 AlH 6 was confirmed

  9. Investigation of chemical and electrochemical reactions mechanisms in a direct carbon fuel cell using olive wood charcoal as sustainable fuel

    Science.gov (United States)

    Elleuch, Amal; Halouani, Kamel; Li, Yongdan

    2015-05-01

    Direct carbon fuel cell (DCFC) is a high temperature fuel cell using solid carbon as fuel. The use of environmentally friendly carbon material constitutes a promising option for the DCFC future. In this context, this paper focuses on the use of biomass-derived charcoal renewable fuel. A practical investigation of Tunisian olive wood charcoal (OW-C) in planar DCFCs is conducted and good power density (105 mW cm-2) and higher current density (550 mA cm-2) are obtained at 700 °C. Analytical and predictive techniques are performed to explore the relationships between fuel properties and DCFC chemical and electrochemical mechanisms. High carbon content, carbon-oxygen groups and disordered structure, are the key parameters allowing the achieved good performance. Relatively complex chain reactions are predicted to explain the gas evolution within the anode. CO, H2 and CH4 participation in the anodic reaction is proved.

  10. Electrochemical characterization of Pt-Ru-Pd catalysts for methanol oxidation reaction in direct methanol fuel cells.

    Science.gov (United States)

    Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

    2011-01-01

    PtRuPd nanoparticles on carbon black were prepared and characterized as electrocatalysts for methanol oxidation reaction in direct methanol fuel cells. Nano-sized Pd (2-4 nm) particles were deposited on Pt/C and PtRu/C (commercial products) by a simple chemical reduction process. The structural and physical information of the PtRuPd/C were confirmed by TEM and XRD, and their electrocatalytic activities were measured by cyclic voltammetry and linear sweep voltammetry. The catalysts containing Pd showed higher electrocatalytic activity for methanol oxidation reaction than the other catalysts. This might be attributed to an increase in the electrochemical surface area of Pt, which is caused by the addition of Pd; this results in increased catalyst utilization.

  11. Type I photosensitized reactions of oxopurines. Kinetics and thermodynamics of the reaction with triplet benzophenone by time-resolved photoacoustic spectroscopy

    Science.gov (United States)

    Murgida, Daniel H.; Erra Balsells, Rosa; Crippa, Pier Raimondo; Viappiani, Cristiano

    1998-09-01

    Benzophenone photosensitized reactions of caffeine, theophylline and theobromine were investigated in acetonitrile by time-resolved laser-induced photoacoustics. In the three cases global quenching rate constants of triplet benzophenone were measured as a function of temperature and it was observed that this is a non-activated process. Besides, for theobromine and theophylline heats for NH hydrogen abstraction reactions were determined. In agreement with semiempirical calculation predictions, hydrogen abstraction is thermodynamically more favorable and faster for theophylline (Δ H=-265 kJ mol -1, kr=9.6×10 8 M -1 s -1) than for theobromine (Δ H=-168 kJ mol -1, kr=3.7×10 8 M -1 s -1).

  12. Kinetics of the F+NO2+M->FNO2+M reaction studied by pulse radiolysis combined with time-resolved IR and UV spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, Palle Bjørn; Sillesen, A.; Jodkowski, J.T.

    1996-01-01

    was studied with SF6 pressures of 5-1000 mbar at 298 K. Comparative studies were carried out by monitoring the decay kinetics of NO2 at 445 nm using pressures of 100-1000 mbar at 295 and 341 K. The observed pressure dependence is represented in terms of a fall-off curve with the following values......The title reaction was initiated by the pulse radiolysis of SF6/NO2 gas mixtures, and the formation of FNO2 was studied by time-resolved infrared spectroscopy employing strong rotational transitions within the nu(1) and nu(4) bands of FNO2. The pressure dependence of the formation kinetics...

  13. Measurement of cross-sections of yttrium (n,xn) threshold reactions by means of gamma spectroscopy

    CERN Document Server

    Chudoba, Petr; Wagner, V; Vrzalova, J; Svoboda, O; Majerle, M; Stefanik, M; Suchopar, M; Kugler, A; Bielewicz, M; Strugalska-Gola, E; Szuta, M; Hervas, D; Herman, T; Geier, B

    2014-01-01

    Neutron activation and gamma spectrometry are usable also f or the determination of cross-sections of different neutron reactions. We have studied the cross-sections of yttrium (n, x n) threshold reactions using quasi-monoenergetic neutron source based on the reaction on 7 Li target at Nuclear Physics Institute of ASCR in Rez. Yttrium (n, x n) threshold reactions are suitable candidates for fast neutron field measurement by activation detectors. Fast neutron field monitoring is necessary already today at a wide range of accelerator facilities and will gain on importance in future fast reactors of generation IV, accelerator transmutation systems or fusion reactors. The knowledge of the cross-sections is crucial for such purpose. Unfortunately, the cross-section is sufficiently known only for 89 Y(n,2n) 88 Y reaction. For higher orders of reactions there are almost no experimental data. Special attention was paid to t he 89 Y(n,3n) 87 Y reaction. The cross-sections of both 89 Y(n,2n) 88 Y and 89 Y(n,3n) 87 Y re...

  14. Advances in Methane Isotope Measurements via Direct Absorption Spectroscopy with Applications to Oil and Gas Source Characterization

    Science.gov (United States)

    Yacovitch, T. I.; Herndon, S. C.; Roscioli, J. R.; Petron, G.; Shorter, J. H.; Jervis, D.; McManus, J. B.; Nelson, D. D.; Zahniser, M. S.; Kolb, C. E., Jr.

    2015-12-01

    Instrumental developments in the measurement of multiple isotopes of methane (12CH4, 13CH4 and 12CH3D) are presented. A first generation 8-micron instrument quantifies 12CH4 and 13CH4 at a 1-second rate via tunable infrared direct absorption spectroscopy (TILDAS). A second generation instrument uses two 3-micron intraband cascade lasers in an Aerodyne dual laser chassis for simultaneous measurement of 12CH4, 13CH4 and 12CH3D. Sensitivity and noise performance improvements are examined. The isotopic signature of methane provides valuable information for emission source identification of this greenhouse gas. A first generation spectrometer has been deployed in the field on a mobile laboratory along with a sophisticated 4-tank calibration system. Calibrations are done on an agressive schedule, allowing for the correction of measured isotope ratios to an absolute isotope scale. Distinct isotopic signatures are found for a number of emission sources in the Denver-Julesburg Basin: oil and gas gathering stations, compressor stations and processing plants; a municipal landfill, and dairy/cattle operations. The isotopic signatures are compared with measured ethane/methane ratios. These direct absorption measurements have larger uncertainties than samples measured via gas chromatography-mass spectrometry, but have several advantages over canister sampling methods: individual sources of short duration are easier to isolate; calibrated isotope ratio results are available immediately; replicate measurements on a single source are easily performed; and the number of sources sampled is not limited by canister availability and processing time.

  15. Feasibility of Traveling Wave Direct Energy Conversion of Fission Reaction Fragments

    Science.gov (United States)

    Tarditi, A. G.; George, J. A.; Miley, G. H.; Scott, J. H.

    2013-01-01

    Fission fragment direct energy conversion has been considered in the past for the purpose of increasing nuclear power plant efficiency and for advanced space propulsion. Since the fragments carry electric charge (typically in the order of 20 e) and have 100 MeV-range kinetic energy, techniques utilizing very high-voltage DC electrodes have been considered. This study is focused on a different approach: the kinetic energy of the charged fission fragments is converted into alternating current by means of a traveling wave coupling scheme (Traveling Wave Direct Energy Converter, TWDEC), thereby not requiring the utilization of high voltage technology. A preliminary feasibility analysis of the concept is introduced based on a conceptual level study and on a particle simulation model of the beam dynamics.

  16. A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kneebone, Jared L. [Univ. of Rochester, Rochester, NY (United States); Daifuku, Stephanie L. [Univ. of Rochester, Rochester, NY (United States); Kehl, Jeffrey A. [Univ. of Rochester, Rochester, NY (United States); Wu, Gang [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Chung, Hoon T. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hu, Michael Y. [Argonne National Lab. (ANL), Argonne, IL (United States); Alp, E. Ercan [Argonne National Lab. (ANL), Argonne, IL (United States); More, Karren L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Zelenay, Piotr [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Holby, Edward F. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Neidig, Michael L. [Univ. of Rochester, Rochester, NY (United States)

    2017-07-06

    While non-precious metal M-N-C (M = Fe or Co) catalysts have been developed that are effective for the oxygen reduction reaction in polymer electrolyte fuel cells, no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for reaction with dioxygen (O2). While multiple studies have developed correlations between Fe distributions in as-prepared catalysts and ORR activity, the direct identification of sites reactive towards O2 or O2-analog molecules remains a significant challenge. In the present study, we demonstrate a new approach to identifying and characterizing potential Fe active sites in complex ORR catalysts that combines an effective probe molecule (NO(g)) Mössbauer spectroscopy and nuclear resonance vibrational spectroscopy (NRVS) with density functional theory (DFT) calculations. Mössbauer spectroscopic studies demonstrate that NO(g) treatment of electrochemically reduced PANI-57Fe-C leads to selective reaction with only a sub-set of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe-ligand vibrations associated with the site reactive towards NO(g). DFT calculations of vibrational properties of a small selection of previously proposed active site structures suggest that graphene zig-zag edge hosted Fe-N structures may be responsible for the observed vibrational behavior with NO(g) probe molecules. Moreover, such sites are likely also reactive to O2, possibly serving as the ORR active sites in the synthesized materials.

  17. Proton transfers in a channelrhodopsin-1 studied by Fourier transform infrared (FTIR) difference spectroscopy and site-directed mutagenesis.

    Science.gov (United States)

    Ogren, John I; Yi, Adrian; Mamaev, Sergey; Li, Hai; Spudich, John L; Rothschild, Kenneth J

    2015-05-15

    Channelrhodopsin-1 from the alga Chlamydomonas augustae (CaChR1) is a low-efficiency light-activated cation channel that exhibits properties useful for optogenetic applications such as a slow light inactivation and a red-shifted visible absorption maximum as compared with the more extensively studied channelrhodopsin-2 from Chlamydomonas reinhardtii (CrChR2). Previously, both resonance Raman and low-temperature FTIR difference spectroscopy revealed that unlike CrChR2, CaChR1 under our conditions exhibits an almost pure all-trans retinal composition in the unphotolyzed ground state and undergoes an all-trans to 13-cis isomerization during the primary phototransition typical of other microbial rhodopsins such as bacteriorhodopsin (BR). Here, we apply static and rapid-scan FTIR difference spectroscopy along with site-directed mutagenesis to characterize the proton transfer events occurring upon the formation of the long-lived conducting P2 (380) state of CaChR1. Assignment of carboxylic C=O stretch bands indicates that Asp-299 (homolog to Asp-212 in BR) becomes protonated and Asp-169 (homolog to Asp-85 in BR) undergoes a net change in hydrogen bonding relative to the unphotolyzed ground state of CaChR1. These data along with earlier FTIR measurements on the CaChR1 → P1 transition are consistent with a two-step proton relay mechanism that transfers a proton from Glu-169 to Asp-299 during the primary phototransition and from the Schiff base to Glu-169 during P2 (380) formation. The unusual charge neutrality of both Schiff base counterions in the P2 (380) conducting state suggests that these residues may function as part of a cation selective filter in the open channel state of CaChR1 as well as other low-efficiency ChRs. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  18. Gas sensing properties and in situ diffuse reflectance infrared Fourier transform spectroscopy study of trichloroethylene adsorption and reactions on SnO2 films

    Science.gov (United States)

    Zhang, Zhenxin; Huang, Kaijin; Yuan, Fangli; Xie, Changsheng

    2014-05-01

    The detection of trichloroethylene has attracted much attention because it has an important effect on human health. The sensitivity of the SnO2 flat-type coplanar gas sensor arrays to 100 ppm trichloroethylene in air was investigated. The adsorption and surface reactions of trichloroethylene were investigated at 100-200 °C by in-situ diffuse reflection Fourier transform infrared spectroscopy (DIRFTS) on SnO2 films. Molecularly adsorbed trichloroethylene, dichloroacetyl chloride (DCAC), phosgene, HCl, CO, H2O, CHCl3, Cl2 and CO2 surface species are formed during trichloroethylene adsorption at 100-200 °C. A possible mechanism of the reaction process is discussed.

  19. Direct costs of managing adverse drug reactions during rifampicin-resistant tuberculosis treatment in South Africa.

    Science.gov (United States)

    Schnippel, K; Firnhaber, C; Berhanu, R; Page-Shipp, L; Sinanovic, E

    2018-04-01

    To estimate the provider costs of managing adverse drug reactions (ADRs) to standard long-course treatment for multidrug- and rifampicin-resistant tuberculosis (MDR/RR-TB) according to South African guidelines. We parameterised a published Markov health state model for MDR/RR-TB with guidelines-based, bottom-up public-sector provider costing of ADR management. Frequency of ADR occurrence was extracted from the literature. Costs were estimated over 10 years, discounted 3% annually and tested using probabilistic sensitivity analysis. On average, guidelines-based costing of moderate ADRs weighted by the frequency of occurrence was US$135.76 (standard deviation [SD] US$17.18) and the cost of serious ADRs was US$521.29 (SD US$55.99). We estimated that the incremental costs of ADR management were US$380.17 annually per patient initiating MDR/RR-TB treatment. The incremental costs of ADR management for the public health sector in South Africa was US$4.76 million, 8.3% of the estimated cohort costs of MDR/RR-TB treatment ($57.55 million) for the 2015 cohort of 12 527 patients. Management of multiple ADRs and serious ADRs, which are common during the first 6 months of standard, long-course MDR/RR-TB treatment, substantially increases provider treatment costs. These results need to be taken into account when comparing regimen costs, and highlight the urgent need to identify drug regimens with improved safety profiles.

  20. Directed surfaces structures and interfaces for enhanced electrocatalyst activity, selectivity, and stability for energy conversion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Jaramillo, Thomas F. [Stanford Univ., CA (United States). Dept. of Chemical Engineering. Shriram Center

    2016-04-20

    In this project, we have employed a systematic approach to develop active, selective, and stable catalyst materials for important electrochemical reactions involving energy conversion. In particular, we have focused our attention on developing active catalyst materials for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). HER: We have synthesized and investigated several highly active and acid stable non-precious metal HER catalysts, including: [Mo3S13]2- nanoclusters (Nature Chemistry, 2014) and molybdenum phosphosulfide (MoP|S) (Angewandte Chemie, 2014). We have also aimed to engineer these catalyst formulations in a membrane electrode assembly (MEA) for fundamental studies of water electrolysis at high current densities, approximately 1 A/cm2 (ChemSusChem, 2015). We furthermore investigated transition metal phosphide (TMP) catalysts for HER by a combined experimental–theoretical approach (Energy & Environmental Science, 2015). By synthesizing different TMPs and comparing experimentally determined HER activities with the hydrogen adsorption free energies, ΔGH, calculated by density functional theory, we showed that the TMPs follow a volcano relationship for the HER. Using our combined experimental–theoretical model, we predicted that the mixed metal TMP, Fe0.5Co0.5P, should have a near-optimal ΔGH. We synthesized several mixtures of Co and Fe phosphides alloys and confirmed that Fe0.5Co0.5P exhibits the highest HER activity of the investigated TMPs (Energy & Environmental Science, 2015). The understanding gained as to how to improve catalytic activity for the HER, particularly for non-precious metal materials, is important to DOE targets for sustainable H2 production. OER: We have developed a SrIrO3/IrOx catalyst for acidic conditions (submitted, 2016). The Sr

  1. A study of the atmospherically important reactions of dimethylsulfide (DMS) with I2 and ICl using infrared matrix isolation spectroscopy and electronic structure calculations.

    Science.gov (United States)

    Beccaceci, Sonya; Armata, Nerina; Ogden, J Steven; Dyke, John M; Rhyman, Lydia; Ramasami, Ponnadurai

    2012-02-21

    The reactions of dimethylsulfide (DMS) with molecular iodine (I(2)) and iodine monochloride (ICl) have been studied by infrared matrix isolation spectroscopy by co-condensation of the reagents in an inert gas matrix. Molecular adducts of DMS + I(2) and DMS + ICl have also been prepared using standard synthetic methods. The vapour above each of these adducts trapped in an inert gas matrix gave the same infrared spectrum as that recorded for the corresponding co-condensation reaction. In each case, the infrared spectrum has been interpreted in terms of a van der Waals adduct, DMS : I(2) and DMS : ICl, with the aid of infrared spectra computed for their minimum energy structures at the MP2 level. Computed relative energies of minima and transition states on the potential energy surfaces of these reactions were used to understand why they do not proceed further than the reactant complexes DMS : I(2) and DMS : ICl. The main findings of this research are compared with results obtained earlier for the DMS + Cl(2) and DMS + Br(2) reactions, and the atmospheric implications of the conclusions are also considered.

  2. In situ Fourier transform infrared spectroscopy and on-line differential electrochemical mass spectrometry study of the NH3BH3 oxidation reaction on gold electrodes

    International Nuclear Information System (INIS)

    Belén Molina Concha, M.; Chatenet, Marian; Lima, Fabio H.B.; Ticianelli, Edson A.

    2013-01-01

    The ammonia borane (NH 3 BH 3 ) oxidation reaction (ABOR) was studied on gold electrodes using the rotating disk electrode (RDE) setup and coupled physical techniques: on-line differential electrochemical mass spectrometry (DEMS) and in situ Fourier transform infrared spectroscopy (FTIR). Non-negligible heterogeneous hydrolysis in the low-potential region was asserted via molecular H 2 detection. As a consequence, the number of electron exchanged per BH 3 OH − species is ca. 3 at low potential, and only reaches ca. 6 above 0.6 V vs. RHE. These figures were confirmed by Levich and Koutecki–Levich calculations using the RDE experiments data. The nature of the ABOR intermediates and products was determined using in situ FTIR. While BH 2 species were detected during the ABOR, it seems that its adsorption onto the Au electrode proceeds via the O atom, in opposition to what happens during the borohydride oxidation reaction (BOR). Therefore, it is likely that the mechanism of the ABOR differs from that of the BOR. From the whole set of data (RDE, DEMS, FTIR), a relevant reaction pathway was proposed, including competition between the BH 3 OH − heterogeneous hydrolysis and oxidation at low potential, and preponderant oxidation at higher potential. Finally, a simplified kinetic modeling accounting with this reaction pathway was proposed, which nicely fits the stationary (i vs. E) ABOR plot

  3. Enhancing the methanol tolerance of platinum nanoparticles for the cathode reaction of direct methanol fuel cells through a geometric design.

    Science.gov (United States)

    Feng, Yan; Ye, Feng; Liu, Hui; Yang, Jun

    2015-11-18

    Mastery over the structure of nanoparticles might be an effective way to enhance their performance for a given application. Herein we demonstrate the design of cage-bell nanostructures to enhance the methanol tolerance of platinum (Pt) nanoparticles while remaining their catalytic activity for oxygen reduction reaction. This strategy starts with the synthesis of core-shell-shell nanoparticles with Pt and silver (Ag) residing respectively in the core and inner shell regions, which are then agitated with saturated sodium chloride (NaCl) solution to eliminate the Ag component from the inner shell region, leading to the formation of bimetallic nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a metal shell with nano-channels, which exhibit superior methanol-tolerant property in catalyzing oxygen reduction reaction due to the different diffusion behaviour of methanol and oxygen in the porous metal shell of cage-bell structured nanoparticles. In particular, the use of remarkably inexpensive chemical agent (NaCl) to promote the formation of cage-bell structured particles containing a wide spectrum of metal shells highlights its engineering merit to produce highly selective electrocatalysts on a large scale for the cathode reaction of direct methanol fuel cells.

  4. Fragmentation and direct transfer reactions for 40Ar incident beam on 27Al target at 1760 MeV

    International Nuclear Information System (INIS)

    Cisse, Ousmane

    1985-01-01

    Peripheral collision studies performed with 40 Ar projectiles at 44 MeV/A and 27 Al target show that both fragmentation and transfer reactions can be discerned in this type of interaction. The experimental observation of fragments with masses charges and velocities close to those of the incident beam are the signature of transfer reactions and a detailed analysis of the energy spectra of such fragments has been carried out and interpreted in terms of a direct diffraction transfer model. On the other hand, for large mass transfer reactions, abrasion is the suitable mechanism. Inclusive fragment measurement together with the appropriate residual nuclei-fragment coincidence results then provides experimental data in good agreement with the theoretical predictions obtained from a participant spectator model. These investigations also indicate that the separation energies of the participant from the spectator nucleus, at least within the framework of the above model, can be interpreted in terms of a friction force which becomes more efficient as the projectile energy decreases. (author) [fr

  5. Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy

    KAUST Repository

    Michalak, William D.

    2013-01-31

    The product selectivity during 1,3-butadiene hydrogenation on monodisperse, colloidally synthesized, Pt nanoparticles was studied under reaction conditions with kinetic measurements and in situ sum frequency generation (SFG) vibrational spectroscopy. SFG was performed with the capping ligands intact in order to maintain nanoparticle size by reduced sintering. Four products are formed at 75 C: 1-butene, cis-2-butene, trans-2-butene, and n-butane. Ensembles of Pt nanoparticles with average diameters of 0.9 and 1.8 nm exhibit a ∼30% and ∼20% increase in the full hydrogenation products, respectively, as compared to Pt nanoparticles with average diameters of 4.6 and 6.7 nm. Methyl and methylene vibrational stretches of reaction intermediates observed under working conditions using SFG were used to correlate the stable reaction intermediates with the product distribution. Kinetic and SFG results correlate with previous DFT predictions for two parallel reaction pathways of 1,3-butadiene hydrogenation. Hydrogenation of 1,3-butadiene can initiate with H-addition at internal or terminal carbons leading to the formation of 1-buten-4-yl radical (metallocycle) and 2-buten-1-yl radical intermediates, respectively. Small (0.9 and 1.8 nm) nanoparticles exhibited vibrational resonances originating from both intermediates, while the large (4.6 and 6.7 nm) particles exhibited vibrational resonances originating predominately from the 2-buten-1-yl radical. This suggests each reaction pathway competes for partial and full hydrogenation and the nanoparticle size affects the kinetic preference for the two pathways. The reaction pathway through the metallocycle intermediate on the small nanoparticles is likely due to the presence of low-coordinated sites. © 2012 American Chemical Society.

  6. Investigation of high-precision Λ hypernuclear spectroscopy via the (e,e'K+) reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kawama, Daisuke [Tohoku Univ., Sendai (Japan)

    2011-01-01

    The study of Λ hypernuclear structure is very interesting in point of the understanding of the interaction between Λ and nucleon (Λ-N interaction) and its strange structure itself due to the containment of a Λ hyperon which has a strangeness as a new degree of freedom. In the several way to study the Lamda hypernuclei, the (e,e'K+) reaction spectroscopy is a powerful tool for the precise investigation of Λ hypernuclear structure. The purpose of the preset thesis is the establishment of the experimental design with the efficient data analysis method for the (e,e'K+) hypernuclear spectroscopic experiment in the wide mass region (from A=7 to A=52). It is very challenging to perform the (e,e'K+) spectroscopic experiment with such a heavy target, because of the huge electron background due to the bremsstrahlung process. In the experiment, it is required to obtain the necessary hypernuclear yield, suppressing the background event ratio. We achieved these requirements by newly constructing the high resolution electron spectrometer (HES) and splitter magnet (SPL) dedicated to the (e,e'K+) spectroscopic experiment. The HES consists of two quadrupole magnets and a dipole magnets (Q-Q-D) with a momentum resolution of dp/p = 3x10-4 at p = 0.84 GeV/c. It was used being vertically tilted by 6.5 degree so as to optimize signal to noise ratio and hypernuclear yield. The SPL is a dipole magnet. The experimental target was placed at the entrance of this magnet. The role of the SPL is to separate four kind of particles; scattered kaons, photons created by the bremsstrahlung, the post beam and scattered electrons. In addition, since the SPL is a part of the kaon and electron spectrometers. We designed the magnet shape carefully considering these points. The experiment was performed with 2.344 GeV/c electron beam from CEBAF at Jefferson Lab. The experimental setup consists of the HES, SPL and HKS (high momentum resolution kaon

  7. Palladium-based electrocatalysts for ethanol oxidation reaction in alkaline direct ethanol fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Moraes, Leticia Poras Reis de; Amico, Sandro Campos; Malfatti, Celia de Fraga, E-mail: leticiamoraes@usp.br [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre (Brazil); Matos, Bruno R.; Santiago, Elisabete Inacio; Fonseca, Fabio Coral [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2016-07-01

    Full text: Direct ethanol fuel cells require adequate electrocatalysts to promote the carbon carbon cleavage of ethanol molecule. Typical electrocatalysts are based on platinum, which have shown improved activity in acidic media. However, Pt-based catalysts have high cost and are easily deactivated by CO poisoning. Therefore, novel catalysts have been developed, and among then, palladium-based materials have shown promising results for the oxidation of ethanol in alkaline media. The present study reports on the performance of alkaline direct ethanol fuel cell (ADEFC) by using carbon-supported Pd, PdSn, PdNi, and PdNiSn produced by impregnation-reduction of the metallic precursors. The effect of chemical functionalization by acid treatment of the carbon support (Vulcan) was investigated. The electrocatalysts were studied by thermogravimetric analysis (TGA), X-rays diffraction (XRD), transmission electron microscopy (TEM), cyclic voltammetry (CV), and ADEFC tests. TGA measurements of functionalized Vulcan evidenced the characteristic weight losses attributed to the presence of surface functional groups due to the acid treatment. A high degree of alloying between Pd and Sn was inferred from XRD data, whereas in both PdNi and PdNiSn, Ni occurs mostly segregated in the oxide form. TEM analyses indicated agglomeration of Pd and PdSn particles, whereas a more uniform particle distribution was observed for PdNi and PdNiSn samples. CV curves showed that the peak potential for the oxidation of ethanol shifts towards negative values for all samples supported on functionalized Vulcan indicating that ethanol oxidation is facilitated. Microstructural and electrochemical features were confirmed by ADEFC tests, which revealed that the highest open circuit voltage and maximum power density were achieved for PdNiSn electrocatalysts supported on functionalized Vulcan with uniform particle distribution and improved triple phase boundaries. (author)

  8. Palladium-based electrocatalysts for ethanol oxidation reaction in alkaline direct ethanol fuel cell

    International Nuclear Information System (INIS)

    Moraes, Leticia Poras Reis de; Amico, Sandro Campos; Malfatti, Celia de Fraga; Matos, Bruno R.; Santiago, Elisabete Inacio; Fonseca, Fabio Coral

    2016-01-01

    Full text: Direct ethanol fuel cells require adequate electrocatalysts to promote the carbon carbon cleavage of ethanol molecule. Typical electrocatalysts are based on platinum, which have shown improved activity in acidic media. However, Pt-based catalysts have high cost and are easily deactivated by CO poisoning. Therefore, novel catalysts have been developed, and among then, palladium-based materials have shown promising results for the oxidation of ethanol in alkaline media. The present study reports on the performance of alkaline direct ethanol fuel cell (ADEFC) by using carbon-supported Pd, PdSn, PdNi, and PdNiSn produced by impregnation-reduction of the metallic precursors. The effect of chemical functionalization by acid treatment of the carbon support (Vulcan) was investigated. The electrocatalysts were studied by thermogravimetric analysis (TGA), X-rays diffraction (XRD), transmission electron microscopy (TEM), cyclic voltammetry (CV), and ADEFC tests. TGA measurements of functionalized Vulcan evidenced the characteristic weight losses attributed to the presence of surface functional groups due to the acid treatment. A high degree of alloying between Pd and Sn was inferred from XRD data, whereas in both PdNi and PdNiSn, Ni occurs mostly segregated in the oxide form. TEM analyses indicated agglomeration of Pd and PdSn particles, whereas a more uniform particle distribution was observed for PdNi and PdNiSn samples. CV curves showed that the peak potential for the oxidation of ethanol shifts towards negative values for all samples supported on functionalized Vulcan indicating that ethanol oxidation is facilitated. Microstructural and electrochemical features were confirmed by ADEFC tests, which revealed that the highest open circuit voltage and maximum power density were achieved for PdNiSn electrocatalysts supported on functionalized Vulcan with uniform particle distribution and improved triple phase boundaries. (author)

  9. Micro-Raman spectroscopy investigation of the carbonation reaction in a lime paste produced with a traditional technology

    Czech Academy of Sciences Publication Activity Database

    Ševčík, Radek; Mácová, Petra; Sotiriadis, Konstantinos; Pérez-Estébanez, Marta; Viani, Alberto; Šašek, Petr

    2016-01-01

    Roč. 47, č. 12 (2016), s. 1452-1457 ISSN 0377-0486 R&D Projects: GA ČR(CZ) GP14-20374P; GA MŠk(CZ) LO1219 Keywords : calcite * carbonation * lime paste * micro-Raman spectroscopy * portlandite Subject RIV: AL - Art, Architecture, Cultural Heritage Impact factor: 2.969, year: 2016 http://onlinelibrary.wiley.com/doi/10.1002/jrs.4929/full

  10. Nuclear Level Densities for Modeling Nuclear Reactions: An Efficient Approach Using Statistical Spectroscopy: Annual Scientific Report July 2004

    International Nuclear Information System (INIS)

    Calvin W. Johnson

    2004-01-01

    The general goal of the project is to develop and implement computer codes and input files to compute nuclear densities of state. Such densities are important input into calculations of statistical neutron capture, and are difficult to access experimentally. In particular, we will focus on calculating densities for nuclides in the mass range A ?????? 50 - 100. We use statistical spectroscopy, a moments method based upon a microscopic framework, the interacting shell model. In this report we present our progress for the past year

  11. Oxidation Half-Reaction of Aqueous Nucleosides and Nucleotides via Photoelectron Spectroscopy Augmented by ab Initio Calculations

    Czech Academy of Sciences Publication Activity Database

    Schroeder, C. A.; Pluhařová, Eva; Seidel, R.; Schroeder, W. P.; Faubel, M.; Slavíček, P.; Winter, B.; Jungwirth, Pavel; Bradforth, S. E.

    2015-01-01

    Roč. 137, č. 1 (2015), s. 201-209 ISSN 0002-7863 R&D Projects: GA ČR GBP208/12/G016 Grant - others:GA ČR(CZ) GA13-34168S Institutional support: RVO:61388963 Keywords : DNA damage * photoelectron spectroscopy * DNA charge migration Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 13.038, year: 2015 http://pubs.acs.org/doi/10.1021/ja508149e

  12. Evaluation of a setting reaction pathway in the novel composite TiHA-CSD bone cement by FT-Raman and FT-IR spectroscopy

    Science.gov (United States)

    Paluszkiewicz, Czesława; Czechowska, Joanna; Ślósarczyk, Anna; Paszkiewicz, Zofia

    2013-02-01

    The aim of this study was to determine a setting reaction pathway in a novel, surgically handy implant material, based on calcium sulfate hemihydrate (CSH) and titanium doped hydroxyapatite (TiHA). The previous studies confirmed superior biological properties of TiHA in comparison to the undoped hydroxyapatite (HA) what makes it highly attractive for future medical applications. In this study the three types of titanium modified HA powders: untreated, calcined at 800 °C, sintered at 1250 °C and CSH were used to produce bone cements. The Fourier Transform-InfraRed (FT-IR) spectroscopy and Raman spectroscopy were applied to evaluate processes taking place during the setting of the studied materials. Our results undoubtedly confirmed that the reaction pathways and the phase compositions differed significantly for set cements and were dependent on the initial heat treatment of TiHA powder. Final materials were multiphase composites consisting of calcium sulfate dihydrate, bassanite, tricalcium phosphate, hydroxyapatite and calcium titanate (perovskite). The FT-IR and Scanning Electron Microscopy (SEM) measurements performed after the incubation of the cement samples in the simulated body fluid (SBF), indicate on high bioactive potential of the obtained bone cements.

  13. Metal oxide nanoparticle mediated enhanced Raman scattering and its use in direct monitoring of interfacial chemical reactions.

    Science.gov (United States)

    Li, Li; Hutter, Tanya; Finnemore, Alexander S; Huang, Fu Min; Baumberg, Jeremy J; Elliott, Stephen R; Steiner, Ullrich; Mahajan, Sumeet

    2012-08-08

    Metal oxide nanoparticles (MONPs) have widespread usage across many disciplines, but monitoring molecular processes at their surfaces in situ has not been possible. Here we demonstrate that MONPs give highly enhanced (×10(4)) Raman scattering signals from molecules at the interface permitting direct monitoring of their reactions, when placed on top of flat metallic surfaces. Experiments with different metal oxide materials and molecules indicate that the enhancement is generic and operates at the single nanoparticle level. Simulations confirm that the amplification is principally electromagnetic and is a result of optical modulation of the underlying plasmonic metallic surface by MONPs, which act as scattering antennae and couple light into the confined region sandwiched by the underlying surface. Because of additional functionalities of metal oxides as magnetic, photoelectrochemical and catalytic materials, enhanced Raman scattering mediated by MONPs opens up significant opportunities in fundamental science, allowing direct tracking and understanding of application-specific transformations at such interfaces. We show a first example by monitoring the MONP-assisted photocatalytic decomposition reaction of an organic dye by individual nanoparticles.

  14. Chemical Analysis of Reaction Rims on Olivine Crystals in Natural Samples of Black Dacite Using Energy-Dispersive X-Ray Spectroscopy, Lassen Peak, CA.

    Science.gov (United States)

    Graham, N. A.

    2014-12-01

    Lassen Volcanic Center is the southernmost volcanic region in the Cascade volcanic arc formed by the Cascadia Subduction Zone. Lassen Peak last erupted in 1915 in an arc related event producing a black dacite material containing xenocrystic olivine grains with apparent orthopyroxene reaction rims. The reaction rims on these olivine grains are believed to have formed by reactions that ensued from a mixing/mingling event that occurred prior to eruption between the admixed mafic andesitic magma and a silicic dacite host material. Natural samples of the 1915 black dacite from Lassen Peak, CA were prepared into 15 polished thin sections and carbon coated for analysis using a FEI Quanta 250 Scanning Electron Microscope (SEM) to identify and measure mineral textures and disequilibrium reaction rims. Observed mineralogical textures related to magma mixing include biotite and amphibole grains with apparent dehydration/breakdown rims, pyroxene-rimmed quartz grains, high concentration of microlites in glass matrix, and pyroxene/amphibole reaction rims on olivine grains. Olivine dissolution is evidenced as increased iron concentration toward convolute edges of olivine grains as observed by Backscatter Electron (BSE) imagery and elemental mapping using NSS spectral imaging software. In an attempt to quantify the area of reaction rim growth on olivine grains within these samples, high-resolution BSE images of 30 different olivine grains were collected along with Energy-Dispersive X-Ray Spectroscopy (EDS) of different phases. Olivine cores and rims were extracted from BSE images using Photoshop and saved as separate image files. ImageJ software was used to calculate the area (μm2) of the core and rim of these grains. Average pyroxene reaction rim width for 30 grains was determined to be 11.68+/-1.65 μm. Rim widths of all 30 grains were averaged together to produce an overall average rim width for the Lassen Peak black dacite. By quantifying the reaction rims on olivine grains

  15. Measurement of (n,xn) reaction cross-sections using prompt {gamma} spectroscopy at neutron beams with high instantaneous flux; Mesure de sections efficaces de reaction (n,xn) par spectroscopie {gamma} prompte aupres d'un faisceau a tres haut flux instantane

    Energy Technology Data Exchange (ETDEWEB)

    Lukic, S

    2004-10-15

    The work presented in this thesis is situated in the context of the GEDEON program of neutron cross-section measurements. This program is motivated by the perspectives recently opened by projects of nuclear waste treatment and energy production. There is an obvious lack of experimental data on (n,xn) reactions in the databases, especially in the case of very radioactive isotopes. An important technique to measure cross-sections of these reactions is the prompt {gamma}-ray spectroscopy at white pulsed neutron beams with very high instantaneous flux. In this work, inelastic scattering and (n,xn) reactions cross-section measurements were performed on a lead sample from threshold to 20 MeV by prompt {gamma}-ray spectroscopy at the white neutron beam generated by GELINA facility in Geel, Belgium. Digital methods were developed to treat HPGe CLOVER detector signals and separate {gamma}-rays induced by the fastest neutrons from those belonging to the flash. Partial cross-sections for the production of several transitions in natural lead were measured and analyzed using theoretical calculations in order to separate the contributions of different reactions leading to the same residual isotope. Total cross-sections of the reactions in question were estimated. The results were compared to the TALYSS code theoretical calculations, as well as to other experimental results. This experiment has served to validate the method and it opens the way to measure (n,xn) reactions cross-sections with high instantaneous neutron flux on actinides, particularly the U{sup 233}(n,2n) reaction which is important for the thorium cycle. (author)

  16. New Directions: Ozone-initiated reaction products indoors may be more harmful than ozone itself

    Science.gov (United States)

    Weschler, Charles J.

    2004-10-01

    Epidemiological studies have found associations between ozone concentrations measured at outdoor monitoring stations and certain adverse health outcomes. As a recent example, Gent et al. (2003, Journal of the American Medical Association 290, 1859-1867) have observed an association between ozone levels and respiratory symptoms as well as the use of maintenance medication by 271 asthmatic children living in Connecticut and the Springfield area of Massachusetts. In another example, Gilliland et al. (2001, Epidemiology 12, 43-54) detected an association between short-term increases in ozone levels and increased absences among 4th grade students from 12 southern California communities during the period from January to June 1996. Although children may spend a significant amount of time outdoors, especially during periods when ozone levels are elevated, they spend a much larger fraction of their time indoors. I hypothesize that exposure to the products of ozone-initiated indoor chemistry is more directly responsible for the health effects observed in the cited epidemiological studies than is exposure to outdoor ozone itself.

  17. Direct comparison of low- and mid-frequency Raman spectroscopy for quantitative solid-state pharmaceutical analysis.

    Science.gov (United States)

    Lipiäinen, Tiina; Fraser-Miller, Sara J; Gordon, Keith C; Strachan, Clare J

    2018-02-05

    This study considers the potential of low-frequency (terahertz) Raman spectroscopy in the quantitative analysis of ternary mixtures of solid-state forms. Direct comparison between low-frequency and mid-frequency spectral regions for quantitative analysis of crystal form mixtures, without confounding sampling and instrumental variations, is reported for the first time. Piroxicam was used as a model drug, and the low-frequency spectra of piroxicam forms β, α2 and monohydrate are presented for the first time. These forms show clear spectral differences in both the low- and mid-frequency regions. Both spectral regions provided quantitative models suitable for predicting the mixture compositions using partial least squares regression (PLSR), but the low-frequency data gave better models, based on lower errors of prediction (2.7, 3.1 and 3.2% root-mean-square errors of prediction [RMSEP] values for the β, α2 and monohydrate forms, respectively) than the mid-frequency data (6.3, 5.4 and 4.8%, for the β, α2 and monohydrate forms, respectively). The better performance of low-frequency Raman analysis was attributed to larger spectral differences between the solid-state forms, combined with a higher signal-to-noise ratio. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Pt and Ru X-ray absorption spectroscopy of PtRu anode catalysts in operating direct methanol fuel cells.

    Science.gov (United States)

    Stoupin, Stanislav; Chung, Eun-Hyuk; Chattopadhyay, Soma; Segre, Carlo U; Smotkin, Eugene S

    2006-05-25

    In situ X-ray absorption spectroscopy, ex situ X-ray fluorescence, and X-ray powder diffraction enabled detailed core analysis of phase segregated nanostructured PtRu anode catalysts in an operating direct methanol fuel cell (DMFC). No change in the core structures of the phase segregated catalyst was observed as the potential traversed the current onset potential of the DMFC. The methodology was exemplified using a Johnson Matthey unsupported PtRu (1:1) anode catalyst incorporated into a DMFC membrane electrode assembly. During DMFC operation the catalyst is essentially metallic with half of the Ru incorporated into a face-centered cubic (FCC) Pt alloy lattice and the remaining half in an amorphous phase. The extended X-ray absorption fine structure (EXAFS) analysis suggests that the FCC lattice is not fully disordered. The EXAFS indicates that the Ru-O bond lengths were significantly shorter than those reported for Ru-O of ruthenium oxides, suggesting that the phases in which the Ru resides in the catalysts are not similar to oxides.

  19. On the performance of laser-induced breakdown spectroscopy for direct determination of trace metals in lubricating oils

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Lijuan [Institut Lumière Matière, UMR5306 Université Lyon 1-CNRS, Université de Lyon, 69622 Villeurbanne Cedex (France); State Key Laboratory of Precision Spectroscopy, East China Normal University, Shanghai 200062 (China); Cao, Fan; Xiu, Junshan; Bai, Xueshi; Motto-Ros, Vincent [Institut Lumière Matière, UMR5306 Université Lyon 1-CNRS, Université de Lyon, 69622 Villeurbanne Cedex (France); Gilon, Nicole [Institut des Sciences Analytiques, UMR5280 Université Lyon 1-CNRS, Université de Lyon, 69622 Villeurbanne Cedex (France); Zeng, Heping [State Key Laboratory of Precision Spectroscopy, East China Normal University, Shanghai 200062 (China); Yu, Jin, E-mail: jin.yu@univ-lyon1.fr [Institut Lumière Matière, UMR5306 Université Lyon 1-CNRS, Université de Lyon, 69622 Villeurbanne Cedex (France); Key Laboratory for Laser Plasmas (Ministry of Education), Department of Physics and Astrophysics, Shanghai Jiao Tong University, Shanghai 200240 (China)

    2014-09-01

    Laser-induced breakdown spectroscopy (LIBS) provides a technique to directly determine metals in viscous liquids and especially in lubricating oils. A specific laser ablation configuration of a thin layer of oil applied on the surface of a pure aluminum target was used to evaluate the analytical figures of merit of LIBS for elemental analysis of lubricating oils. Among the analyzed oils, there were a certified 75cSt blank mineral oil, 8 virgin lubricating oils (synthetic, semi-synthetic, or mineral and of 2 different manufacturers), 5 used oils (corresponding to 5 among the 8 virgin oils), and a cooking oil. The certified blank oil and 4 virgin lubricating oils were spiked with metallo-organic standards to obtain laboratory reference samples with different oil matrix. We first established calibration curves for 3 elements, Fe, Cr, Ni, with the 5 sets of laboratory reference samples in order to evaluate the matrix effect by the comparison among the different oils. Our results show that generalized calibration curves can be built for the 3 analyzed elements by merging the measured line intensities of the 5 sets of spiked oil samples. Such merged calibration curves with good correlation of the merged data are only possible if no significant matrix effect affects the measurements of the different oils. In the second step, we spiked the remaining 4 virgin oils and the cooking oils with Fe, Cr and Ni. The accuracy and the precision of the concentration determination in these prepared oils were then evaluated using the generalized calibration curves. The concentrations of metallic elements in the 5 used lubricating oils were finally determined. - Highlights: • Direct determination of wear metals in lubricating oils using LIBS. • Generalized calibration curves for different oils. • Ablation of a thin oil layer on a pure metallic target.

  20. Implementation of Near-Infrared Spectroscopy for In-Line Monitoring of a Dehydration Reaction in a Tubular Laminar Reactor

    DEFF Research Database (Denmark)

    Mitic, Aleksandar; Cervera Padrell, Albert Emili; Mortensen, Asmus R.

    2016-01-01

    are the main benefits. A good approach to achieve this is to perform continuous manufacturing together with satisfying process analytical technology (PAT) requirements. The example studied here is the dehydration reaction of 9-allyl-2-chlorothioxanthen-9-ol (“N714-allylcarbinol”) to give a mixture of cis...

  1. Probing the Energy Transfer Dynamics of Photosynthetic Reaction Center Complexes Through Hole-Burning and Single-Complex Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Riley, Kerry Joseph [Iowa State Univ., Ames, IA (United States)

    2007-01-01

    Photosynthesis is the process by which light energy is used to drive reactions that generate sugars to supply energy for cellular processes. It is one of the most important fundamental biological reactions and occurs in both prokaryotic (e.g. bacteria) and eukaryotic (e.g. plants and algae) organisms. Photosynthesis is also remarkably intricate, requiring the coordination of many different steps and reactions in order to successfully transform absorbed solar energy into a biochemical usable form of energy. However, the net reaction for all photosynthetic organisms can be reduced to the following, deceptively general, equation developed by Van Niel[1] H2 - D + Aimplieshv A - H2 + D where H2-D is the electron donor, e.g. H2O, H2S. A is the electron acceptor, e.g. CO2, and A-H2 is the synthesized sugar. Amazingly, this simple net equation is responsible for creating the oxidizing atmosphere of Earth and the recycling of CO2, both of which are necessary for the sustainment of the global ecosystem.

  2. Reaction Kinetics of Acetone Peroxide Formation and Structure Investigations Using Raman Spectroscopy and X-ray Diffraction

    DEFF Research Database (Denmark)

    Jensen, Lars; Mortensen, Peter Mølgaard; Trane, Rasmus

    2009-01-01

    functional theory (DFT)/Hartree-Fock approach. It was not possible from this to assess with certainty which intermediate products formed most extensively in an acetone/hydrogen peroxide mixture. However, it was concluded that the most likely reaction mixture is a mixture of the different intermediate...

  3. Intermediates detected by visible spectroscopy during the reaction of nitrite with deoxyhemoglobin: the effect of nitrite concentration and diphosphoglycerate.

    Science.gov (United States)

    Nagababu, Enika; Ramasamy, Somasundaram; Rifkind, Joseph M

    2007-10-16

    The reaction of nitrite with deoxyhemoglobin (deoxyHb) results in the reduction of nitrite to NO, which binds unreacted deoxyHb forming Fe(II)-nitrosylhemoglobin (Hb(II)NO). The tight binding of NO to deoxyHb is, however, inconsistent with reports implicating this reaction with hypoxic vasodilation. This dilemma is resolved by the demonstration that metastable intermediates are formed in the course of the reaction of nitrite with deoxyHb. The level of intermediates is quantitated by the excess deoxyHb consumed over the concentrations of the final products formed. The dominant intermediate has a spectrum that does not correspond to that of Hb(III)NO formed when NO reacts with methemoglobin (MetHb), but is similar to metHb resulting in the spectroscopic determinations of elevated levels of metHb. It is a delocalized species involving the heme iron, the NO, and perhaps the beta-93 thiol. The putative role for red cell reacted nitrite on vasodilation is associated with reactions involving the intermediate. (1) The intermediate is less stable with a 10-fold excess of nitrite and is not detected with a 100-fold excess of nitrite. This observation is attributed to the reaction of nitrite with the intermediate producing N2O3. (2) The release of NO quantitated by the formation of Hb(II)NO is regulated by changes in the distal heme pocket as shown by the 4.5-fold decrease in the rate constant in the presence of 2,3-diphosphoglycerate. The regulated release of NO or N2O3 as well as the formation of the S-nitroso derivative of hemoglobin, which has also been reported to be formed from the intermediates generated during nitrite reduction, should be associated with any hypoxic vasodilation attributed to the RBC.

  4. Molecular typing for blood group antigens within 40 min by direct polymerase chain reaction from plasma or serum.

    Science.gov (United States)

    Wagner, Franz F; Flegel, Willy A; Bittner, Rita; Döscher, Andrea

    2017-03-01

    Determining blood group antigens by serological methods may be unreliable in certain situations, such as in patients after chronic or massive transfusion. Red cell genotyping offers a complementary approach, but current methods may take much longer than conventional serological typing, limiting their utility in urgent situations. To narrow this gap, we devised a rapid method using direct polymerase chain reaction (PCR) amplification while avoiding the DNA extraction step. DNA was amplified by PCR directly from plasma or serum of blood donors followed by a melting curve analysis in a capillary rapid-cycle PCR assay. We evaluated the single nucleotide polymorphisms underlying the clinically relevant Fy a , Fy b , Jk a and Jk b antigens, with our analysis being completed within 40 min of receiving a plasma or serum sample. The positive predictive value was 100% and the negative predictive value at least 84%. Direct PCR with melting point analysis allowed faster red cell genotyping to predict blood group antigens than any previous molecular method. Our assay may be used as a screening tool with subsequent confirmatory testing, within the limitations of the false-negative rate. With fast turnaround times, the rapid-cycle PCR assay may eventually be developed and applied to red cell genotyping in the hospital setting. © 2016 John Wiley & Sons Ltd.

  5. An investigation of the effect of pore scale flow on average geochemical reaction rates using direct numerical simulation

    Energy Technology Data Exchange (ETDEWEB)

    Molins, Sergi [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Division; Trebotich, David [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division; Steefel, Carl I. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Division; Shen, Chaopeng [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division

    2012-03-30

    The scale-dependence of geochemical reaction rates hinders their use in continuum scale models intended for the interpretation and prediction of chemical fate and transport in subsurface environments such as those considered for geologic sequestration of CO2. Processes that take place at the pore scale, especially those involving mass transport limitations to reactive surfaces, may contribute to the discrepancy commonly observed between laboratory-determined and continuum-scale or field rates. In this study we investigate the dependence of mineral dissolution rates on the pore structure of the porous media by means of pore scale modeling of flow and multicomponent reactive transport. The pore scale model is composed of high-performance simulation tools and algorithms for incompressible flow and conservative transport combined with a general-purpose multicomponent geochemical reaction code. The model performs direct numerical simulation of reactive transport based on an operator-splitting approach to coupling transport and reactions. The approach is validated with a Poiseuille flow single-pore experiment and verified with an equivalent 1-D continuum-scale model of a capillary tube packed with calcite spheres. Using the case of calcite dissolution as an example, the high-resolution model is used to demonstrate that nonuniformity in the flow field at the pore scale has the effect of decreasing the overall reactivity of the system, even when systems with identical reactive surface area are considered. In conclusion, the effect becomes more pronounced as the heterogeneity of the reactive grain packing increases, particularly where the flow slows sufficiently such that the solution approaches equilibrium locally and the average rate becomes transport-limited.

  6. High temperature synthesis of ceramic composition by directed reaction of molten titanium or zirconium with boron carbide

    International Nuclear Information System (INIS)

    Johnson, W.B.

    1990-01-01

    Alternative methods of producing ceramics and ceramic composites include sintering, hot pressing and more recently hot isostatic pressing (HIP) and self-propagating high temperature synthesis (SHS). Though each of these techniques has its advantages, each suffers from several restrictions as well. Sintering may require long times at high temperatures and for most materials requires sintering aids to get full density. These additives can, and generally do, change (often degrade) the properties of the ceramic. Hot pressing and hot isostatic pressing are convenient methods to quickly prepare samples of some materials to full density, but generally are expensive and may damage some types of reinforcements during densification. This paper focuses on the preparation and processing of composites prepared by the directed reaction of molten titanium or zirconium with boron carbide. Advantages and disadvantages of this approach when compared to traditional methods are discussed, with reference to specific examples. Examples of microstructure are properties of these materials are reported

  7. Kinetics of iron redox reactions in silicate liquids: A high-temperature X-ray absorption and Raman spectroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Magnien, V. [Physique des Mineraux et Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France); CEA VALRHO Marcoule, SCDV, LEBV, BP 17171, 30207 Bagnols/Ceze (France); Neuville, D.R. [Physique des Mineraux et Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France)]. E-mail: neuville@ipgp.jussieu.fr; Cormier, L. [IMPMC, CNRS UMR 7590, Universites Paris 6 and 7 and IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France); Roux, J. [Physique des Mineraux et Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France); Hazemann, J.-L. [Laboratoire de cristallographie, UPR 5031, CNRS, 38043 Grenoble (France); Pinet, O. [CEA VALRHO Marcoule, SCDV, LEBV, BP 17171, 30207 Bagnols/Ceze (France); Richet, P. [Physique des Mineraux et Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France)

    2006-06-30

    The oxidation kinetics of a Fe-bearing supercooled liquid of the system SiO{sub 2}-CaO-MgO-Na{sub 2}O-FeO has been determined near the glass transition range by X-ray absorption near edge structure (XANES) and Raman spectroscopies. Both techniques yield room-temperature iron redox ratios in accord with wet chemical, Moessbauer and electron microprobe analyses. Similar oxidation kinetics have also been observed with both methods. At constant temperature, the kinetics obey an exponential law with a characteristic time that follows an Arrhenian temperature dependence. As redox changes are too fast to be accounted for in terms of diffusion of either ionic or molecular oxygen, these results lend further support to the idea that the rate-limiting factor for oxidation near the glass transition is diffusion of network-modifying cations along with a flux of electron holes.

  8. Redox reactions of cytochrome c in isolated mitochondria exposed to blue or red lasers using resonance Raman spectroscopy

    Science.gov (United States)

    Denton, Michael L.; Gonzalez, Cherry C.; Noojin, Gary D.; Yakovlev, Vladislav V.

    2018-02-01

    Resonance Raman spectroscopy of cytochrome c was used to follow reduction/oxidation (redox) states of isolated mitochondria in response to blue or red laser exposure. Mitochondria were isolated from hTERT-RPE1 cells and were kept in a buffer formulation known to be conducive to electron transport chain (ETC) activity. Using either pyruvate or succinate as substrates for ETC, we found differences in the redox responses of cytochrome c for different exposure laser irradiance and excitation wavelength. We anticipate that the proposed new method will be valuable in the study of metabolic processes in mitochondria in response to low level laser exposure, and thus aid in elucidating the mechanism(s) of photobiomodulation.

  9. A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Nicholas H. C.; Dong, Hui; Oliver, Thomas A. A.; Fleming, Graham R., E-mail: grfleming@lbl.gov [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720 (United States)

    2015-09-28

    Two dimensional electronic spectroscopy has proved to be a valuable experimental technique to reveal electronic excitation dynamics in photosynthetic pigment-protein complexes, nanoscale semiconductors, organic photovoltaic materials, and many other types of systems. It does not, however, provide direct information concerning the spatial structure and dynamics of excitons. 2D infrared spectroscopy has become a widely used tool for studying structural dynamics but is incapable of directly providing information concerning electronic excited states. 2D electronic-vibrational (2DEV) spectroscopy provides a link between these domains, directly connecting the electronic excitation with the vibrational structure of the system under study. In this work, we derive response functions for the 2DEV spectrum of a molecular dimer and propose a method by which 2DEV spectra could be used to directly measure the electronic site populations as a function of time following the initial electronic excitation. We present results from the response function simulations which show that our proposed approach is substantially valid. This method provides, to our knowledge, the first direct experimental method for measuring the electronic excited state dynamics in the spatial domain, on the molecular scale.

  10. Recent results on solvation dynamics of electron and spur reactions of solvated electron in polar solvents studied by femtosecond laser spectroscopy and picosecond pulse radiolysis

    International Nuclear Information System (INIS)

    Mostafavi, M.

    2006-01-01

    Here, we report several studies done recently at ELYSE laboratory on the solvation dynamics of electron and on the kinetics of solvated electron in the spur reactions, performed by femtosecond laser spectroscopy and picosecond pulse radiolysis, respectively. Solvated electrons have been produced in polyol (1,2-Etanediol, 1,2-Propanediol and 1,3-Propanediol) by two-photon ionization of the solvent with 263 nm femtosecond laser pulses at room temperature. The two-photon absorption coefficient of these solvents at 263 nm has been determined. The dynamics of electron solvation in polyols has been studied by pump-probe transient absorption spectroscopy. So, time resolved absorption spectra ranging from 430 to 720 nm have been measured (Figure 1). A blue shift of the spectra is observed for the first tens of picoseconds. Using Bayesian data analysis method, the observed solvation dynamics are reconstructed with different models: stepwise mechanisms, continuous relaxation models or combinations of stepwise and continuous relaxation. That analysis clearly indicates that it is not obvious to select a unique model to describe the solvation dynamics of electron in diols. We showed that several models are able to reproduce correctly the data: a two-step model, a heterogeneous or bi-exponential continuous relaxation model and even a hybrid model with a stepwise transition and homogeneous continuous relaxation. Nevertheless, the best fits are given by the continuous spectral relaxation models. The fact that the time-evolution of the absorption spectrum of the solvated electron in diols can be accurately described by the temperature dependent absorption spectrum of the ground state solvated electron suggests that the spectral blue shift is mostly caused by the continuous relaxation of the electron trapped in a large distribution of solvent cages. Similar trends on electron solvation dynamics are observed in the cases of 1,2-ethanediol, 1,3-propanediol and 1,2 propanediol

  11. Use of functional near-infrared spectroscopy to monitor cortical plasticity induced by transcranial direct current stimulation

    Science.gov (United States)

    Khan, Bilal; Hervey, Nathan; Stowe, Ann; Hodics, Timea; Alexandrakis, George

    2013-03-01

    Electrical stimulation of the human cortex in conjunction with physical rehabilitation has been a valuable approach in facilitating the plasticity of the injured brain. One such method is transcranial direct current stimulation (tDCS) which is a non-invasive method to elicit neural stimulation by delivering current through electrodes placed on the scalp. In order to better understand the effects tDCS has on cortical plasticity, neuroimaging techniques have been used pre and post tDCS stimulation. Recently, neuroimaging methods have discovered changes in resting state cortical hemodynamics after the application of tDCS on human subjects. However, analysis of the cortical hemodynamic activity for a physical task during and post tDCS stimulation has not been studied to our knowledge. A viable and sensitive neuroimaging method to map changes in cortical hemodynamics during activation is functional near-infrared spectroscopy (fNIRS). In this study, the cortical activity during an event-related, left wrist curl task was mapped with fNIRS before, during, and after tDCS stimulation on eight healthy adults. Along with the fNIRS optodes, two electrodes were placed over the sensorimotor hand areas of both brain hemispheres to apply tDCS. Changes were found in both resting state cortical connectivity and cortical activation patterns that occurred during and after tDCS. Additionally, changes to surface electromyography (sEMG) measurements of the wrist flexor and extensor of both arms during the wrist curl movement, acquired concurrently with fNIRS, were analyzed and related to the transient cortical plastic changes induced by tDCS.

  12. Direct Vpr-Vpr Interaction in Cells monitored by two Photon Fluorescence Correlation Spectroscopy and Fluorescence Lifetime Imaging

    Directory of Open Access Journals (Sweden)

    Mély Yves

    2008-09-01

    Full Text Available Abstract Background The human immunodeficiency virus type 1 (HIV-1 encodes several regulatory proteins, notably Vpr which influences the survival of the infected cells by causing a G2/M arrest and apoptosis. Such an important role of Vpr in HIV-1 disease progression has fuelled a large number of studies, from its 3D structure to the characterization of specific cellular partners. However, no direct imaging and quantification of Vpr-Vpr interaction in living cells has yet been reported. To address this issue, eGFP- and mCherry proteins were tagged by Vpr, expressed in HeLa cells and their interaction was studied by two photon fluorescence lifetime imaging microscopy and fluorescence correlation spectroscopy. Results Results show that Vpr forms homo-oligomers at or close to the nuclear envelope. Moreover, Vpr dimers and trimers were found in the cytoplasm and in the nucleus. Point mutations in the three α helices of Vpr drastically impaired Vpr oligomerization and localization at the nuclear envelope while point mutations outside the helical regions had no effect. Theoretical structures of Vpr mutants reveal that mutations within the α-helices could perturb the leucine zipper like motifs. The ΔQ44 mutation has the most drastic effect since it likely disrupts the second helix. Finally, all Vpr point mutants caused cell apoptosis suggesting that Vpr-mediated apoptosis functions independently from Vpr oligomerization. Conclusion We report that Vpr oligomerization in HeLa cells relies on the hydrophobic core formed by the three α helices. This oligomerization is required for Vpr localization at the nuclear envelope but not for Vpr-mediated apoptosis.

  13. Dilepton spectroscopy at intermediate energies; the carbon - carbon reaction at 1 GeV/A; Spectroscopie des dileptons aux energies intermediaires; la reaction carbone - carbone A 1 GeV/A

    Energy Technology Data Exchange (ETDEWEB)

    Prunet, M

    1995-06-01

    The Physics context of this work is heavy ion collisions at relativistic energies where di-electron provide informations on the produced hot and dense nuclear matter. The experiment is performed by the DiLepton Spectrometer (DLS) Collaboration at the Lawrence Berkeley`s Bevalac. After a description of the apparatus, we review the whole program and the main results so far obtained: first evidence of a significant di-electron signal at energies above 1 GeV/A; improvement of the understanding of di-electron production (electromagnetic decays of hadrons, {pi}{sup +}{pi}{sup -} annihilation and hadronic Bremsstrahlung). The results of p-p, p-d reactions from 1 to 4.9 GeV/A show that hadronic Bremsstrahlung (pp, pn) should be reformulated. Our analysis, optimized on the reaction Carbon-Carbon at 1 GeV/A, has been applied to {alpha}-Ca and d-Ca. We have developed two main aspects: improvement of the time resolution (500 ps) in order to eliminate all of the protons. Improvement of the space resolution (300 {mu}) for better mass resolution, in particular in the {rho} region. We obtain the cross section of di-electron production as a function of mass, transverse momentum and rapidity from the C-C, {alpha}-Ca and d-Ca reactions at 1 GeV/A. We also compare the cross section for all of the measured systems at 1 GeV/A, including Ca-Ca, and we show a (ApAt){sup {alpha}} dependence with {alpha} {approx_equal} 1.1. A study of the associated multiplicity has also been performed. Nevertheless, the limited acceptance of the DLS and its poor mass resolution to identify the {rho}, {omega} vector mesons, do not allow to conclude on hadron behaviour in nuclear matter. This point is one of the main goal of the HADES project at GSI (Darmstadt), which we give a brief description of the main features. (authors). 60 refs.

  14. Reaction Coordinate Leading to H2 Production in [FeFe]-Hydrogenase Identified by Nuclear Resonance Vibrational Spectroscopy and Density Functional Theory.

    Science.gov (United States)

    Pelmenschikov, Vladimir; Birrell, James A; Pham, Cindy C; Mishra, Nakul; Wang, Hongxin; Sommer, Constanze; Reijerse, Edward; Richers, Casseday P; Tamasaku, Kenji; Yoda, Yoshitaka; Rauchfuss, Thomas B; Lubitz, Wolfgang; Cramer, Stephen P

    2017-11-22

    [FeFe]-hydrogenases are metalloenzymes that reversibly reduce protons to molecular hydrogen at exceptionally high rates. We have characterized the catalytically competent hydride state (H hyd ) in the [FeFe]-hydrogenases from both Chlamydomonas reinhardtii and Desulfovibrio desulfuricans using 57 Fe nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT). H/D exchange identified two Fe-H bending modes originating from the binuclear iron cofactor. DFT calculations show that these spectral features result from an iron-bound terminal hydride, and the Fe-H vibrational frequencies being highly dependent on interactions between the amine base of the catalytic cofactor with both hydride and the conserved cysteine terminating the proton transfer chain to the active site. The results indicate that H hyd is the catalytic state one step prior to H 2 formation. The observed vibrational spectrum, therefore, provides mechanistic insight into the reaction coordinate for H 2 bond formation by [FeFe]-hydrogenases.

  15. Multipulse spectroscopy on the wild-type and YM210W Bacterial Reaction Centre uncovers a new intermediate state in the special pair excited state

    Science.gov (United States)

    Cohen Stuart, T. A.; van Grondelle, R.

    2009-06-01

    The Bacterial Reaction Centre (BRC) has a complex electronic excited state, P ∗, that evolves into subsequent charge separated product states P +H - and P +B -. Pump-dump-probe spectroscopy on the wild-type BRC and on YM210W, a mutant with a stabilized, long-lived P ∗ excited state, has uncovered a new charge-separated state in both BRC's. When P ∗ is dumped, a fraction of its population is transferred to this state that has a strong Stark shift in the accessory bacteriochlorophyll (B M) region which serves as a signature for P + and a lifetime highly comparable to the slow phase of P ∗ decay. This lead us propose this intermediate to be P +/P -.

  16. Kinetics of the addition reaction of methyl radicals with nitric oxide studied by pulse radiolysis combined with infrared diode laser spectroscopy

    DEFF Research Database (Denmark)

    Jodkowski, J.T.; Ratajczak, E.; Sillesen, A.

    1993-01-01

    The reaction CH3 + NO (+ M) --> CH3NO ( + M) was initiated by pulse radiolysis of acetone/nitric oxide mixtures and the kinetics of methyl radicals was studied by time-resolved infrared absorption spectroscopy. The rate constant was found to be strongly pressure dependent in the range of p (M) = 6.......5-150 mbar at 298 K with M = acetone as the third body. The experimental results are represented in terms of a fall-off curve centered at 37 mbar with limiting high- and low-pressure rate constants of k(rec,infinity) = (6.6 +/- 0.9) x 10(9) x (T/300)0.6 M-1 s-1 and k(rec,0)/[M] = (4.4 +/- 0.4) x 10(12) x (T...

  17. Tight-binding model of the photosystem II reaction center: application to two-dimensional electronic spectroscopy

    International Nuclear Information System (INIS)

    Gelzinis, Andrius; Valkunas, Leonas; Abramavicius, Darius; Fuller, Franklin D; Ogilvie, Jennifer P; Mukamel, Shaul

    2013-01-01

    We propose an optimized tight-binding electron–hole model of the photosystem II (PSII) reaction center (RC). Our model incorporates two charge separation pathways and spatial correlations of both static disorder and fast fluctuations of energy levels. It captures the main experimental features observed in time-resolved two-dimensional (2D) optical spectra at 77 K: peak pattern, lineshapes and time traces. Analysis of 2D spectra kinetics reveals that specific regions of the 2D spectra of the PSII RC are sensitive to the charge transfer states. We find that the energy disorder of two peripheral chlorophylls is four times larger than the other RC pigments. (paper)

  18. Tight-binding model of the photosystem II reaction center: application to two-dimensional electronic spectroscopy

    Science.gov (United States)

    Gelzinis, Andrius; Valkunas, Leonas; Fuller, Franklin D.; Ogilvie, Jennifer P.; Mukamel, Shaul; Abramavicius, Darius

    2013-07-01

    We propose an optimized tight-binding electron-hole model of the photosystem II (PSII) reaction center (RC). Our model incorporates two charge separation pathways and spatial correlations of both static disorder and fast fluctuations of energy levels. It captures the main experimental features observed in time-resolved two-dimensional (2D) optical spectra at 77 K: peak pattern, lineshapes and time traces. Analysis of 2D spectra kinetics reveals that specific regions of the 2D spectra of the PSII RC are sensitive to the charge transfer states. We find that the energy disorder of two peripheral chlorophylls is four times larger than the other RC pigments.

  19. Non-linear effects in the radiolysis-optically detected ESR of radical-ion pairs in liquid and glassy solutions. Reactions and motion of organic radicals as studied by ESR and OD ESR spectroscopy

    International Nuclear Information System (INIS)

    Antzutkin, O.

    1992-01-01

    This thesis is divided into two sections. The first part covers an introduction to the Optically Detected Electron Spin Resonance (OD ESR) spectroscopy and a short description of the OD ESR spectrometer built in Linkoeping University in 1991. In the second section the following topics are discussed: Non-linear effects in OD ESR spectroscopy and Reactions and motion of organic radicals trapped in freon matrices. (19 refs.)

  20. Precipitation of gold by the reaction of aqueous gold(III)-chloride with cyanobacteria at 25-80 C -- Studied by x-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Lengke, M. F.; Ravel, B.; Fleet, M. E.; Wanger, G.; Gordon, R. A.; Southam, G.

    2007-01-01

    The mechanisms of gold precipitation by the interaction of cyanobacteria (Plectonema boryanum UTEX 485) and gold(III) chloride aqueous solutions (7.6 mmol/L final gold) have been studied at 25, 60, and 80 C, using both laboratory and real-time synchrotron radiation absorption spectroscopy experiments. Addition of aqueous gold(III) chloride to the cyanobacterial culture initially promoted the precipitation of amorphous gold(I) sulfide at the cell walls and finally caused the formation of octahedral (111) platelets (<1 to 6 (micro)m) of gold metal near cell surfaces and in solutions. X-ray absorption spectroscopy results confirmed that the reduction mechanism of gold(III) chloride to elemental gold by cyanobacteria involves the formation of an intermediate Au(I) species, gold(I) sulfide, with sulfur originating from cyanobacterial proteins, presumably cysteine or methionine. Although the bioreduction of gold(III) chloride to gold(I) sulfide was relatively rapid at all temperatures, the reaction rate increased with the increase in temperature. At the completion of the experiments, elemental gold was the major species present at all temperatures

  1. A Comparative Analysis of Polymerase Chain Reaction and Direct Fluorescent Antibody Test for Diagnosis of Genital Herpes.

    Science.gov (United States)

    Patwardhan, Vrushali; Bhalla, Preena; Rawat, Deepti; Garg, Vijay Kumar; Sardana, Kabir; Sethi, Sumit

    2017-01-01

    To compare laboratory tests that can simultaneously detect and type herpes simplex virus (HSV) directly from the genital ulcer specimens in clinically suspected cases of genital herpes. A study was conducted over 10 months and 44 adult male and female patients clinically suspected with genital herpes were recruited. Genital ulcer swab specimens were subjected to glycoprotein-G gene-based conventional polymerase chain reaction (PCR) and commercially available direct fluorescent antibody (DFA) test and the results were compared. PCR for HSV was positive in 82% (36/44) cases. DFA was positive in 68.2% (30/44) cases. There was 100% agreement between HSV types detected by DFA and PCR. The strength of agreement between the results was better in primary genital herpes than recurrent cases. PCR was found to be better in the detection of HSV in recurrent genital herpes patients. It is a better modality, especially when genital herpes clinically presents with ulcerative or crusted lesions, and is also a cheaper alternative as compared to DFA.

  2. Resonance Raman spectroscopy of 2H-labelled spheroidenes in petroleum ether and in the Rhodobacter sphaeroides reaction centre.

    Science.gov (United States)

    Kok, P; Köhler, J; Groenen, E J; Gebhard, R; van der Hoef, I; Lugtenburg, J; Farhoosh, R; Frank, H A

    1997-03-01

    As a step towards the structural analysis of the carotenoid spheroidene in the Rhodobacter sphaeroides reaction centre, we present the resonance Raman spectra of 14-2H, 15-2H, 15'-2H, 14'-2H, 14,15'-2H2 and 15-15'-2H2 spheroidenes in petroleum ether and, except for 14,15'-2H2 spheroidene, in the Rb. sphaeroides R26 reaction center (RC). Analysis of the spectral changes upon isotopic substitution allows a qualitative assignment of most of the vibrational bands to be made. For the all-trans spheroidenes in solution the resonance enhancement of the Raman bands is determined by the participation of carbon carbon stretching modes in the centre of the conjugated chain, the C9 to C15' region. For the RC-bound 15,15'-cis spheroidenes, enhancement is determined by the participation of carbon-carbon stretching modes in the centre of the molecule, the C13 to C13' region. Comparison of the spectra in solution and in the RC reveals evidence for an out-of-plane distortion of the RC-bound spheroidene in the central C14 to C14' region of the carotenoid. The characteristic 1240 cm-1 band in the spectrum of the RC-bound spheroidene has been assigned to a normal mode that contains the coupled C12-C13 and C13'-C12' stretch vibrations.

  3. Monitoring of petroleum hydrocarbon pollution in surface waters by a direct comparison of fluorescence spectroscopy and remote sensing techniques

    Energy Technology Data Exchange (ETDEWEB)

    De Domenico, L.; Crisafi, E. (Consiglio Nazionale delle Ricerche, Messina (Italy). Thalassografic Inst.); Magazzu, G. (Lecce Univ. (Italy). Dept. of Biology); Puglisi, A. (Mediterranean Oceanological Centre (CEOM), Palermo (Italy)); La Rosa, A. (Air-Survey, Italy s.r.l., Catania (Italy))

    1994-10-01

    Oil pollution levels were estimated using simultaneous acquisition of data from remote sensing by helicopter and fluorescence spectroscopy on surface samples. Laboratory quantitative analysis of hydrocarbons was used to calibrate remotely sensed data. The data were treated using a computer to generate a colour-coded map not attainable with conventional methods representing seawater pollution. Results were in good agreement and indicated that remotely sensed data together with those achieved by fluorescence spectroscopy are applicable for monitoring hydrocarbon pollution. (author)

  4. Monitoring of petroleum hydrocarbon pollution in surface waters by a direct comparison of fluorescence spectroscopy and remote sensing techniques

    International Nuclear Information System (INIS)

    De Domenico, L.; Crisafi, E.; La Rosa, A.

    1994-01-01

    Oil pollution levels were estimated using simultaneous acquisition of data from remote sensing by helicopter and fluorescence spectroscopy on surface samples. Laboratory quantitative analysis of hydrocarbons was used to calibrate remotely sensed data. The data were treated using a computer to generate a colour-coded map not attainable with conventional methods representing seawater pollution. Results were in good agreement and indicated that remotely sensed data together with those achieved by fluorescence spectroscopy are applicable for monitoring hydrocarbon pollution. (author)

  5. Giant resonance spectroscopy of 40Ca with the (e,e'x) reaction (I): Experiments and overview of results

    International Nuclear Information System (INIS)

    Diesener, H.; Helm, U.; Neumann-Cosel, P. von; Richter, A.; Schrieder, G.; Stascheck, A.; Stiller, A.; Carter, J.

    2001-01-01

    The 40 Ca(e,e'x; x=p,α) reaction has been measured in the giant resonance excitation region for E x ≅8-26 MeV. The present article is the first out of three describing the experiments and giving an overview of the results. Data were taken at four momentum transfers in the range q=0.26-0.66 fm -1 . Angular correlations for decay to the ground state and low-lying states of 39 K and 36 Ar could be extracted as a function of excitation energy in 40 Ca. Excitation energy spectra integrated over the particle emission angle were generated for the various resolved decay channels. Comparisons of the giant resonance cross-section distributions with results using other electromagnetic or hadronic probes have been made and good agreement is found in most cases

  6. $\\gamma$ -spectroscopy of n-rich $^{95,96}$Rb nuclei by the incomplete fusion reaction of $^{94}$Kr on $^{7}$Li

    CERN Multimedia

    We propose an experiment with MINIBALL coupled to T-REX to investigate n-rich $^{95,96}$Rb nuclei by the incomplete fusion reaction of $^{94}$Kr on $^{7}$Li. The nuclei of interest will be populated by transfer of a triton into $^{94}$Kr, forming the excited $^{97}$Rb nucleus, followed by the emission of an alpha particle, which will be detected in the Si telescopes of T-REX. The $^{97}$Rb product will evaporate 1 or 2 (with the highest probability) neutrons leading to $^{96}$Rb or $^{95}$Rb, respectively. The aim of the experiment is twofold: \\\\ i) to perform a $\\gamma$- spectroscopy study of $^{95,96}$Rb nuclei with N=58,59, the structure of which is of particular interest in investigating the transition towards stable deformation at N=60, \\\\ ii) to acquire experience in using incomplete fusion reactions with the weakly bound $^{7}$Li target, in order to perform, at a later stage with HIE-ISOLDE, similar measurements induced by n-rich radioactive beams of Sn and Hg, for which at least 5 MeV/nucleon are need...

  7. Measurement of key resonances for the 24Al(p ,γ )25Si reaction rate using in-beam γ -ray spectroscopy

    Science.gov (United States)

    Longfellow, B.; Gade, A.; Brown, B. A.; Richter, W. A.; Bazin, D.; Bender, P. C.; Bowry, M.; Elman, B.; Lunderberg, E.; Weisshaar, D.; Williams, S. J.

    2018-05-01

    Energy levels and branching ratios for the rp-process nucleus 25Si were determined from the reactions 9Be(26Si,25Si)X and 9Be(25Al,25Si)X using in-beam γ -ray spectroscopy with both high-efficiency and high-resolution detector arrays. Proton-unbound states at 3695(14) and 3802(11) keV were identified and assigned tentative spins and parities based on comparison to theory and the mirror nucleus. The 24Al(p ,γ )25Si reaction rate was calculated using the experimental states and states from charge-dependent USDA and USDB shell-model calculations with downward shifts of the 1 s1 /2 proton orbital to account for the observed Thomas-Ehrman shift, leading to a factor of 10-100 increase in rate for the temperature region of 0.22 GK as compared to a previous calculation. These shifts may be applicable to neighboring nuclei, impacting the proton capture rates in this region of the chart.

  8. Optical Spectroscopy

    DEFF Research Database (Denmark)

    Thyrhaug, Erling

    The work presented in this thesis is broadly concerned with how complexation reactions and molecular motion can be characterized with the standard techniques in optical spectroscopy. The thesis aims to show a relatively broad range of methods for probing physico-chemical properties in fluorophore...... information about chemical equilibria, kinetics and molecular motion by monitoring changes in optical properties of the system. The five presented research projects are largely unrelated to each other both in aim and in what property is probed, however they are all connected in that they are fluorophore...... reactions by optical spectroscopy. In project 1 simple steady-state absorption and fluorescence spectroscopy is used to determine the stoichiometries and equilibrium constants in the inclusion complex formation between cyclodextrins and derivatives of the water-insoluble oligo(phenylene vinylene) in aqueous...

  9. Intensity-Stabilized Fast-Scanned Direct Absorption Spectroscopy Instrumentation Based on a Distributed Feedback Laser with Detection Sensitivity down to 4 × 10−6

    Directory of Open Access Journals (Sweden)

    Gang Zhao

    2016-09-01

    Full Text Available A novel, intensity-stabilized, fast-scanned, direct absorption spectroscopy (IS-FS-DAS instrumentation, based on a distributed feedback (DFB diode laser, is developed. A fiber-coupled polarization rotator and a fiber-coupled polarizer are used to stabilize the intensity of the laser, which significantly reduces its relative intensity noise (RIN. The influence of white noise is reduced by fast scanning over the spectral feature (at 1 kHz, followed by averaging. By combining these two noise-reducing techniques, it is demonstrated that direct absorption spectroscopy (DAS can be swiftly performed down to a limit of detection (LOD (1σ of 4 × 10−6, which opens up a number of new applications.

  10. Dynamical observation of lithium insertion/extraction reaction during charge-discharge processes in Li-ion batteries by in situ spatially resolved electron energy-loss spectroscopy.

    Science.gov (United States)

    Shimoyamada, Atsushi; Yamamoto, Kazuo; Yoshida, Ryuji; Kato, Takehisa; Iriyama, Yasutoshi; Hirayama, Tsukasa

    2015-12-01

    All-solid-state Li-ion batteries (LIBs) with solid electrolytes are expected to be the next generation devices to overcome serious issues facing conventional LIBs with liquid electrolytes. However, the large Li-ion transfer resistance at the electrode/solid-electrolyte interfaces causes low power density and prevents practical use. In-situ-formed negative electrodes prepared by decomposing the solid electrolyte Li(1+x+3z)Alx(Ti,Ge)(2-x)Si(3z)P(3-z)O12 (LASGTP) with an excess Li-ion insertion reaction are effective electrodes providing low Li-ion transfer resistance at the interfaces. Prior to our work, however, it had still been unclear how the negative electrodes were formed in the parent solid electrolytes. Here, we succeeded in dynamically visualizing the formation by in situ spatially resolved electron energy-loss spectroscopy in a transmission electron microscope mode (SR-TEM-EELS). The Li-ions were gradually inserted into the solid electrolyte region around 400 nm from the negative current-collector/solid-electrolyte interface in the charge process. Some of the ions were then extracted in the discharge process, and the rest were diffused such that the distribution was almost flat, resulting in the negative electrodes. The redox reaction of Ti(4+)/Ti(3+) in the solid electrolyte was also observed in situ during the Li insertion/extraction processes. The in situ SR-TEM-EELS revealed the mechanism of the electrochemical reaction in solid-state batteries. © The Author 2015. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  11. Enzymatic conversion of sucrose to glucose and its anomerization by quantitative NMR spectroscopy: Application of a simple consecutive reaction rates approach

    Science.gov (United States)

    Singh, Jaideep; Her, Cheenou; Krishnan, V. V.

    2018-02-01

    The anomerization of carbohydrates is an essential process that determines the relative stabilization of stereoisomers in an aqueous solution. In a typical real-time enzyme kinetics experiment, the substrate (sucrose) is converted to glucose and fructose by the enzyme invertase. The product (α-D-glucose) starts to convert to β-D-glucose immediately by hydrolysis. Though the anomerization process is independent of the enzyme catalysis, the progress curve describing the production of β-D-glucose from α-D-glucose is directly affected by the kinetics of consecutive reactions. When α-D-glucose is continually converted to β-D-glucose, by the enzymatic action, the time course of both α- and β-D-glucose is influenced by the enzyme kinetics. Thus, a reversible first-order rate equation is not adequate to model the reaction mechanism, leading to erroneous results on the rates of formation of the glucose anomers. In this manuscript, we incorporate an approximate method to address consecutive general reactions involving enzyme kinetics and first-order reaction processes. The utility of the approach is demonstrated in the real-time NMR measurement of the anomerization process of α-D-glucose (enzymatically produced from sucrose) to β-D-glucose, as a function of invertase enzyme concentration. Variable temperature experiments were used to estimate the thermodynamic parameters of the anomerization process and are consistent with literature values.

  12. Direct determination of energy level alignment and charge transport at metal-Alq3 interfaces via ballistic-electron-emission spectroscopy.

    Science.gov (United States)

    Jiang, J S; Pearson, J E; Bader, S D

    2011-04-15

    Using ballistic-electron-emission spectroscopy (BEES), we directly determined the energy barrier for electron injection at clean interfaces of Alq(3) with Al and Fe to be 2.1 and 2.2 eV, respectively. We quantitatively modeled the sub-barrier BEES spectra with an accumulated space charge layer, and found that the transport of nonballistic electrons is consistent with random hopping over the injection barrier.

  13. Photoelectron Spectroscopy of CdSe Nanocrystals in the Gas Phase: A Direct Measure of the Evanescent Electron Wave Function of Quantum Dots

    Science.gov (United States)

    2013-01-01

    researchers have used ultrafast transient absorption spectros - copy to show that the charge separation rate of Type II core− shell QDs depends on the extent...the first direct measurement of the evanescent electron density of the QD exciton. We use ultrafast two-photon photoelectron spectros - copy (2PPE) to...clusters are well preserved after the aerosol system, as observed using UV − visible spectroscopy (Supporting Information Figure S1). The isolation of the

  14. Spectroscopy of 919395Nb and 9395Tc via the (3He,d) reaction at 25 MeV

    International Nuclear Information System (INIS)

    Cooney, P.J.

    1975-01-01

    Low-lying and analog states in 91 93 95 Nb and 93 95 Tc have been studied using the ( 3 He,d) reaction at a 3 He lab energy of 25 MeV. Outgoing deuteron angular distributions were measured using cooled surface barrier detector telescopes with a typical energy resolution of 70 keV and were compared with DWBA calculations in order to obtain l-values and proton spectroscopic factors. Reasonable agreement with sum rule limits for low-lying g-, p-, and f-states was obtained without any ad hoc adjustment of the calculated differential cross sections. Considerable fragmentation of the T/sub less than/ component of the d 5 / 2 single proton strength was observed, particularly in 93 95 Nb and its centroid was found to shift to lower excitation energies with increasing neutron number. The spectroscopic factors of the analog states were extracted using previously untried wavefunctions and were in good agreement with those of the parent states. Finally, the splitting between the analog and anti-analog d 5 / 2 states was found to be proportional to (T/sub A/ + 1 / 2 ), the constant of proportionality being about 150 MeV/A

  15. Direct dynamics trajectory study of the reaction of formaldehyde cation with D2: vibrational and zero-point energy effects on quasiclassical trajectories.

    Science.gov (United States)

    Liu, Jianbo; Song, Kihyung; Hase, William L; Anderson, Scott L

    2005-12-22

    Quasiclassical, direct dynamics trajectories have been used to study the reaction of formaldehyde cation with molecular hydrogen, simulating the conditions in an experimental study of H2CO+ vibrational effects on this reaction. Effects of five different H2CO+ modes were probed, and we also examined different approaches to treating zero-point energy in quasiclassical trajectories. The calculated absolute cross-sections are in excellent agreement with experiments, and the results provide insight into the reaction mechanism, product scattering behavior, and energy disposal, and how they vary with impact parameter and reactant state. The reaction is sharply orientation-dependent, even at high collision energies, and both trajectories and experiment find that H2CO+ vibration inhibits reaction. On the other hand, the trajectories do not reproduce the anomalously strong effect of nu2(+) (the CO stretch). The origin of the discrepancy and approaches for minimizing such problems in quasiclassical trajectories are discussed.

  16. MoS2 nanosheets direct supported on reduced graphene oxide: An advanced electrocatalyst for hydrogen evolution reaction.

    Directory of Open Access Journals (Sweden)

    Jiamu Cao

    Full Text Available Molybdenum disulfide nanosheets/reduced graphene oxide (MoS2 NSs/rGO nanohybrid as a highly effective catalyst for hydrogen evolution reaction (HER have been successfully synthesized by a facile microwave-assisted method. The results clearly reveal that direct grown of MoS2 NSs on rGO have been achieved. Electrochemical tests show that the as-prepared hybrid material exhibited excellent HER activity, with a small Tafel slope of 57 mV dec-1, an overpotential of 130 mV and remarkable cycling stability. After analysis, the observed outstanding catalytic performance can be attributed to the uniform distribution of the MoS2 NSs, which are characterized by the presence of multiple active sites as well as the effective electron transport route provided by the conductive rGO substrate. Moreover, according to the classic theory, the mechanism governing of the catalytic HER on the MoS2 NSs/rGO nanohybrid has been clarified.

  17. An ab initio chemical reaction model for the direct simulation Monte Carlo study of non-equilibrium nitrogen flows.

    Science.gov (United States)

    Mankodi, T K; Bhandarkar, U V; Puranik, B P

    2017-08-28

    A new ab initio based chemical model for a Direct Simulation Monte Carlo (DSMC) study suitable for simulating rarefied flows with a high degree of non-equilibrium is presented. To this end, Collision Induced Dissociation (CID) cross sections for N 2 +N 2 →N 2 +2N are calculated and published using a global complete active space self-consistent field-complete active space second order perturbation theory N 4 potential energy surface and quasi-classical trajectory algorithm for high energy collisions (up to 30 eV). CID cross sections are calculated for only a selected set of ro-vibrational combinations of the two nitrogen molecules, and a fitting scheme based on spectroscopic weights is presented to interpolate the CID cross section for all possible ro-vibrational combinations. The new chemical model is validated by calculating equilibrium reaction rate coefficients that can be compared well with existing shock tube and computational results. High-enthalpy hypersonic nitrogen flows around a cylinder in the transition flow regime are simulated using DSMC to compare the predictions of the current ab initio based chemical model with the prevailing phenomenological model (the total collision energy model). The differences in the predictions are discussed.

  18. Two gap superconductivity in Ba0.55K0.45Fe2As2 single crystals studied by the directional point-contact Andreev reflection spectroscopy

    International Nuclear Information System (INIS)

    Szabo, P.; Pribulova, Z.; Pristas, G.; Bud'ko, S.L.; Canfield, P.C.; Samuely, P.

    2009-01-01

    First directional point-contact Andreev reflection spectroscopy on the Ba 0.55 K 0.45 Fe 2 As 2 single crystals is presented. The spectra show significant differences when measured in the ab plane in comparison with those measured in the c direction. In the latter case no traces of superconducting energy gap could be found, just a reduced point-contact conductance persisting up to about 100 K and indicating reduced density of states. On the other hand within the ab plane two nodeless superconducting energy gaps Δ S ∼2-5 meV and Δ L ∼9-11 meV are detected.

  19. Reaction mechanisms

    International Nuclear Information System (INIS)

    Nguyen Trong Anh

    1988-01-01

    The 1988 progress report of the Reaction Mechanisms laboratory (Polytechnic School, France), is presented. The research topics are: the valence bond methods, the radical chemistry, the modelling of the transition states by applying geometric constraints, the long range interactions (ion - molecule) in gaseous phase, the reaction sites in gaseous phase and the mass spectroscopy applications. The points of convergence between the investigations of the mass spectroscopy and the theoretical chemistry teams, as well as the purposes guiding the research programs, are discussed. The published papers, the conferences, the congress communications and the thesis, are also reported [fr

  20. Direct observation of an isopolyhalomethane O-H insertion reaction with water: Picosecond time-resolved resonance Raman (ps-TR3) study of the isobromoform reaction with water to produce a CHBr2OH product

    International Nuclear Information System (INIS)

    Kwok, W.M.; Zhao Cunyuan; Li Yunliang; Guan Xiangguo; Phillips, David Lee

    2004-01-01

    Picosecond time-resolved resonance Raman (ps-TR 3 ) spectroscopy was used to obtain the first definitive spectroscopic observation of an isopolyhalomethane O-H insertion reaction with water. The ps-TR 3 spectra show that isobromoform is produced within several picoseconds after photolysis of CHBr 3 and then reacts on the hundreds of picosecond time scale with water to produce a CHBr 2 OH reaction product. Photolysis of low concentrations of bromoform in aqueous solution resulted in noticeable formation of HBr strong acid. Ab initio calculations show that isobromoform can react with water to produce a CHBr 2 (OH) O-H insertion reaction product and a HBr leaving group. This is consistent with both the ps-TR 3 experiments that observe the reaction of isobromoform with water to form a CHBr 2 (OH) product and photolysis experiments that show HBr acid formation. We briefly discuss the implications of these results for the phase dependent behavior of polyhalomethane photochemistry in the gas phase versus water solvated environments

  1. Study of ions - molecules reactions in the gas phase with collision reaction cell devices: Applications to the direct resolution of spectroscopic interferences in ICP-MS

    International Nuclear Information System (INIS)

    Favre, G.

    2008-12-01

    Inductively Coupled Plasma Mass Spectrometry emerged as the most widespread mass spectrometry technique in inorganic analytical chemistry for determining the concentration of a given isotope or an isotope ratio. The problem of spectroscopic interferences, inherent to this technique, finds a solution through the use of reaction cell devices. An in situ interference removal is feasible with the addition of a well selected gas in the cell. The understanding of the chemistry of ions-molecules interactions in the gas phase is however fundamental to optimize the efficiency of such devices. An accurate knowledge of experimental conditions in the reaction zone according to instrumental parameters appears crucial in order to interpret observed reactivities. This preliminary study is then used for the resolution of two nuclear field characteristic interferences. (author)

  2. Nuclear reactions

    International Nuclear Information System (INIS)

    Lane, A.M.

    1980-01-01

    In reviewing work at Harwell over the past 25 years on nuclear reactions it is stated that a balance has to be struck in both experiment and theory between work on cross-sections of direct practical relevance to reactors and on those relevant to an overall understanding of reaction processes. The compound nucleus and direct process reactions are described. Having listed the contributions from AERE, Harwell to developments in nuclear reaction research in the period, work on the optical model, neutron capture theory, reactions at doorway states with fine structure, and sum-rules for spectroscopic factors are considered in more detail. (UK)

  3. Direct determination of lycopene content in tomatoes (Lycopersicon esculentum) by attenuated total reflectance infrared spectroscopy and multivariate analysis.

    Science.gov (United States)

    Halim, Yuwana; Schwartz, Steven J; Francis, David; Baldauf, Nathan A; Rodriguez-Saona, Luis E

    2006-01-01

    Lycopene is a potent antioxidant that has been shown to play critical roles in disease prevention. Efficient assays for detection and quantification of lycopene are desirable as alternatives to time- and labor-intensive methods. Attenuated total reflectance infrared (ATR-IR) spectroscopy was used for quantification of lycopene in tomato varieties. Calibration models were developed by partial least-squares regression (PLSR) using quantitative measures of lycopene concentration from liquid chromatography as reference method. IR spectra showed a distinct marker band at 957 cm(-1) for trans Carbon-Hydrogen (CH) deformation vibration of lycopene. PLSR models predicted the lycopene content accurately and reproducibly with a correlation coefficient (sigma) of 0.96 and standard error of cross-validation ATR-IR spectroscopy allowed for rapid, simple, and accurate determination of lycopene in tomatoes with minimal sample preparation. Results suggest that the ATR-IR method is applicable for high-throughput quantitative analysis and screening for lycopene in tomatoes.

  4. Resonant elastic scattering of {sup 15}O and a new reaction path in the CNO cycle; Spectroscopie par diffusion elastique resonante d' {sup 15}O et nouveau chemin de reaction dans le cycle CNO

    Energy Technology Data Exchange (ETDEWEB)

    Stefan, Gheorghe Iulian [Ecole doctorale SIMEM, U.F.R. Sciences, Universite de Caen Basse-Normandie, 14032 Caen Cedex (France)

    2006-12-15

    direction. There are stressed the advantages of this approach and one gives details concerning the method of separation of the reaction products from beam particles. The separation is based on the magnetic rigidity values different for the nuclei composing the beam from the ones of the reaction products under study. The new results obtained were confronted with the computed rate of the reaction {sup 15}O(p,{beta}{sup +}){sup 16}O in comparison with the rate estimations for {sup 15}O({alpha},{gamma}){sup 19}Ne. For the first time one underlines the significance of the low energy tail of a resonance in an unbound nucleus. The effect would be an enhancement of the beta decay of {sup 16}F. The consequences for astrophysical processes are underlined. New sequential reactions are suggested and two new reaction cycles from {sup 15}O trough again {sup 15}O are described on this basis. These newly suggested cycles can enhance the energy generation in an explosive environment. To study thoroughly their influence these two new cycles should be introduced in advanced simulation astrophysical codes particularly into those simulating the X bursts.

  5. Measurement of glass transition temperature, residual heat of reaction and mixing ratio of epoxy resins using near infrared spectroscopy: a preliminary study

    DEFF Research Database (Denmark)

    Houmøller, Lars Plejdrup; Laursen, Peter Clemen

    2003-01-01

    As a measure of the degree of curing of epoxy resins, the glass transition temperature, Tg, and the residual heat of reaction, DeltaHr, are often used. In this study, near infrared spectroscopy and multivariate calibration (partial least squares regression (PLSR)) have been used to monitor the two...... variables, using differential scanning calorimetry (DSC) as the reference method. The epoxy under study was a commercial system consisting of the resin, trimethylolpropanetriglycidylether, and the hardener, 3-aminomethyl-3,5,5,-trimethylcyclohexylamine. Using samples cured under different conditions......, calibrations resulted in root mean square errors of cross-validation (RMSECV) of 18 J/g for DeltaHr (range for Hr: 6.1-231.3 J/g) and 7.2ºC for Tg (range for Tg: 41.5-98.8ºC). Also, a PLSR model for mixing ratio of hardener and resin was obtained, resulting in a RMSECV of 0.0040 (range for mixing ratio: 0.180-0.380)...

  6. Chemical and physical factors which control the substitution reactions of direct fission-produced iodine with gaseous methane and the methyl halides

    International Nuclear Information System (INIS)

    Kikuchi, M.; Church, L.B.

    1976-01-01

    The factors controlling the hydrogen and halogen substitution reactions resulting from direct fission-produced iodine isotopes (*I) with gaseous methane and methyl halides were investigated. The chemical reaction probabilities, corrected for any secondary decomposition, were compared as a function of various chemical and physical parameters. These include carbon-halogen bond strength, halogen electronegativity, volume and cross sectional area of the substituted and neighboring atoms. On the basis of this analysis, it is concluded that *I-for-X (where X = H, F, Cl, Br and I) substitution reactions are controlled by the cross sectional area of the X atom. The *I-for-H substitution probability is reduced in proportion to the volume of X, suggesting that steric interference is the dominant factor influencing the reaction probability. (orig.) [de

  7. Cu-catalyzed C(sp³)-H bond activation reaction for direct preparation of cycloallyl esters from cycloalkanes and aromatic aldehydes.

    Science.gov (United States)

    Zhao, Jincan; Fang, Hong; Han, Jianlin; Pan, Yi

    2014-05-02

    Cu-catalyzed dehydrogenation-olefination and esterification of C(sp(3))-H bonds of cycloalkanes with TBHP as an oxidant has been developed. The reaction involves four C-H bond activations and gives cycloallyl ester products directly from cycloalkanes and aromatic aldehydes.

  8. Reaction dynamics of O({sup 1}D) + HCOOD/DCOOH investigated with time-resolved Fourier-transform infrared emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Shang-Chen; Putikam, Raghunath; Lin, M. C., E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw; Tsuchiya, Soji, E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Nghia, N. T. [School of Chemical Engineering - Hanoi University of Science and Technology, Hanoi (Viet Nam); Nguyen, Hue M. T. [Center for Computational Science and Faculty of Chemistry, Hanoi National University of Education, Hanoi (Viet Nam); Lee, Yuan-Pern, E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan (China)

    2014-10-21

    We investigated the reaction dynamics of O({sup 1}D) towards hydrogen atoms of two types in HCOOH. The reaction was initiated on irradiation of a flowing mixture of O{sub 3} and HCOOD or DCOOH at 248 nm. The relative vibration-rotational populations of OH and OD (1 ≦ v ≦ 4, J ≤ 15) states were determined from time-resolved IR emission recorded with a step-scan Fourier-transform spectrometer. In the reaction of O({sup 1}D) + HCOOD, the rotational distribution of product OH is nearly Boltzmann, whereas that of OD is bimodal. The product ratio [OH]/[OD] is 0.16 ± 0.05. In the reaction of O({sup 1}D) + DCOOH, the rotational distribution of product OH is bimodal, but the observed OD lines are too weak to provide reliable intensities. The three observed OH/OD channels agree with three major channels of production predicted with quantum-chemical calculations. In the case of O({sup 1}D) + HCOOD, two intermediates HOC(O)OD and HC(O)OOD are produced in the initial C−H and O−D insertion, respectively. The former undergoes further decomposition of the newly formed OH or the original OD, whereas the latter produces OD via direct decomposition. Decomposition of HOC(O)OD produced OH and OD with similar vibrational excitation, indicating efficient intramolecular vibrational relaxation, IVR. Decomposition of HC(O)OOD produced OD with greater rotational excitation. The predicted [OH]/[OD] ratio is 0.20 for O({sup 1}D) + HCOOD and 4.08 for O({sup 1}D) + DCOOH; the former agrees satisfactorily with experiments. We also observed the v{sub 3} emission from the product CO{sub 2}. This emission band is deconvoluted into two components corresponding to internal energies E = 317 and 96 kJ mol{sup −1} of CO{sub 2}, predicted to be produced via direct dehydration of HOC(O)OH and secondary decomposition of HC(O)O that was produced via decomposition of HC(O)OOH, respectively.

  9. Novel Rearrangements in the Reactions Directed Toward Preparation of Spiro-N,N-ketals: Reactions of Naphthalene-1,8-diamine with Ninhydrin and Isatin

    Directory of Open Access Journals (Sweden)

    Keiji Kobayashi

    2012-11-01

    Full Text Available Spiro-N,N-ketal 5, consisting of a phthaloperine heterocyclic ring and a naphtha[1,8-ef][1,4]diazepine ring, was obtained along with spiro-N,N-ketal 2 via 2,2-condensation in the reaction of ninhydrin with naphthalene-1,8-diamine. Their molecular structures were elucidated by X-ray crystal structural analysis. Aside from these spiro compounds, the diazapleiadiene compound 3 formed by 1,2-condensation and the 1,4-isoquinolinedione compound 4 arising from ring expansion were isolated. When isatin was reacted with naphthalene-1,8-diamine, spiro-N,N-ketal 6 and the two 1H-perimidine-based compounds 7 and 8 were isolated. Compound 8 was revealed to undergo a fast dynamic prototropic tautomerization in solution. Plausible mechanisms of the formation of the products are proposed.

  10. Giant resonance spectroscopy of 40Ca with the (e,e'x) reaction (II): Multipole decomposition of 4π-integrated spectra and angular correlations

    International Nuclear Information System (INIS)

    Diesener, H.; Helm, U.; Huck, V.; Neumann-Cosel, P. von; Rangacharyulu, C.; Richter, A.; Schrieder, G.; Stascheck, A.; Strauch, S.; Ryckebusch, J.; Carter, J.

    2001-01-01

    The present article is the second out of three on a study of the 40 Ca(e,e'x) reaction discussing the multipole decomposition of the measured cross sections and the analysis of angular correlations. The decomposition of the strongly overlapping E0, E1 and E2 giant resonance strengths using the (e,e'x; x=p,α) reaction in 40 Ca is discussed for excitation energies between 10 and about 21 MeV. Two extraction methods are presented based on the variation of the form factors for the different multipoles. The resulting B(E1) strength distribution is in good agreement with (γ,x) photoabsorption data. The summed B(E2) and B(E0) strength is highly fragmented and spread out over the energy region investigated. Microscopic continuum RPA calculations including the coupling of the basic particle-hole states to the low-lying surface vibrations are capable of reproducing the strength distributions quite accurately. Exhaustion of the energy-weighted sum rules (EWSR) for the various decay channels is presented. A complete decomposition of E0, E1 and E2 contributions in 40 Ca is possible for (e,e'α) angular correlations populating the 36 Ar ground state. Contrary to expectations, the form factors of isoscalar E0 and E2 strengths in the 40 Ca(e,e'α 0 ) reaction exhibit increasing differences towards smaller momentum transfers. Angular correlations for proton decay into low-lying states of 39 K are compared to a self-consistent continuum RPA calculation which allows a systematic description of the strong variations observed as a function of 40 Ca excitation energy and momentum transfer. The success implies that direct knock-out models of the 40 Ca(e,e'p) reaction are too simple. Furthermore, the shapes of the angular correlations seem to be determined largely by the final-state interaction, in particular by charge exchange reactions in the nuclear medium

  11. Direct Kinetic Evidence for the Formation of an Acylpyridinium Intermediate in Synthetic p-Nitrophenyl Esterase-Catalyzed Hydrolysis Reactions

    National Research Council Canada - National Science Library

    Wang, Guang-Jia

    1996-01-01

    .... The deacylation rate was also found to exhibit a maximum for the same substrate 2 (n=6). These results are similar to those previously reported with cholesterol esterase as catalyst for the same hydrolysis reaction...

  12. Direct asymmetric vinylogous aldol reaction of allyl ketones with isatins: Divergent synthesis of 3-hydroxy-2-oxindole derivatives

    KAUST Repository

    Zhu, Bo; Zhang, Wen; Lee, Richmond; Han, Zhiqiang; Yang, Wenguo; Tan, Davin; Huang, Kuo-Wei; Jiang, Zhiyong

    2013-01-01

    6 in 1: The highly enantioselective title reaction is mediated by a bifunctional catalyst and leads to E-configured vinylogous aldol products (see scheme). These products are used as common intermediates in the synthesis of six biologically active 3

  13. X-ray photoelectron spectroscopy studies of nitridation on 4H-SiC (0001) surface by direct nitrogen atomic source

    International Nuclear Information System (INIS)

    Chai, J. W.; Pan, J. S.; Zhang, Z.; Wang, S. J.; Chen, Q.; Huan, C. H. A.

    2008-01-01

    A Si 3 N 4 passivation layer has been successfully grown on the 4H-SiC (0001) surface by direct atomic source nitridation at various substrate temperatures. In situ x-ray photoelectron spectroscopy measurements show that higher substrate temperature leads to higher nitridation rate and good crystallinity of the passivation layer. A thin oxynitride layer on the top of the Si 3 N 4 was observed due to the residual O in the vacuum system, but was decomposed during annealing. In the meantime, excess C was found to be effectively removed by the reactive atomic N source

  14. Determination of diffusion coefficients of hydrogen in fused silica between 296 and 523 K by Raman spectroscopy and application of fused silica capillaries in studying redox reactions

    Science.gov (United States)

    Shang, L.; Chou, I-Ming; Lu, W.; Burruss, Robert; Zhang, Y.

    2009-01-01

    Diffusion coefficients (D) of hydrogen in fused silica capillaries (FSC) were determined between 296 and 523 K by Raman spectroscopy using CO2 as an internal standard. FSC capsules (3.25 × 10−4 m OD, 9.9 × 10−5 m ID, and ∼0.01 m long) containing CO2 and H2were prepared and the initial relative concentrations of hydrogen in these capsules were derived from the Raman peak-height ratios between H2 (near 587 cm−1) and CO2 (near 1387 cm−1). The sample capsules were then heated at a fixed temperature (T) at one atmosphere to let H2 diffuse out of the capsule, and the changes of hydrogen concentration were monitored by Raman spectroscopy after quench. This process was repeated using different heating durations at 296 (room T), 323, 375, 430, 473, and 523 K; the same sample capsule was used repeatedly at each temperature. The values of D (in m2 s−1) in FSC were obtained by fitting the observed changes of hydrogen concentration in the FSC capsule to an equation based on Fick’s law. Our D values are in good agreement with the more recent of the two previously reported experimental data sets, and both can be represented by:lnD=-(16.471±0.035)-44589±139RT(R2=0.99991)">lnD=-(16.471±0.035)-44589±139RT(R2=0.99991)where R is the gas constant (8.3145 J/mol K), T in Kelvin, and errors at 1σ level. The slope corresponds to an activation energy of 44.59 ± 0.14 kJ/mol.The D in FSC determined at 296 K is about an order of magnitude higher than that in platinum at 723 K, indicating that FSC is a suitable membrane for hydrogen at temperature between 673 K and room temperature, and has a great potential for studying redox reactions at these temperatures, especially for systems containing organic material and/or sulphur.

  15. X-ray absorption spectroscopy study of the LixFePO4 cathode during cycling using a novel electrochemical in situ reaction cell

    International Nuclear Information System (INIS)

    Deb, A.; Bergmann, U.; Cairns, E.L.; California Univ., Berkeley, CA; Cramer, S.P.; California Univ., Davis, CA

    2004-01-01

    The extraction and insertion of lithium in LiFePO 4 has been investigated in practical Li-ion intercalation electrodes for Li-ion batteries using Fe K-edge X-ray absorption spectroscopy (XAS). A versatile electrochemical in situ reaction cell was utilized, specifically designed for long-term X-ray experiments on battery electrodes during the lithium-extraction/insertion process in electrode materials for Li-ion batteries. The electrode contained about 7.7 mg of LiFePO 4 on a 20 μm-thick Al foil. In order to determine the charge compensation mechanism and structural perturbations occurring in the system during cycling, in situ X-ray absorption fine-structure spectroscopy (XAFS) measurements were conducted on the cell at a moderate rate using typical Li-ion battery operating voltages (3.0-4.1 V versus Li/Li + ).XAS studies of the LiFePO 4 electrode measured at the initial state (LiFePO 4 ) showed iron to be in the Fe(II) state corresponding to the initial state (0.0 mAh) of the battery, whereas in the delithiated state (FePO 4 ) iron was found to be in the FE(III) state corresponding to the final charged state (3 m Ah) of the battery. The X-ray absorption near-edge structure (XANES) region of the XAS spectra revealed a high-spin configuration for the two states [Fe(II), d 6 and Fe(III), d 5 ]. The XAFS data analysis confirmed that the olivine structure of the LeFePO 4 and FePO 4 is retained by the electrodes, which is in agreement with the X-ray diffraction observations on these compounds. The XAFS data that were collected continuously during cycling revealed details about the response of the cathode to Li insertion and extraction. These measurements on the LiFePO 4 cathode show that the material retains good structural short-range order leading to superior cycling

  16. Evaluation of the extent of initial Maillard reaction during cooking some vegetables by direct measurement of the Amadori compounds.

    Science.gov (United States)

    Yu, Jiahao; Zhang, Shuqin; Zhang, Lianfu

    2018-01-01

    During vegetable cooking, one of the most notable and common chemical reactions is the Maillard reaction, which occurs as a result of thermal treatment and dehydration. Amadori compound determination provides a very sensitive indicator for early detection of quality changes caused by the Maillard reaction, as well as to retrospectively assess the heat treatment or storage conditions to which the product has been subjected. In this paper, a hydrophilic interaction liquid chromatographic-electrospray ionization-tandem mass spectrometric method was developed for the analysis of eight Amadori compounds, and the initial steps of the Maillard reaction during cooking (steaming, frying and baking) bell pepper, red pepper, yellow onion, purple onion, tomato and carrot were also assessed by quantitative determination of these Amadori compounds. These culinary treatments reduced moisture and increased the total content of Amadori compounds, which was not dependent on the type of vegetable or cooking method. Moreover, the effect of steaming on Amadori compound content and water loss was less than that by baking and frying vegetables. Further studies showed that the combination of high temperature and short time may lead to lower formation of Amadori compounds when baking vegetables. Culinary methods differently affected the extent of initial Maillard reaction when vegetables were made into home-cooked products. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  17. Direct Imaging of Transient Fano Resonances in N_{2} Using Time-, Energy-, and Angular-Resolved Photoelectron Spectroscopy.

    Science.gov (United States)

    Eckstein, Martin; Yang, Chung-Hsin; Frassetto, Fabio; Poletto, Luca; Sansone, Giuseppe; Vrakking, Marc J J; Kornilov, Oleg

    2016-04-22

    Autoionizing Rydberg states of molecular N_{2} are studied using time-, energy-, and angular-resolved photoelectron spectroscopy. A femtosecond extreme ultraviolet pulse with a photon energy of 17.5 eV excites the resonance and a subsequent IR pulse ionizes the molecule before the autoionization takes place. The angular-resolved photoelectron spectra depend on pump-probe time delay and allow for the distinguishing of two electronic states contributing to the resonance. The lifetime of one of the contributions is determined to be 14±1  fs, while the lifetime of the other appears to be significantly shorter than the time resolution of the experiment. These observations suggest that the Rydberg states in this energy region are influenced by the effect of interference stabilization and merge into a complex resonance.

  18. High-sensitivity ultraviolet photoemission spectroscopy technique for direct detection of gap states in organic thin films

    Energy Technology Data Exchange (ETDEWEB)

    Bussolotti, Fabio, E-mail: fabio@ims.ac.jp

    2015-10-01

    Highlights: • Density of gap states in organic thin film was detected by photoemission spectroscopy. • Inert gas exposure affects the density of gap states in organic thin films. • Density of gap states controls the energy level alignment at the organic/inorganic and organic/organic interfaces. - Abstract: We developed ultrahigh sensitivity, low-background ultraviolet photoemission spectroscopy (UPS) technique which does not introduce detectable radiation damages into organic materials. The UPS allows to detect density of states of the order of ∼10{sup 16} states eV{sup −1} cm{sup −3} even for radiation-sensitive organic films, this results being comparable to electrical measurements of charge trapping centers. In this review we introduce the method of ultrahigh sensitivity photoemission measurement and we present some results on the energy distribution of gap states in pentacene (Pn) films deposited on SiO{sub 2} and Au(1 1 1) substrate. For Pn/SiO{sub 2} thin film the results show that exposure to inert gas (N{sub 2} and Ar) atmosphere produces a sharp rise in gap states from 10{sup 16} to 10{sup 18} states eV{sup −1} cm{sup −3} and pushes the Fermi level closer to the valence band (0.15–0.17 eV), as does exposure to O{sub 2} (0.20 eV), while no such gas-induced effects are observed for Pn/Au(1 1 1) system. The results demonstrate that these gap states originate from small imperfections in the Pn packing structure, which are induced by gas penetration into the film through the Pn crystal grain boundaries. Similar results were obtained for CuPc/F{sub 16}CuPc thin films, a prototypical example of donor/acceptor interface for photovoltaic application.

  19. Using surface-enhanced Raman spectroscopy and electrochemically driven melting to discriminate Yersinia pestis from Y. pseudotuberculosis based on single nucleotide polymorphisms within unpurified polymerase chain reaction amplicons.

    Science.gov (United States)

    Papadopoulou, Evanthia; Goodchild, Sarah A; Cleary, David W; Weller, Simon A; Gale, Nittaya; Stubberfield, Michael R; Brown, Tom; Bartlett, Philip N

    2015-02-03

    The development of sensors for the detection of pathogen-specific DNA, including relevant species/strain level discrimination, is critical in molecular diagnostics with major impacts in areas such as bioterrorism and food safety. Herein, we use electrochemically driven denaturation assays monitored by surface-enhanced Raman spectroscopy (SERS) to target single nucleotide polymorphisms (SNPs) that distinguish DNA amplicons generated from Yersinia pestis, the causative agent of plague, from the closely related species Y. pseudotuberculosis. Two assays targeting SNPs within the groEL and metH genes of these two species have been successfully designed. Polymerase chain reaction (PCR) was used to produce Texas Red labeled single-stranded DNA (ssDNA) amplicons of 262 and 251 bases for the groEL and metH targets, respectively. These amplicons were used in an unpurified form to hybridize to immobilized probes then subjected to electrochemically driven melting. In all cases electrochemically driven melting was able to discriminate between fully homologous DNA and that containing SNPs. The metH assay was particularly challenging due to the presence of only a single base mismatch in the middle of the 251 base long PCR amplicon. However, manipulation of assay conditions (conducting the electrochemical experiments at 10 °C) resulted in greater discrimination between the complementary and mismatched DNA. Replicate data were collected and analyzed for each duplex on different days, using different batches of PCR product and different sphere segment void (SSV) substrates. Despite the variability introduced by these differences, the assays are shown to be reliable and robust providing a new platform for strain discrimination using unpurified PCR samples.

  20. Chalcogenide oxygen reduction reaction catalysis: X-ray photoelectron spectroscopy with Ru, Ru/Se and Ru/S samples emersed from aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Lewera, A. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw (Poland); Inukai, J. [Clean Energy Research Center, University of Yamanashi, 7-32 Miyamae-cho, Kofu 400-0006 (Japan); Zhou, W.P. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Cao, D. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Duong, H.T. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Alonso-Vante, N. [Laboratory of Electrocatalysis, UMR-CNRS 6503, University of Poitiers, F-86022 Poitiers (France)]. E-mail: Nicolas.Alonso.Vante@univ-poitiers.fr; Wieckowski, A. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States)]. E-mail: andrzej@scs.uiuc.edu

    2007-05-10

    Oxygen reduction Ru/Se and Ru/S fuel cell surface chalcogenide catalysts were prepared via chemical reaction of reduced Ru nanoparticles with selenium and sulfur in xylenes [D. Cao, A. Wieckowski, J. Inukai, N. Alonso-Vante, J. Electrochem. Soc. 153 (2006) A869]. The chalcogenide samples - as well as the starting chalcogens-free Ru nanoparticle material - were immobilized on a gold disk for X-ray Photoelectron Spectroscopy (XPS) characterization. While we found oxygen in most of the samples, predominantly from Ru oxides, we conclude that the oxygen on Ru/S may be located in subsurface sites: the subsurface oxygen. We also found that the transformation of the oxidized Ru black to metallic Ru required intensive electrochemical treatment, including hydrogen evolution. In contrast, five cyclic voltammetric scans in the potential range from 0.00 and 0.75 V versus RHE were sufficient to remove the oxygen forms from Ru/Se and, to a large extent, from Ru/S. We therefore conclude that Ru metal is protected against oxidation to Ru oxides by the chalcogens additives. The voltammetric treatment in the 0.00 and 0.75 V range also removed the SeO{sub 2} or SO {sub x} forms leaving anionic/elemental Se or S on the surface. Upon larger amplitude voltammetric cycling, from 0.00 to 1.20 V versus RHE, both Se and S were dissolved and the dissolution process was coincidental with the oxygen growth in/on the Ru samples.

  1. Chalcogenide oxygen reduction reaction catalysis: X-ray photoelectron spectroscopy with Ru, Ru/Se and Ru/S samples emersed from aqueous media

    International Nuclear Information System (INIS)

    Lewera, A.; Inukai, J.; Zhou, W.P.; Cao, D.; Duong, H.T.; Alonso-Vante, N.; Wieckowski, A.

    2007-01-01

    Oxygen reduction Ru/Se and Ru/S fuel cell surface chalcogenide catalysts were prepared via chemical reaction of reduced Ru nanoparticles with selenium and sulfur in xylenes [D. Cao, A. Wieckowski, J. Inukai, N. Alonso-Vante, J. Electrochem. Soc. 153 (2006) A869]. The chalcogenide samples - as well as the starting chalcogens-free Ru nanoparticle material - were immobilized on a gold disk for X-ray Photoelectron Spectroscopy (XPS) characterization. While we found oxygen in most of the samples, predominantly from Ru oxides, we conclude that the oxygen on Ru/S may be located in subsurface sites: the subsurface oxygen. We also found that the transformation of the oxidized Ru black to metallic Ru required intensive electrochemical treatment, including hydrogen evolution. In contrast, five cyclic voltammetric scans in the potential range from 0.00 and 0.75 V versus RHE were sufficient to remove the oxygen forms from Ru/Se and, to a large extent, from Ru/S. We therefore conclude that Ru metal is protected against oxidation to Ru oxides by the chalcogens additives. The voltammetric treatment in the 0.00 and 0.75 V range also removed the SeO 2 or SO x forms leaving anionic/elemental Se or S on the surface. Upon larger amplitude voltammetric cycling, from 0.00 to 1.20 V versus RHE, both Se and S were dissolved and the dissolution process was coincidental with the oxygen growth in/on the Ru samples

  2. Histochemical detection of the in vivo produced cellular aldehydes by means of direct Schiff's reaction in CCl/sub 4/ intoxicated rat liver

    Energy Technology Data Exchange (ETDEWEB)

    Taper, H.S.; Somer, M.P.; Lans, M.; Gerlache, J. de; Roberfroid, M.

    1988-04-01

    A histochemical technique for detection of the in vivo induced cellular aldehydes based on the direct Schiff's reaction is reported in this paper. CCl/sub 4/-intoxicated rat liver was used as an experimental model. Fresh and non-pretreated rat liver cryostat sections fixed in 10% formol calcium solution and washed in distilled water were exposed to Schiff's reagent. The sections were then immersed in two baths of sodium bisulphite solution, then in water, dehydrated in ethanol, cleared in xylene and mounted in a synthetic anhydrous mounting medium. As Schiff positive areas presented well circumscribed foci which increased with time following intoxication, semiquantitative planimetric measurements were feasible. The direct Schiff's reaction detects cellular aldehydes in a sensitive, rapid histologically and topographically estimable way. The appearance of these aldehydes precedes distinctly morphological alterations detectable by other histochemical of histological techniques. No positive results were obtained in control, non-intocicated rat livers. Inhibitons of this direct Schiff's was obtained in positive control rat liver sections preincubated in solutions of aldehyde blockers. Histochemical detection of aldehydes may give useful information on different aspects of tissue and organ intoxication such as their topography, appearance, evolution, extension, consequences and effects of treatment. The direct Schiff's reaction can be considered as a valuable tool in fundamental and applied reasearch dealing with various toxicological, environmental, pathological, cancer-related and therapeutic problems.

  3. Direct and inverse reactions of LiH+ with He(1S) from quantum calculations: mechanisms and rates.

    Science.gov (United States)

    Tacconi, M; Bovino, S; Gianturco, F A

    2012-01-14

    The gas-phase reaction of LiH(+) (X(2)Σ) with He((1)S) atoms, yielding Li(+)He with a small endothermicity for the rotovibrational ground state of the reagents, is analysed using the quantum reactive approach that employs the Negative Imaginary Potential (NIP) scheme discussed earlier in the literature. The dependence of low-T rates on the initial vibrational state of LiH(+) is analysed and the role of low-energy Feshbach resonances is also discussed. The inverse destruction reaction of LiHe(+), a markedly exothermic process, is also investigated and the rates are computed in the same range of temperatures. The possible roles of these reactions in early universe astrophysical networks, in He droplets environments or in cold traps are briefly discussed.

  4. Direct measurement of the 7Be(n, α4 He reaction cross sections for the cosmological Li problem

    Directory of Open Access Journals (Sweden)

    Kawabata Takahiro

    2017-01-01

    Full Text Available The cross sections of the 7Be(n, α4He reaction for p-wave neutrons were experimentally determined at Ec.m. = 0.20−0.81 MeV close to the Big Bang nucleosynthesis (BBN energy window for the first time on the basis of the detailed balance principle by measuring the time-reverse reaction. The obtained cross sections are much larger than the cross sections for s-wave neutrons inferred from the recent measurement at the n_TOF facility in CERN, but significantly smaller than the theoretical estimation widely used in the BBN calculations. The present results suggest the 7Be(n, α4 He reaction rate is not large enough to solve the cosmological lithium problem

  5. The Brønsted Acid-Catalyzed, Enantioselective Aza-Diels-Alder Reaction for the Direct Synthesis of Chiral Piperidones.

    Science.gov (United States)

    Weilbeer, Claudia; Sickert, Marcel; Naumov, Sergei; Schneider, Christoph

    2017-01-12

    We disclose herein the first enantioselective aza-Diels-Alder reaction of β-alkyl-substituted vinylketene silyl-O,O-acetals and imines furnishing a broad range of optically highly enriched 4-alkyl-substituted 2-piperidones. As a catalyst for this one-pot reaction we employed a chiral phosphoric acid which effects a vinylogous Mannich reaction directly followed by ring-closure to the lactam. Subsequent fully diastereoselective transformations including hydrogenation, enolate alkylation, and lactam alkylation/reduction processes converted the cycloadducts into various highly substituted piperidines of great utility for the synthesis of natural products and medicinally active compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Evaluation of the AGCU Expressmarker 16 and 22 PCR Amplification Kits Using Biological Samples Applied to FTA Micro Cards in Reduced Volume Direct PCR Amplification Reactions

    Directory of Open Access Journals (Sweden)

    Samantha J Ogden

    2015-01-01

    Full Text Available This study evaluated the performance of the  Wuxi AGCU ScienTech Incorporation (HuiShan, Wuxi, China AGCU Expressmarker 16 (EX 16 and 22 (EX22 short tandem repeat (STR amplification kits in reduced reaction volumes using direct polymerase chain reaction (PCR amplification workflows. The commercially available PowerPlex® 21 (PP21 System (Promega, Wisconsin, USA, which follows similar direct workflows, was used as a reference. Anticoagulate blood applied to chemically impregnated  FTA TM Micro Cards (GE Healthcare UK Limited, Amersham Place, Little Chalfont, Buckinghamshire, HP7 9NA, UK was used to represent a complex biological sample. Allelic concordance, first-pass success rate, average peak heights, heterozygous peak height ratios (HPHRs, and intracolor and intercolor peak height balance were determined. In reduced volume PCR reactions, the performances of both the EX16 and EX22 STR amplification kits were comparable to that of the PP21 System. The level of performance was maintained at PCR reaction volumes, which are 40% of that recommended. The EX22 and PP21 System kits possess comparable overlapping genome coverage. This study evaluated the performance of the AGCU EX16 and EX22 STR amplification kits in reduced PCR reaction volumes using direct workflows in combination with whole blood applied to FTA TM Micro Cards. Allelic concordance, first-pass success rate, average peak heights, HPHRs, and intracolor and intercolor peak height balance were determined. A concordance analysis was completed that compared the performance of the EX16 and EX22 kits using human blood applied to FTA Micro Cards in combination with full, half, and reduced PCR reaction volumes. The PP21 System (Promega was used as a reference kit. Where appropriate, the distributions of data were assessed using the Shapiro-Wilk test. For normally-distributed data, statistics were calculated using analysis of variance (ANOVA and for nonparametric data the Wilcoxon

  7. Model independent spectroscopic information from an analysis of peripheral direct radiative capture reaction and its application for an extrapolation of an astrophysical S-factor to stellar energies

    International Nuclear Information System (INIS)

    Igamov, S.B.; Tursunmuratov, T.M.; Yarmukhamedov, R.

    2003-01-01

    In this work, within the framework of the cluster potential approach we develop a method which can be used an independent source of getting information on the value of the nuclear vertex constant (NVC) (or respective asymptotical normalization coefficient (ANC)) from the analysis of the direct radiative capture cross section σ(E)(or the astrophysical S-factor S(E)) at extremely low energies by a model independent way as possible. The main idea of the proposed method is that at stellar energies peripheral direct radiative capture reaction of astrophysical interest proceeds mainly through the tail of the overlap integral, which is completely determined by the binding energy and the respective ANC (or NVC). The main advantage of the proposed method is that it allows us to determine both the absolute value of NVC (or ANC) and the astrophysical S-factor S(E) at solar energies (0-50 keV) by means of the analysis of the same experimental astrophysical S-factor S exp (E) in a correct self consistent way using the same potential both for the bound state and for scattering state. The method has been applied for an investigation of the direct radiative capture t(α, γ) 7 Li and 3 He(α, γ) 7 Be reactions at extremely low energies. At first, this method was used for analysis of the S exp (E) to determine values of the modulus squared of the NVC's (or the respective ANC's). The values of NVC's are presented. Then, the obtained NVC's are used by us for extrapolation of the S(E) of the reactions considered to stellar energies (E=0-50 keV) for the 3 He(α, γ) 7 Be reaction and for the t(α, γ) 7 Li reaction. The obtained results are compared with those other authors

  8. A Ring Polymer Molecular Dynamics Approach to Study the Transition between Statistical and Direct Mechanisms in the H2 + H3+ → H3+ + H2 Reaction.

    Science.gov (United States)

    Suleimanov, Yury V; Aguado, Alfredo; Gómez-Carrasco, Susana; Roncero, Octavio

    2018-05-03

    Because of its fundamental importance in astrochemistry, the H 2 + H 3 + → H 3 + + H 2 reaction has been studied experimentally in a wide temperature range. Theoretical studies of the title reaction significantly lag primarily because of the challenges associated with the proper treatment of the zero-point energy (ZPE). As a result, all previous theoretical estimates for the ratio between a direct proton-hop and indirect exchange (via the H 5 + complex) channels deviate from the experiment, in particular, at lower temperatures where the quantum effects dominate. In this work, the ring polymer molecular dynamics (RPMD) method is applied to study this reaction, providing very good agreement with the experiment. RPMD is immune to the shortcomings associated with the ZPE leakage and is able to describe the transition from direct to indirect mechanisms below room temperature. We argue that RPMD represents a useful tool for further studies of numerous ZPE-sensitive chemical reactions that are of high interest in astrochemistry.

  9. Characterization of direct current He-N{sub 2} mixture plasma using optical emission spectroscopy and mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Flores, O.; Castillo, F.; Martinez, H. [Laboratorio de Espectroscopia, Instituto de Ciencias Físicas, Universidad Nacional Autónoma de México, Apartado Postal 48-3, 62251, Cuernavaca, Morelos (Mexico); Villa, M.; Reyes, P. G. [Facultad de Ciencias, Universidad Autónoma del Estado de México, Estado de México (Mexico); Villalobos, S. [Laboratorio de Espectroscopia, Instituto de Ciencias Físicas, Universidad Nacional Autónoma de México, Apartado Postal 48-3, 62251, Cuernavaca, Morelos (Mexico); Facultad de Ingeniería, Universidad Nacional Autónoma de México, México D.F. (Mexico)

    2014-05-15

    This study analyses the glow discharge of He and N{sub 2} mixture at the pressure of 2.0 Torr, power of 10 W, and flow rate of 16.5 l/min, by using optical emission spectroscopy and mass spectrometry. The emission bands were measured in the wavelength range of 200–1100 nm. The principal species observed were N{sub 2}{sup +} (B{sup 2}Σ{sup +}{sub u}→X{sup 2}Σ{sup +}{sub g}), N{sub 2} (C{sup 3}Π{sub u}→B{sup 3}Π{sub g}), and He, which are in good agreement with the results of mass spectrometry. Besides, the electron temperature and ion density were determined by using a double Langmuir probe. Results indicate that the electron temperature is in the range of 1.55–2.93 eV, and the electron concentration is of the order of 10{sup 10} cm{sup −3}. The experimental results of electron temperature and ion density for pure N{sub 2} and pure He are in good agreement with the values reported in the literature.

  10. Direct spectral analysis and determination of high content of carcinogenic bromine in bread using UV pulsed laser induced breakdown spectroscopy.

    Science.gov (United States)

    Mehder, A O; Gondal, Mohammed A; Dastageer, Mohamed A; Habibullah, Yusuf B; Iqbal, Mohammed A; Oloore, Luqman E; Gondal, Bilal

    2016-01-01

    Laser induced breakdown spectroscopy (LIBS) was applied for the detection of carcinogenic elements like bromine in four representative brands of loaf bread samples and the measured bromine concentrations were 352, 157, 451, and 311 ppm, using Br I (827.2 nm) atomic transition line as the finger print atomic transition. Our LIBS system is equipped with a pulsed laser of wavelength 266 nm with energy 25 mJ pulse(-1), 8 ns pulse duration, 20 Hz repetition rate, and a gated ICCD camera. The LIBS system was calibrated with the standards of known concentrations in the sample (bread) matrix and such plot is linear in 20-500 ppm range. The capability of our system in terms of limit of detection and relative accuracy with respect to the standard inductively coupled plasma mass spectrometry (ICPMS) technique was evaluated and these values were 5.09 ppm and 0.01-0.05, respectively, which ensures the applicability of our system for Br trace level detection, and LIBS results are in excellent agreement with that of ICPMS results.

  11. Reaction of a chemotherapeutic agent, 6-mercaptopurine, with a direct-acting, electrophilic carcinogen, benzo[a]pyrene-7,8-diol 9,10-epoxide.

    Science.gov (United States)

    MacLeod, M C; Stewart, E; Daylong, A; Lew, L K; Evans, F E

    1991-01-01

    The chemotherapeutic agent 6-mercaptopurine (6-MP) has been shown to react covalently with the ultimate carcinogenic metabolite of benzo[a]pyrene, 7-r,8-t-dihydroxy-9-t,10-t-oxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BPDE), in aqueous solution, forming a single adduct. NMR studies of the HPLC-purified product were consistent with its identification as 10(S)-(6'-mercaptopurinyl)-7,8,9-trihydroxy-7,8,9,10- tetrahydrobenzo[a]pyrene. Reaction kinetics were analyzed by using both HPLC separation of the products formed and a spectrophotometric assay for adduct formation. A simple model in which direct reaction between 6-MP and BPDE takes place without formation of a physical complex was found to adequately predict the dependence of product ratios on 6-MP concentration. Variations in the observed rate constant for this reaction with changes in temperature, pH, and buffer concentration were determined and compared to the effects of these variables on the observed rate constant for BPDE hydrolysis. In each case, the processes were affected quite differently, suggesting that different rate-determining steps are involved. The data suggest that the reaction mechanism involves SN2 attack of the anion of 6-MP, formed by ionization of the sulfhydryl group, on carbon 10 of BPDE, resulting in a trans-9,10 reaction product.

  12. Production of the charmonium states in the direct channel of pantip annihilation and description of a new experimental method. Exclusive reactions pantip#-> #e+e-

    International Nuclear Information System (INIS)

    Brom, J.M.

    1985-06-01

    The experiment R704 at the CERN Intersecting Storages Rings (ISR) utilised a completely new technique for charmonium spectroscopy, using a cooled antiprotons beam in collision with protons of a dense, molecular H 2 ''jet target''. ISR operations, jet target and experimental apparatus are described. Observation of the reaction pantip#-> #J/Ψ#-> #e + e - (193 evts for an integrated luminosity of 141 nb -1 ) and estimation of the J/Ψ mass using the beam parameters (3096.95±0.1±0.27 MeV) are used to test the method, the energy calibration and the reproductibility of the ISR. From these results, a very good precision of ± 300 KeV is expected in the later results on J PC ≠ 1 -- states. In addition, we give new upper limits for the magnetic form factor of the proton at high transfer [fr

  13. Evolution of direct mechanisms with incident energy from the Coulomb-barrier to relativistic energies. - Two-center effects in nucleon transfer between nuclei. - Signatures of nucleon promotion in heavy ion reactions at barrier energies

    International Nuclear Information System (INIS)

    Oertzen, W. von; Voit, H.; Imanishi, B.

    1988-10-01

    This report contains a review article considering the evolution of direct mechanisms with incident energy in heavy ion reactions and two theoretical articles concerning two-center effects in transfer reactions between heavy ions and the nucleon promotion in heavy ion reactions. See hints under the relevant topics. (HSI)

  14. Directional errors of movements and their correction in a discrete tracking task. [pilot reaction time and sensorimotor performance

    Science.gov (United States)

    Jaeger, R. J.; Agarwal, G. C.; Gottlieb, G. L.

    1978-01-01

    Subjects can correct their own errors of movement more quickly than they can react to external stimuli by using three general categories of feedback: (1) knowledge of results, primarily visually mediated; (2) proprioceptive or kinaesthetic such as from muscle spindles and joint receptors, and (3) corollary discharge or efference copy within the central nervous system. The effects of these feedbacks on simple reaction time, choice reaction time, and error correction time were studied in four normal human subjects. The movement used was plantarflexion and dorsiflexion of the ankle joint. The feedback loops were modified, by changing the sign of the visual display to alter the subject's perception of results, and by applying vibration at 100 Hz simultaneously to both the agonist and antagonist muscles of the ankle joint. The central processing was interfered with when the subjects were given moderate doses of alcohol (blood alcohol concentration levels of up to 0.07%). Vibration and alcohol increase both the simple and choice reaction times but not the error correction time.

  15. Single-Molecule Force Spectroscopy Trajectories of a Single Protein and Its Polyproteins Are Equivalent: A Direct Experimental Validation Based on A Small Protein NuG2.

    Science.gov (United States)

    Lei, Hai; He, Chengzhi; Hu, Chunguang; Li, Jinliang; Hu, Xiaodong; Hu, Xiaotang; Li, Hongbin

    2017-05-22

    Single-molecule force spectroscopy (SMFS) has become a powerful tool in investigating the mechanical unfolding/folding of proteins at the single-molecule level. Polyproteins made of tandem identical repeats have been widely used in atomic force microscopy (AFM)-based SMFS studies, where polyproteins not only serve as fingerprints to identify single-molecule stretching events, but may also improve statistics of data collection. However, the inherent assumption of such experiments is that all the domains in the polyprotein are equivalent and one SMFS trajectory of stretching a polyprotein made of n domains is equivalent to n trajectories of stretching a single domain. Such an assumption has not been validated experimentally. Using a small protein NuG2 and its polyprotein (NuG2) 4 as model systems, here we use optical trapping (OT) to directly validate this assumption. Our results show that OT experiments on NuG2 and (NuG2) 4 lead to identical parameters describing the unfolding and folding kinetics of NuG2, demonstrating that indeed stretching a polyprotein of NuG2 is equivalent to stretching single NuG2 in force spectroscopy experiments and thus validating the use of polyproteins in SMFS experiments. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Gold nanoparticles bridging infra-red spectroscopy and laser desorption/ionization mass spectrometry for direct analysis of over-the-counter drug and botanical medicines.

    Science.gov (United States)

    Chau, Siu-Leung; Tang, Ho-Wai; Ng, Kwan-Ming

    2016-05-05

    With a coating of gold nanoparticles (AuNPs), over-the-counter (OTC) drugs and Chinese herbal medicine granules in KBr pellets could be analyzed by Fourier Transform Infra-red (FT-IR) spectroscopy and Surface-assisted Laser Desorption/Ionization mass spectrometry (SALDI-MS). FT-IR spectroscopy allows fast detection of major active ingredient (e.g., acetaminophen) in OTC drugs in KBr pellets. Upon coating a thin layer of AuNPs on the KBr pellet, minor active ingredients (e.g., noscapine and loratadine) in OTC drugs, which were not revealed by FT-IR, could be detected unambiguously using AuNPs-assisted LDI-MS. Moreover, phytochemical markers of Coptidis Rhizoma (i.e. berberine, palmatine and coptisine) could be quantified in the concentrated Chinese medicine (CCM) granules by the SALDI-MS using standard addition method. The quantitative results matched with those determined by high-performance liquid chromatography with ultraviolet detection. Being strongly absorbing in UV yet transparent to IR, AuNPs successfully bridged FT-IR and SALDI-MS for direct analysis of active ingredients in the same solid sample. FT-IR allowed the fast analysis of major active ingredient in drugs, while SALDI-MS allowed the detection of minor active ingredient in the presence of excipient, and also quantitation of phytochemicals in herbal granules. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. In-Source Laser Spectroscopy with the Laser Ion Source and Trap: First Direct Study of the Ground-State Properties of ^{217,219}Po

    Directory of Open Access Journals (Sweden)

    D. A. Fink

    2015-02-01

    Full Text Available A Laser Ion Source and Trap (LIST for a thick-target, isotope-separation on-line facility has been implemented at CERN ISOLDE for the production of pure, laser-ionized, radioactive ion beams. It offers two modes of operation, either as an ion guide, which performs similarly to the standard ISOLDE resonance ionization laser ion source (RILIS, or as a more selective ion source, where surface-ionized ions from the hot ion-source cavity are repelled by an electrode, while laser ionization is done within a radio-frequency quadrupole ion guide. The first physics application of the LIST enables the suppression of francium contamination in ion beams of neutron-rich polonium isotopes at ISOLDE by more than 1000 with a reduction in laser-ionization efficiency of only 20. Resonance ionization spectroscopy is performed directly inside the LIST device, allowing the study of the hyperfine structure and isotope shift of ^{217}Po for the first time. Nuclear decay spectroscopy of ^{219}Po is performed for the first time, revealing its half-life, α-to-β-decay branching ratio, and α-particle energy. This experiment demonstrates the applicability of the LIST at radioactive ion-beam facilities for the production and study of pure beams of exotic isotopes.

  18. Calibration strategies for the direct determination of Ca, K, and Mg in commercial samples of powdered milk and solid dietary supplements using laser-induced breakdown spectroscopy (LIBS).

    Science.gov (United States)

    Dos Santos Augusto, Amanda; Barsanelli, Paulo Lopes; Pereira, Fabiola Manhas Verbi; Pereira-Filho, Edenir Rodrigues

    2017-04-01

    This study describes the application of laser-induced breakdown spectroscopy (LIBS) for the direct determination of Ca, K and Mg in powdered milk and solid dietary supplements. The following two calibration strategies were applied: (i) use of the samples to calculate calibration models (milk) and (ii) use of sample mixtures (supplements) to obtain a calibration curve. In both cases, reference values obtained from inductively coupled plasma optical emission spectroscopy (ICP OES) after acid digestion were used. The emission line selection from LIBS spectra was accomplished by analysing the regression coefficients of partial least squares (PLS) regression models, and wavelengths of 534.947, 766.490 and 285.213nm were chosen for Ca, K and Mg, respectively. In the case of the determination of Ca in supplements, it was necessary to perform a dilution (10-fold) of the standards and samples to minimize matrix interference. The average accuracy for powdered milk ranged from 60% to 168% for Ca, 77% to 152% for K and 76% to 131% for Mg. In the case of dietary supplements, standard error of prediction (SEP) varied from 295 (Mg) to 3782mgkg -1 (Ca). The proposed method presented an analytical frequency of around 60 samples per hour and the step of sample manipulation was drastically reduced, with no generation of toxic chemical residues. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Direct speciation analysis of arsenic in sub-cellular compartments using micro-X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Bacquart, Thomas; Deves, Guillaume; Ortega, Richard

    2010-01-01

    Identification of arsenic chemical species at a sub-cellular level is a key to understanding the mechanisms involved in arsenic toxicology and antitumor pharmacology. When performed with a microbeam, X-ray absorption near-edge structure (μ-XANES) enables the direct speciation analysis of arsenic in sub-cellular compartments avoiding cell fractionation and other preparation steps that might modify the chemical species. This methodology couples tracking of cellular organelles in a single cell by confocal or epifluorescence microscopy with local analysis of chemical species by μ-XANES. Here we report the results obtained with a μ-XANES experimental setup based on Kirkpatrick-Baez X-ray focusing optics that maintains high flux of incoming radiation (>10 11 ph/s) at micrometric spatial resolution (1.5x4.0 μm 2 ). This original experimental setup enabled the direct speciation analysis of arsenic in sub-cellular organelles with a 10 -15 g detection limit. μ-XANES shows that inorganic arsenite, As(OH) 3 , is the main form of arsenic in the cytosol, nucleus, and mitochondrial network of cultured cancer cells exposed to As 2 O 3 . On the other hand, a predominance of As(III) species is observed in HepG2 cells exposed to As(OH) 3 with, in some cases, oxidation to a pentavalent form in nuclear structures of HepG2 cells. The observation of intra-nuclear mixed redox states suggests an inter-individual variability in a cell population that can only be evidenced with direct sub-cellular speciation analysis.

  20. Direct observation of high-spin states in manganese dimer and trimer cations by x-ray magnetic circular dichroism spectroscopy in an ion trap

    Energy Technology Data Exchange (ETDEWEB)

    Zamudio-Bayer, V. [Physikalisches Institut, Universität Freiburg, Stefan-Meier-Straße 21, 79104 Freiburg (Germany); Institut für Methoden und Instrumentierung der Forschung mit Synchrotronstrahlung, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Straße 15, 12489 Berlin (Germany); Hirsch, K.; Langenberg, A.; Kossick, M. [Institut für Methoden und Instrumentierung der Forschung mit Synchrotronstrahlung, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Straße 15, 12489 Berlin (Germany); Institut für Optik und Atomare Physik, Technische Universität Berlin, Hardenbergstraße 36, 10623 Berlin (Germany); Ławicki, A.; Lau, J. T., E-mail: tobias.lau@helmholtz-berlin.de [Institut für Methoden und Instrumentierung der Forschung mit Synchrotronstrahlung, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Straße 15, 12489 Berlin (Germany); Terasaki, A. [Cluster Research Laboratory, Toyota Technological Institute, 717-86 Futamata, Ichikawa, Chiba 272-0001 (Japan); Department of Chemistry, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Issendorff, B. von [Physikalisches Institut, Universität Freiburg, Stefan-Meier-Straße 21, 79104 Freiburg (Germany)

    2015-06-21

    The electronic structure and magnetic moments of free Mn{sub 2}{sup +} and Mn{sub 3}{sup +} are characterized by 2p x-ray absorption and x-ray magnetic circular dichroism spectroscopy in a cryogenic ion trap that is coupled to a synchrotron radiation beamline. Our results directly show that localized magnetic moments of 5 μ{sub B} are created by 3d{sup 5}({sup 6}S) states at each ionic core, which are coupled ferromagnetically to form molecular high-spin states via indirect exchange that is mediated in both cases by a delocalized valence electron in a singly occupied 4s derived antibonding molecular orbital with an unpaired spin. This leads to total magnetic moments of 11 μ{sub B} for Mn{sub 2}{sup +} and 16 μ{sub B} for Mn{sub 3}{sup +}, with no contribution of orbital angular momentum.

  1. Direct evaluation of electrical dipole moment and oxygen density ratio at high-k dielectrics/SiO2 interface by X-ray photoelectron spectroscopy analysis

    Science.gov (United States)

    Fujimura, Nobuyuki; Ohta, Akio; Ikeda, Mitsuhisa; Makihara, Katsunori; Miyazaki, Seiichi

    2018-04-01

    The electrical dipole moment at an ultrathin high-k (HfO2, Al2O3, TiO2, Y2O3, and SrO)/SiO2 interface and its correlation with the oxygen density ratio at the interface have been directly evaluated by X-ray photoelectron spectroscopy (XPS) under monochromatized Al Kα radiation. The electrical dipole moment at the high-k/SiO2 interface has been measured from the change in the cut-off energy of secondary photoelectrons. Moreover, the oxygen density ratio at the interface between high-k and SiO2 has been estimated from cation core-line signals, such as Hf 4f, Al 2p, Y 3d, Ti 2p, Sr 3d, and Si 2p. We have experimentally clarified the relationship between the measured electrical dipole moment and the oxygen density ratio at the high-k/SiO2 interface.

  2. Direct asymmetric vinylogous aldol reaction of allyl ketones with isatins: Divergent synthesis of 3-hydroxy-2-oxindole derivatives

    KAUST Repository

    Zhu, Bo

    2013-05-03

    6 in 1: The highly enantioselective title reaction is mediated by a bifunctional catalyst and leads to E-configured vinylogous aldol products (see scheme). These products are used as common intermediates in the synthesis of six biologically active 3-hydroxy-2-oxindole derivatives (e.g., CPC-1). Computational studies indicated that the observed stereoselectivity is a result of favorable secondary π-π* and H-bonding interactions in the transition state. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Oligopolistic Reaction and Foreign Direct Investment: The Case of the U.S. Tire and Textiles Industries

    OpenAIRE

    Chwo-Ming J Yu; Kiyohiko Ito

    1988-01-01

    This paper empirically tests the impact of oligopolistic reaction and some firm–related and host country–related factors on FDI activities in the U.S. tire and textile industries. The results reveal that in an oligopolistic industry, firms' motivation of FDI is based on the behavior of rivals as well as host country–related and firm–related factors, while in a more competitively structured industry, firms do not actively counter the competitors' FDI activities.© 1988 JIBS. Journal of Internat...

  4. Perspective: Spectroscopy and kinetics of small gaseous Criegee intermediates

    International Nuclear Information System (INIS)

    Lee, Yuan-Pern

    2015-01-01

    The Criegee intermediates, carbonyl oxides proposed by Criegee in 1949 as key intermediates in the ozonolysis of alkenes, play important roles in many aspects of atmospheric chemistry. Because direct detection of these gaseous intermediates was unavailable until recently, previous understanding of their reactions, derived from indirect experimental evidence, had great uncertainties. Recent laboratory detection of the simplest Criegee intermediate CH 2 OO and some larger members, produced from ultraviolet irradiation of corresponding diiodoalkanes in O 2 , with various methods such as photoionization, ultraviolet absorption, infrared absorption, and microwave spectroscopy opens a new door to improved understanding of the roles of these Criegee intermediates. Their structures and spectral parameters have been characterized; their significant zwitterionic nature is hence confirmed. CH 2 OO, along with other products, has also been detected directly with microwave spectroscopy in gaseous ozonolysis reactions of ethene. The detailed kinetics of the source reaction, CH 2 I + O 2 , which is critical to laboratory studies of CH 2 OO, are now understood satisfactorily. The kinetic investigations using direct detection identified some important atmospheric reactions, including reactions with NO 2 , SO 2 , water dimer, carboxylic acids, and carbonyl compounds. Efforts toward the characterization of larger Criegee intermediates and the investigation of related reactions are in progress. Some reactions of CH 3 CHOO are found to depend on conformation. This perspective examines progress toward the direct spectral characterization of Criegee intermediates and investigations of the associated reaction kinetics, and indicates some unresolved problems and prospective challenges for this exciting field of research

  5. Direct assessment of hepatic mitochondrial oxidative and anaplerotic fluxes in humans using dynamic 13C magnetic resonance spectroscopy

    DEFF Research Database (Denmark)

    Befroy, Douglas E; Perry, Rachel J; Jain, Nimit

    2014-01-01

    that rates of mitochondrial oxidation and anaplerosis in human liver can be directly determined noninvasively. Using this approach, we found the mean rates of hepatic tricarboxylic acid (TCA) cycle flux (VTCA) and anaplerotic flux (VANA) to be 0.43 ± 0.04 μmol g(-1) min(-1) and 0.60 ± 0.11 μmol g(-1) min(-1......), respectively, in twelve healthy, lean individuals. We also found the VANA/VTCA ratio to be 1.39 ± 0.22, which is severalfold lower than recently published estimates using an indirect approach. This method will be useful for understanding the pathogenesis of nonalcoholic fatty liver disease and type 2 diabetes...

  6. Direct Synthesis of 5-Aryl Barbituric Acids by Rhodium(II)-Catalyzed Reactions of Arenes with Diazo Compounds**

    Science.gov (United States)

    Best, Daniel; Burns, David J; Lam, Hon Wai

    2015-01-01

    A commercially available rhodium(II) complex catalyzes the direct arylation of 5-diazobarbituric acids with arenes, allowing straightforward access to 5-aryl barbituric acids. Free N—H groups are tolerated on the barbituric acid, with no complications arising from N—H insertion processes. This method was applied to the concise synthesis of a potent matrix metalloproteinase (MMP) inhibitor. PMID:25959544

  7. Construction of mussel-inspired coating via the direct reaction of catechol and polyethyleneimine for efficient heparin immobilization

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yujie [School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); The Institute of Biomaterials and Surface Engineering, Southwest Jiaotong University, Chengdu 610031 (China); Luo, Rifang, E-mail: lrifang@126.com [School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); The Institute of Biomaterials and Surface Engineering, Southwest Jiaotong University, Chengdu 610031 (China); Shen, Fangyu; Tang, Linlin [School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); The Institute of Biomaterials and Surface Engineering, Southwest Jiaotong University, Chengdu 610031 (China); Wang, Jin, E-mail: jinxxwang@263.net [School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); The Institute of Biomaterials and Surface Engineering, Southwest Jiaotong University, Chengdu 610031 (China); Huang, Nan [School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); The Institute of Biomaterials and Surface Engineering, Southwest Jiaotong University, Chengdu 610031 (China)

    2015-02-15

    Highlights: • Catechol (CA) and PEI copolymerization was a mimetic and dopamine-like coating method. • CA/PEI film provided amine groups and was effective in heparin immobilization. • CA/PEI coating could inhibit smooth muscle cell proliferation. • CA/PEI coating did not show any significant cytotoxicity to endothelial cell. - Abstract: Dopamine could self-polymerize to form the coating on various substrates and the co-existence of catechols and amines was crucial in performing such polymerization process. In this work, a mimetic approach of coating formation was carried out based on the co-polymerization of catechol (CA) and polyethyleneimine (PEI). Mussel-inspired CA/PEI coating was deposited on 316L stainless steel (SS). Fourier transform infrared spectra (FTIR) and X-ray photoelectron spectroscopy (XPS) demonstrated the successful coating formation. QCM measurement showed good affinity of heparin immobilization on CA/PEI coating surface ascribed to the amine groups. Herein, vascular cell-material interactions like endothelial cells (ECs) and smooth muscle cells (SMCs) were also investigated. Interestingly, CA/PEI and heparin modified coatings presented no cytotoxicity to ECs, however to a certain extent, decreased SMCs proliferation. Moreover, heparin-binding surface presented significant anti-platelet adhesion and activation properties. These results effectively suggested that the mussel-inspired CA/PEI coating might be promising when served as a platform for biomolecule immobilization.

  8. Direct RNA detection without nucleic acid purification and PCR: Combining sandwich hybridization with signal amplification based on branched hybridization chain reaction.

    Science.gov (United States)

    Xu, Yao; Zheng, Zhi

    2016-05-15

    We have developed a convenient, robust and low-cost RNA detection system suitable for high-throughput applications. This system uses a highly specific sandwich hybridization to capture target RNA directly onto solid support, followed by on-site signal amplification via 2-dimensional, branched hybridizing chain polymerization through toehold-mediated strand displacement reaction. The assay uses SYBR Green to detect targets at concentrations as low as 1 pM, without involving nucleic acid purification or any enzymatic reaction, using ordinary oligonucleotides without modification or labeling. The system was demonstrated in the detection of malaria RNA in blood and GAPDH gene expression in cell lysate. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Electroadsorption-assisted direct determination of trace arsenic without interference using transmission X-ray fluorescence spectroscopy.

    Science.gov (United States)

    Jiang, Tian-Jia; Guo, Zheng; Liu, Jin-Huai; Huang, Xing-Jiu

    2015-08-18

    An analytical technique based on electroadsorption and transmission X-ray fluorescence (XRF) for the quantitative determination of arsenic in aqueous solution with ppb-level limits of detection (LOD) is proposed. The approach uses electroadsorption to enhance the sensitivity and LOD of the arsenic XRF response. Amine-functionalized carbonaceous microspheres (NH2-CMSs) are found to be the ideal materials for both the quantitative adsorption of arsenic and XRF analysis due to the basic amine sites on the surface and their noninterference in the XRF spectrum. In electroadsorptive X-ray fluorescence (EA-XRF), arsenic is preconcentrated by a conventional three-electrode system with a positive electricity field around the adsorbents. Then, the quantification of arsenic on the adsorbents is achieved using XRF. The electroadsorption preconcentration can realize the fast transfer of arsenic from the solution to the adsorbents and improve the LOD of conventional XRF compared with directly determining arsenic solution by XRF alone. The sensitivity of 0.09 cnt ppb(-1) is obtained without the interferences from coexisted metal ions in the determination of arsenic, and the LOD is found to be 7 ppb, which is lower than the arsenic guideline value of 10 ppb given by the World Health Organization (WHO). These results demonstrated that XRF coupled with electroadsorption was able to determine trace arsenic in real water sample.

  10. Windowed direct exponential curve resolution quantification of nuclear magnetic resonance spectroscopy with applications to amniotic fluid metabonomics

    International Nuclear Information System (INIS)

    Botros, L.L.

    2007-01-01

    This thesis presents a quantitative protocol of proton nuclear magnetic resonance ( 1 H NMR) that allows the determination of human amniotic fluid metabolite concentrations, which are then used in a metabonomic study to establish patient health during gestation. 1 H NMR free inductive decays (FIDs) of 258 human amniotic fluid samples from a 500MHz spectrometer are acquired. Quantitative analyses methods in both the frequency- and time-domain are carried out and compared. Frequency-domain analysis is accomplished by integration of the metabolite peaks before and after the inclusion of a known standard addition of alanine. Time-domain analysis is accomplished by the direct exponential curve resolution algorithm (DECRA). Both techniques are assessed by applications to calibration biological solutions and a simulated data set. The DECRA method proves to be a more accurate and precise route for quantitative analysis, and is included in the developed protocol. Well-defined peaks of various components are visible in the frequency-domain 1 H NMR spectra, including lactate, alanine, acetate, citrate, choline, glycine, and glucose. All are quantified with the proposed protocol. Statistical t-test and notched box and whisker plots are used to compare means of metabolite concentrations for diabetic and normal patients. Glucose, glycine, and choline are all found to correlate with gestational diabetes mellitus early in gestation. With further development, time-domain quantitative 1 H NMR has potential to become a robust diagnostic tool for gestational health. (author)

  11. Windowed direct exponential curve resolution quantification of nuclear magnetic resonance spectroscopy with applications to amniotic fluid metabonomics

    Energy Technology Data Exchange (ETDEWEB)

    Botros, L.L

    2007-07-01

    This thesis presents a quantitative protocol of proton nuclear magnetic resonance ({sup 1}H NMR) that allows the determination of human amniotic fluid metabolite concentrations, which are then used in a metabonomic study to establish patient health during gestation. {sup 1}H NMR free inductive decays (FIDs) of 258 human amniotic fluid samples from a 500MHz spectrometer are acquired. Quantitative analyses methods in both the frequency- and time-domain are carried out and compared. Frequency-domain analysis is accomplished by integration of the metabolite peaks before and after the inclusion of a known standard addition of alanine. Time-domain analysis is accomplished by the direct exponential curve resolution algorithm (DECRA). Both techniques are assessed by applications to calibration biological solutions and a simulated data set. The DECRA method proves to be a more accurate and precise route for quantitative analysis, and is included in the developed protocol. Well-defined peaks of various components are visible in the frequency-domain {sup 1}H NMR spectra, including lactate, alanine, acetate, citrate, choline, glycine, and glucose. All are quantified with the proposed protocol. Statistical t-test and notched box and whisker plots are used to compare means of metabolite concentrations for diabetic and normal patients. Glucose, glycine, and choline are all found to correlate with gestational diabetes mellitus early in gestation. With further development, time-domain quantitative {sup 1}H NMR has potential to become a robust diagnostic tool for gestational health. (author)

  12. Lesion-induced DNA weak structural changes detected by pulsed EPR spectroscopy combined with site-directed spin labelling.

    Science.gov (United States)

    Sicoli, Giuseppe; Mathis, Gérald; Aci-Sèche, Samia; Saint-Pierre, Christine; Boulard, Yves; Gasparutto, Didier; Gambarelli, Serge

    2009-06-01

    Double electron-electron resonance (DEER) was applied to determine nanometre spin-spin distances on DNA duplexes that contain selected structural alterations. The present approach to evaluate the structural features of DNA damages is thus related to the interspin distance changes, as well as to the flexibility of the overall structure deduced from the distance distribution. A set of site-directed nitroxide-labelled double-stranded DNA fragments containing defined lesions, namely an 8-oxoguanine, an abasic site or abasic site analogues, a nick, a gap and a bulge structure were prepared and then analysed by the DEER spectroscopic technique. New insights into the application of 4-pulse DEER sequence are also provided, in particular with respect to the spin probes' positions and the rigidity of selected systems. The lesion-induced conformational changes observed, which were supported by molecular dynamics studies, confirm the results obtained by other, more conventional, spectroscopic techniques. Thus, the experimental approaches described herein provide an efficient method for probing lesion-induced structural changes of nucleic acids.

  13. Direct visualization of exciton reequilibration in the LH1 and LH2 complexes of Rhodobacter sphaeroides by multipulse spectroscopy.

    Science.gov (United States)

    Cohen Stuart, Thomas A; Vengris, Mikas; Novoderezhkin, Vladimir I; Cogdell, Richard J; Hunter, C Neil; van Grondelle, Rienk

    2011-05-04

    The dynamics of the excited states of the light-harvesting complexes LH1 and LH2 of Rhodobacter sphaeroides are governed, mainly, by the excitonic nature of these ring-systems. In a pump-dump-probe experiment, the first pulse promotes LH1 or LH2 to its excited state and the second pulse dumps a portion of the excited state. By selective dumping, we can disentangle the dynamics normally hidden in the excited-state manifold. We find that by using this multiple-excitation technique we can visualize a 400-fs reequilibration reflecting relaxation between the two lowest exciton states that cannot be directly explored by conventional pump-probe. An oscillatory feature is observed within the exciton reequilibration, which is attributed to a coherent motion of a vibrational wavepacket with a period of ∼150 fs. Our disordered exciton model allows a quantitative interpretation of the observed reequilibration processes occurring in these antennas. Copyright © 2011 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  14. Monte Carlo FLUKA code simulation for study of {sup 68}Ga production by direct proton-induced reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mokhtari Oranj, Leila; Kakavand, Tayeb [Physics Faculty, Zanjan University, P.O. Box 451-313, Zanjan (Iran, Islamic Republic of); Sadeghi, Mahdi, E-mail: msadeghi@nrcam.org [Agricultural, Medical and Industrial Research School, Nuclear Science and Technology Research Institute, P.O. Box 31485-498, Karaj (Iran, Islamic Republic of); Aboudzadeh Rovias, Mohammadreza [Agricultural, Medical and Industrial Research School, Nuclear Science and Technology Research Institute, P.O. Box 31485-498, Karaj (Iran, Islamic Republic of)

    2012-06-11

    {sup 68}Ga is an important radionuclide for positron emission tomography. {sup 68}Ga can be produced by the {sup 68}Zn(p,n){sup 68}Ga reaction in a common biomedical cyclotrons. To facilitate optimization of target design and study activation of materials, Monte Carlo code can be used to simulate the irradiation of the target materials with charged hadrons. In this paper, FLUKA code simulation was employed to prototype a Zn target for the production of {sup 68}Ga by proton irradiation. Furthermore, the experimental data were compared with the estimated values for the thick target yield produced in the irradiation time according to FLUKA code. In conclusion, FLUKA code can be used for estimation of the production yield.

  15. Direct measurements of the total rate constant of the reaction NCN + H and implications for the product branching ratio and the enthalpy of formation of NCN.

    Science.gov (United States)

    Fassheber, Nancy; Dammeier, Johannes; Friedrichs, Gernot

    2014-06-21

    The overall rate constant of the reaction (2), NCN + H, which plays a key role in prompt-NO formation in flames, has been directly measured at temperatures 962 K rate constants are best represented by the combination of two Arrhenius expressions, k2/(cm(3) mol(-1) s(-1)) = 3.49 × 10(14) exp(-33.3 kJ mol(-1)/RT) + 1.07 × 10(13) exp(+10.0 kJ mol(-1)/RT), with a small uncertainty of ±20% at T = 1600 K and ±30% at the upper and lower experimental temperature limits.The two Arrhenius terms basically can be attributed to the contributions of reaction channel (2a) yielding CH + N2 and channel (2b) yielding HCN + N as the products. A more refined analysis taking into account experimental and theoretical literature data provided a consistent rate constant set for k2a, its reverse reaction k1a (CH + N2 → NCN + H), k2b as well as a value for the controversial enthalpy of formation of NCN, ΔfH = 450 kJ mol(-1). The analysis verifies the expected strong temperature dependence of the branching fraction ϕ = k2b/k2 with reaction channel (2b) dominating at the experimental high-temperature limit. In contrast, reaction (2a) dominates at the low-temperature limit with a possible minor contribution of the HNCN forming recombination channel (2d) at T < 1150 K.

  16. Degradation mechanism of Direct Pink 12B treated by iron-carbon micro-electrolysis and Fenton reaction.

    Science.gov (United States)

    Wang, Xiquan; Gong, Xiaokang; Zhang, Qiuxia; Du, Haijuan

    2013-12-01

    The Direct Pink 12B dye was treated by iron-carbon micro-electrolysis (ICME) and Fenton oxidation. The degradation pathway of Direct Pink 12B dye was inferred by ultraviolet visible (UV-Vis), infrared absorption spectrum (IR) and high performance liquid chromatography-mass spectrometry (HPLC-MS). The major reason of decolorization was that the conjugate structure was disrupted in the iron-carbon micro-electrolysis (ICME) process. However, the dye was not degraded completely because benzene rings and naphthalene rings were not broken. In the Fenton oxidation process, the azo bond groups surrounded by higher electron cloud density were first attacked by hydroxyl radicals to decolorize the dye molecule. Finally benzene rings and naphthalene rings were mineralized to H2O and CO2 under the oxidation of hydroxyl radicals. Copyright © 2013 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

  17. Probing the influence of the center atom coordination structure in iron phthalocyanine multi-walled carbon nanotube-based oxygen reduction reaction catalysts by X-ray absorption fine structure spectroscopy

    Science.gov (United States)

    Peng, Yingxiang; Li, Zhipan; Xia, Dingguo; Zheng, Lirong; Liao, Yi; Li, Kai; Zuo, Xia

    2015-09-01

    Three different pentacoordinate iron phthalocyanine (FePc) electrocatalysts with an axial ligand (pyridyl group, Py) anchored to multi-walled carbon nanotubes (MWCNTs) are prepared by a microwave method as high performance composite electrocatalysts (FePc-Py/MWCNTs) for the oxygen reduction reaction (ORR). For comparison, tetracoordinate FePc electrocatalysts without an axial ligand anchored to MWCNTs (FePc/MWCNTs) are assembled in the same way. Ultraviolet-visible spectrophotometry (UV-Vis), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HRTEM) are used to characterize the obtained electrocatalysts. The electrocatalytic activity of the samples is measured by linear sweep voltammetry (LSV), and the onset potential of all of the FePc-Py/MWCNTs electrocatalysts is found to be more positive than that of their FePc/MWCNTs counterparts. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy are employed to elucidate the relationship between molecular structure and electrocatalytic activity. XPS indicates that higher concentrations of Fe3+ and pyridine-type nitrogen play critical roles in determining the electrocatalytic ORR activity of the samples. XAFS spectroscopy reveals that the FePc-Py/MWCNTs electrocatalysts have a coordination geometry around Fe that is closer to the square pyramidal structure, a higher concentration of Fe3+, and a smaller phthalocyanine ring radius compared with those of FePc/MWCNTs.

  18. Direct band gap measurement of Cu(In,Ga)(Se,S)2 thin films using high-resolution reflection electron energy loss spectroscopy

    International Nuclear Information System (INIS)

    Heo, Sung; Lee, Hyung-Ik; Park, Jong-Bong; Ko, Dong-Su; Chung, JaeGwan; Kim, KiHong; Kim, Seong Heon; Yun, Dong-Jin; Ham, YongNam; Park, Gyeong Su; Song, Taewon; Lee, Dongho; Nam, Junggyu; Kang, Hee Jae; Choi, Pyung-Ho; Choi, Byoung-Deog

    2015-01-01

    To investigate the band gap profile of Cu(In 1−x ,Ga x )(Se 1−y S y ) 2 of various compositions, we measured the band gap profile directly as a function of in-depth using high-resolution reflection energy loss spectroscopy (HR-REELS), which was compared with the band gap profile calculated based on the auger depth profile. The band gap profile is a double-graded band gap as a function of in-depth. The calculated band gap obtained from the auger depth profile seems to be larger than that by HR-REELS. Calculated band gaps are to measure the average band gap of the spatially different varying compositions with respect to considering its void fraction. But, the results obtained using HR-REELS are to be affected by the low band gap (i.e., out of void) rather than large one (i.e., near void). Our findings suggest an analytical method to directly determine the band gap profile as function of in-depth

  19. Simultaneous determination of glucose, triglycerides, urea, cholesterol, albumin and total protein in human plasma by Fourier transform infrared spectroscopy: direct clinical biochemistry without reagents.

    Science.gov (United States)

    Jessen, Torben E; Höskuldsson, Agnar T; Bjerrum, Poul J; Verder, Henrik; Sørensen, Lars; Bratholm, Palle S; Christensen, Bo; Jensen, Lene S; Jensen, Maria A B

    2014-09-01

    Direct measurement of chemical constituents in complex biologic matrices without the use of analyte specific reagents could be a step forward toward the simplification of clinical biochemistry. Problems related to reagents such as production errors, improper handling, and lot-to-lot variations would be eliminated as well as errors occurring during assay execution. We describe and validate a reagent free method for direct measurement of six analytes in human plasma based on Fourier-transform infrared spectroscopy (FTIR). Blood plasma is analyzed without any sample preparation. FTIR spectrum of the raw plasma is recorded in a sampling cuvette specially designed for measurement of aqueous solutions. For each analyte, a mathematical calibration process is performed by a stepwise selection of wavelengths giving the optimal least-squares correlation between the measured FTIR signal and the analyte concentration measured by conventional clinical reference methods. The developed calibration algorithms are subsequently evaluated for their capability to predict the concentration of the six analytes in blinded patient samples. The correlation between the six FTIR methods and corresponding reference methods were 0.87albumin and total protein in human plasma. Copyright © 2014 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

  20. Direct band gap measurement of Cu(In,Ga)(Se,S){sub 2} thin films using high-resolution reflection electron energy loss spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Heo, Sung [Analytical Engineering Group, Samsung Advanced Institute of Technology, 130 Samsung-ro, Yeongtong-gu, Suwon-si, Gyeonggi-do 443-803 (Korea, Republic of); College of Information and Communication Engineering, Sungkyunkwan University, Cheoncheon-dong 300, Jangan-gu, Suwon 440-746 (Korea, Republic of); Lee, Hyung-Ik; Park, Jong-Bong; Ko, Dong-Su; Chung, JaeGwan; Kim, KiHong; Kim, Seong Heon; Yun, Dong-Jin; Ham, YongNam; Park, Gyeong Su [Analytical Engineering Group, Samsung Advanced Institute of Technology, 130 Samsung-ro, Yeongtong-gu, Suwon-si, Gyeonggi-do 443-803 (Korea, Republic of); Song, Taewon [Energy lab, Samsung Advanced Institute of Technology, 130 Samsung-ro, Yeongtong-gu, Suwon-si, Gyeonggi-do 443-803 (Korea, Republic of); Lee, Dongho, E-mail: dhlee0333@gmail.com; Nam, Junggyu [PV Development Team, Energy Solution Business Division, Samsung SDI, 467 Beonyeong-ro, Cheonan-si, Chungcheongnam-do 331-330 (Korea, Republic of); Kang, Hee Jae [Department of Physics, Chungbuk National University, Gaesin-dong, Heungdeok-gu, Cheongju, 361-763 (Korea, Republic of); Choi, Pyung-Ho; Choi, Byoung-Deog, E-mail: bdchoi@skku.edu [College of Information and Communication Engineering, Sungkyunkwan University, Cheoncheon-dong 300, Jangan-gu, Suwon 440-746 (Korea, Republic of)

    2015-06-29

    To investigate the band gap profile of Cu(In{sub 1−x},Ga{sub x})(Se{sub 1−y}S{sub y}){sub 2} of various compositions, we measured the band gap profile directly as a function of in-depth using high-resolution reflection energy loss spectroscopy (HR-REELS), which was compared with the band gap profile calculated based on the auger depth profile. The band gap profile is a double-graded band gap as a function of in-depth. The calculated band gap obtained from the auger depth profile seems to be larger than that by HR-REELS. Calculated band gaps are to measure the average band gap of the spatially different varying compositions with respect to considering its void fraction. But, the results obtained using HR-REELS are to be affected by the low band gap (i.e., out of void) rather than large one (i.e., near void). Our findings suggest an analytical method to directly determine the band gap profile as function of in-depth.

  1. Direct measurements of OH and other product yields from the HO2  + CH3C(OO2 reaction

    Directory of Open Access Journals (Sweden)

    F. A. F. Winiberg

    2016-03-01

    Full Text Available The reaction CH3C(OO2 + HO2  →  CH3C(OOOH + O2 (Reaction R5a, CH3C(OOH + O3 (Reaction R5b, CH3 + CO2 + OH + O2 (Reaction R5c was studied in a series of experiments conducted at 1000 mbar and (293 ± 2 K in the HIRAC simulation chamber. For the first time, products, (CH3C(OOOH, CH3C(OOH, O3 and OH from all three branching pathways of the reaction have been detected directly and simultaneously. Measurements of radical precursors (CH3OH, CH3CHO, HO2 and some secondary products HCHO and HCOOH further constrained the system. Fitting a comprehensive model to the experimental data, obtained over a range of conditions, determined the branching ratios α(R5a  =  0.37 ± 0.10, α(R5b =  0.12 ± 0.04 and α(R5c =  0.51 ± 0.12 (errors at 2σ level. Improved measurement/model agreement was achieved using k(R5  =  (2.4 ± 0.4  ×  10−11 cm3 molecule−1 s−1, which is within the large uncertainty of the current IUPAC and JPL recommended rate coefficients for the title reaction. The rate coefficient and branching ratios are in good agreement with a recent study performed by Groß et al. (2014b; taken together, these two studies show that the rate of OH regeneration through Reaction (R5 is more rapid than previously thought. GEOS-Chem has been used to assess the implications of the revised rate coefficients and branching ratios; the modelling shows an enhancement of up to 5 % in OH concentrations in tropical rainforest areas and increases of up to 10 % at altitudes of 6–8 km above the equator, compared to calculations based on the IUPAC recommended rate coefficient and yield. The enhanced rate of acetylperoxy consumption significantly reduces PAN in remote regions (up to 30 % with commensurate reductions in background NOx.

  2. Monitoring of an esterification reaction by on-line direct liquid sampling mass spectrometry and in-line mid infrared spectrometry with an attenuated total reflectance probe

    International Nuclear Information System (INIS)

    Owen, Andrew W.; McAulay, Edith A.J.; Nordon, Alison; Littlejohn, David; Lynch, Thomas P.; Lancaster, J. Steven; Wright, Robert G.

    2014-01-01

    Highlights: • High efficiency thermal vaporiser designed and used for on-line reaction monitoring. • Concentration profiles of all reactants and products obtained from mass spectra. • By-product formed from the presence of an impurity detected by MS but not MIR. • Mass spectrometry can detect trace and bulk components unlike molecular spectrometry. - Abstract: A specially designed thermal vaporiser was used with a process mass spectrometer designed for gas analysis to monitor the esterification of butan-1-ol and acetic anhydride. The reaction was conducted at two scales: in a 150 mL flask and a 1 L jacketed batch reactor, with liquid delivery flow rates to the vaporiser of 0.1 and 1.0 mL min −1 , respectively. Mass spectrometry measurements were made at selected ion masses, and classical least squares multivariate linear regression was used to produce concentration profiles for the reactants, products and catalyst. The extent of reaction was obtained from the butyl acetate profile and found to be 83% and 76% at 40 °C and 20 °C, respectively, at the 1 L scale. Reactions in the 1 L reactor were also monitored by in-line mid-infrared (MIR) spectrometry; off-line gas chromatography (GC) was used as a reference technique when building partial least squares (PLS) multivariate calibration models for prediction of butyl acetate concentrations from the MIR spectra. In validation experiments, good agreement was achieved between the concentration of butyl acetate obtained from in-line MIR spectra and off-line GC. In the initial few minutes of the reaction the profiles for butyl acetate derived from on-line direct liquid sampling mass spectrometry (DLSMS) differed from those of in-line MIR spectrometry owing to the 2 min transfer time between the reactor and mass spectrometer. As the reaction proceeded, however, the difference between the concentration profiles became less noticeable. DLSMS had advantages over in-line MIR spectrometry as it was easier to generate

  3. Use of the polymerase chain reaction to directly detect malaria parasites in blood samples from the Venezuelan Amazon.

    Science.gov (United States)

    Laserson, K F; Petralanda, I; Hamlin, D M; Almera, R; Fuentes, M; Carrasquel, A; Barker, R H

    1994-02-01

    We have examined the reproducibility, sensitivity, and specificity of detecting Plasmodium falciparum using the polymerase chain reaction (PCR) and the species-specific probe pPF14 under field conditions in the Venezuelan Amazon. Up to eight samples were field collected from each of 48 consenting Amerindians presenting with symptoms of malaria. Sample processing and analysis was performed at the Centro Amazonico para la Investigacion y Control de Enfermedades Tropicales Simon Bolivar. A total of 229 samples from 48 patients were analyzed by PCR methods using four different P. falciparum-specific probes. One P. vivax-specific probe and by conventional microscopy. Samples in which results from PCR and microscopy differed were reanalyzed at a higher sensitivity by microscopy. Results suggest that microscopy-negative, PCR-positive samples are true positives, and that microscopy-positive and PCR-negative samples are true negatives. The sensitivity of the DNA probe/PCR method was 78% and its specificity was 97%. The positive predictive value of the PCR method was 88%, and the negative predictive value was 95%. Through the analysis of multiple blood samples from each individual, the DNA probe/PCR methodology was found to have an inherent reproducibility that was highly statistically significant.

  4. Investigation of a Pt-Fe/C catalyst for oxygen reduction reaction in direct ethanol fuel cells

    International Nuclear Information System (INIS)

    Castro Luna, A. M.; Bonesi, A.; Triaca, W. E.; Blasi, A. Di; Stassi, A.; Baglio, V.; Antonucci, V.; Arico, A. S.

    2010-01-01

    Three cathode catalysts (60% Pt/C, 30% Pt/C and 60% Pt-Fe/C), with a particle size of about 2-3 nm, were prepared to investigate the effect of ethanol cross-over on cathode surfaces. All samples were studied in terms of structure and morphology by using X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. Their electrocatalytic behavior in terms of oxygen reduction reaction (ORR) was investigated and compared using a rotating disk electrode (RDE). The tolerance of cathode catalysts in the presence of ethanol was evaluated. The Pt-Fe/C catalyst showed both higher ORR activity and tolerance to ethanol cross-over than Pt/C catalysts. Moreover, the more promising catalysts were tested in 5 cm 2 DEFC single cells at 60 and 80 o C. An improvement in single cell performance was observed in the presence of the Pt-Fe catalyst, due to an enhancement in the oxygen reduction kinetics. The maximum power density was 53 mW cm -2 at 2 bar rel. cathode pressure and 80 o C.

  5. Direct Synthesis of 5-Aryl Barbituric Acids by Rhodium(II)-Catalyzed Reactions of Arenes with Diazo Compounds.

    Science.gov (United States)

    Best, Daniel; Burns, David J; Lam, Hon Wai

    2015-06-15

    A commercially available rhodium(II) complex catalyzes the direct arylation of 5-diazobarbituric acids with arenes, allowing straightforward access to 5-aryl barbituric acids. Free N-H groups are tolerated on the barbituric acid, with no complications arising from N-H insertion processes. This method was applied to the concise synthesis of a potent matrix metalloproteinase (MMP) inhibitor. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  6. Modified two-body potential approach to the peripheral direct capture astrophysical a+A->B+γ reaction and asymptotic normalization coefficients

    International Nuclear Information System (INIS)

    Igamov, S.B.; Yarmukhamedov, R.

    2007-01-01

    A modified two-body potential approach is proposed for determination of both the asymptotic normalization coefficient (ANC) (or the respective nuclear vertex constant (NVC)) for the A+a->B (for the virtual decay B->A+a) from an analysis of the experimental S-factor for the peripheral direct capture a+A->B+γ reaction and the astrophysical S-factor, S(E), at low experimentally inaccessible energy regions. The approach proposed involves two additional conditions which verify the peripheral character of the considered reaction and expresses S(E) in terms of the ANC. The connection between NVC (ANC) and the effective range parameters for Aa-scattering is derived. To test this approach we reanalyse the precise experimental astrophysical S-factors for t+α->Li7+γ reaction at energies E= Li7(g.s.), α+t->Li7(0.478 MeV) and of S(E) at E=<50 keV. These ANC values have been used for getting information about the ''indirect'' measured values of the effective range parameters and the p-wave phase shift for αt-scattering in the energy range of 100-bar E-bar 180 keV

  7. Direct detection of OH formation in the reactions of HO2 with CH3C(OO2 and other substituted peroxy radicals

    Directory of Open Access Journals (Sweden)

    J. N. Crowley

    2008-08-01

    Full Text Available This work details the first direct observation of OH as a product from (R1: HO2+CH3C(OO2→(products, which has generally been considered an atmospheric radical termination process. The technique of pulsed laser photolysis radical generation, coupled to calibrated laser induced fluorescence detection was used to measure an OH product yield for (R1 of α1(298 K=(0.5±0.2. This study of (R1 included the measurement of a rate coefficient k1(298 K=(1.4±0.5×10−11cm3 molecule−1 s−1, substantially reducing the uncertainties in modelling this important atmospheric reaction. OH was also detected as a product from the reactions of HO2 with three other carbonyl-containing peroxy radicals, albeit at smaller yield, e.g. (R2: HO2+CH3C(OCH2O2→(products, α2≈0.15. By contrast, OH was not observed (α<0.06 as a major product from reactions where carbonyl functionality was absent, e.g. HO2+HOCH2CH2O2 (R8, and HO2+CH3CH(OHCH2O2 (R9.

  8. Study of the direct electron production in the reaction π-p at 70 GeV/c

    International Nuclear Information System (INIS)

    Hennion, P.

    1980-06-01

    This experiment tries to answer the following questions. What is the dependence with the transverse impulsion psub(T) of the production rate l/π. Are the direct leptons produced alone or by pairs. If they are produced alone, are they issued from a charm particle. Are there lepton pairs whose origin is not understood. This experiment is a collaboration between Bologne, Glasgow, Rutherford, Saclay and Turin laboratories. Data are from the CERN bubble chamber, equipped with a sensitive target. This equipment is described in the chapter one, together with experimental process. In chapter two, results on single electron production are given. Pairs production is studied in chapter three. Pairs issuing from the π zero decay in e + , e - and gamma are also analyzed [fr

  9. Directed evolution and in silico analysis of reaction centre proteins reveal molecular signatures of photosynthesis adaptation to radiation pressure.

    Directory of Open Access Journals (Sweden)

    Giuseppina Rea

    2011-01-01

    Full Text Available Evolutionary mechanisms adopted by the photosynthetic apparatus to modifications in the Earth's atmosphere on a geological time-scale remain a focus of intense research. The photosynthetic machinery has had to cope with continuously changing environmental conditions and particularly with the complex ionizing radiation emitted by solar flares. The photosynthetic D1 protein, being the site of electron tunneling-mediated charge separation and solar energy transduction, is a hot spot for the generation of radiation-induced radical injuries. We explored the possibility to produce D1 variants tolerant to ionizing radiation in Chlamydomonas reinhardtii and clarified the effect of radiation-induced oxidative damage on the photosynthetic proteins evolution. In vitro directed evolution strategies targeted at the D1 protein were adopted to create libraries of chlamydomonas random mutants, subsequently selected by exposures to radical-generating proton or neutron sources. The common trend observed in the D1 aminoacidic substitutions was the replacement of less polar by more polar amino acids. The applied selection pressure forced replacement of residues more sensitive to oxidative damage with less sensitive ones, suggesting that ionizing radiation may have been one of the driving forces in the evolution of the eukaryotic photosynthetic apparatus. A set of the identified aminoacidic substitutions, close to the secondary plastoquinone binding niche and oxygen evolving complex, were introduced by site-directed mutagenesis in un-transformed strains, and their sensitivity to free radicals attack analyzed. Mutants displayed reduced electron transport efficiency in physiological conditions, and increased photosynthetic performance stability and oxygen evolution capacity in stressful high-light conditions. Finally, comparative in silico analyses of D1 aminoacidic sequences of organisms differently located in the evolution chain, revealed a higher ratio of residues

  10. Direct Detection of a Chemical Equilibrium between a Localized Singlet Diradical and Its σ-Bonded Species by Time-Resolved UV/Vis and IR Spectroscopy.

    Science.gov (United States)

    Yoshidomi, Shohei; Mishima, Megumi; Seyama, Shin; Abe, Manabu; Fujiwara, Yoshihisa; Ishibashi, Taka-Aki

    2017-03-06

    Localized singlet diradicals are key intermediates in bond homolyses. The singlet diradicals are energetically much less stable than the σ-bonded species. In general, only one-way reactions from diradicals to σ-bonded species are observed. In this study, a thermal equilibrium between a singlet 1,2-diazacyclopentane-3,5-diyl diradical and the corresponding σ-bonded species was directly observed. The singlet diradical was more stable than the σ-bonded species. The solvent effect clarified key features, such as the zwitterionic character of the singlet diradical. The effect of the nitrogen atoms is discussed in detail. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy

    KAUST Repository

    Michalak, William D.; Krier, James M.; Komvopoulos, Kyriakos; Somorjai, Gabor A.

    2013-01-01

    hydrogenation and the nanoparticle size affects the kinetic preference for the two pathways. The reaction pathway through the metallocycle intermediate on the small nanoparticles is likely due to the presence of low-coordinated sites. © 2012 American Chemical

  12. Site-specific growth of Au-Pd alloy horns on Au nanorods: A platform for highly sensitive monitoring of catalytic reactions by surface enhancement raman spectroscopy

    KAUST Repository

    Huang, Jianfeng; Zhu, Yihan; Lin, Ming; Wang, Qingxiao; Zhao, Lan; Yang, Yang; Yao, Kexin; Han, Yu

    2013-01-01

    Surface-enhanced Raman scattering (SERS) is a highly sensitive probe for molecular detection. The aim of this study was to develop an efficient platform for investigating the kinetics of catalytic reactions with SERS. To achieve this, we synthesized

  13. The role of direct parameter specification and attentional capture in near-threshold priming of motor reactions

    Directory of Open Access Journals (Sweden)

    Rob H. J. van der Lubbe

    2006-01-01

    Full Text Available The priming of motor responses can be induced by preceding visual stimuli that have been made invisible by metacontrast masking ('primes'. According to the concept of direct parameter specification (DPS;Neumann,1990, strong similarity between prime and target results in the processing operations that are to be applied to the target being also induced by the prime. As targets have to be attended to, this also implies that attention is captured by the location of a prime, thereby facilitating motor priming effects. This hypothetical effect may be viewed as a form of top-down attentional capture. In some subliminal priming experiments (e.g. Jaśkowski, Skalska, & Verleger, 2003, however, attentional capture may have been unrelated to target identity, as stimuli with unique features (singletons are known to induce bottom-up attentional capture. Three experiments were performed that largely confirmed the view that the result sof these earlier experiments were due to top-down attentional capture, in line with DPS. However, the priming effect was also evoked by a singleton irrelevant to the participants' task, although this effect was weaker than in case of strong similarity between prime and target. Priming effects remained when singletons were absent from one side of the visual field,suggesting that the presence of singletons is not a requirement for the observation of motor priming effects.

  14. [Study on the method for the determination of trace boron, molybdenum, silver, tin and lead in geochemical samples by direct current arc full spectrum direct reading atomic emission spectroscopy (DC-Arc-AES)].

    Science.gov (United States)

    Hao, Zhi-hong; Yao, Jian-zhen; Tang, Rui-ling; Zhang, Xue-mei; Li, Wen-ge; Zhang, Qin

    2015-02-01

    The method for the determmation of trace boron, molybdenum, silver, tin and lead in geochemical samples by direct current are full spectrum direct reading atomic emission spectroscopy (DC-Arc-AES) was established. Direct current are full spectrum direct reading atomic emission spectrometer with a large area of solid-state detectors has functions of full spectrum direct reading and real-time background correction. The new electrodes and new buffer recipe were proposed in this paper, and have applied for national patent. Suitable analytical line pairs, back ground correcting points of elements and the internal standard method were selected, and Ge was used as internal standard. Multistage currents were selected in the research on current program, and each current set different holding time to ensure that each element has a good signal to noise ratio. Continuous rising current mode selected can effectively eliminate the splash of the sample. Argon as shielding gas can eliminate CN band generating and reduce spectral background, also plays a role in stabilizing the are, and argon flow 3.5 L x min(-1) was selected. Evaporation curve of each element was made, and it was concluded that the evaporation behavior of each element is consistent, and combined with the effects of different spectrographic times on the intensity and background, the spectrographic time of 35s was selected. In this paper, national standards substances were selected as a standard series, and the standard series includes different nature and different content of standard substances which meet the determination of trace boron, molybdenum, silver, tin and lead in geochemical samples. In the optimum experimental conditions, the detection limits for B, Mo, Ag, Sn and Pb are 1.1, 0.09, 0.01, 0.41, and 0.56 microg x g(-1) respectively, and the precisions (RSD, n=12) for B, Mo, Ag, Sn and Pb are 4.57%-7.63%, 5.14%-7.75%, 5.48%-12.30%, 3.97%-10.46%, and 4.26%-9.21% respectively. The analytical accuracy was

  15. Use of functional near-infrared spectroscopy to evaluate the effects of anodal transcranial direct current stimulation on brain connectivity in motor-related cortex

    Science.gov (United States)

    Yan, Jiaqing; Wei, Yun; Wang, Yinghua; Xu, Gang; Li, Zheng; Li, Xiaoli

    2015-04-01

    Transcranial direct current stimulation (tDCS) is a noninvasive, safe and convenient neuro-modulatory technique in neurological rehabilitation, treatment, and other aspects of brain disorders. However, evaluating the effects of tDCS is still difficult. We aimed to evaluate the effects of tDCS using hemodynamic changes using functional near-infrared spectroscopy (fNIRS). Five healthy participants were employed and anodal tDCS was applied to the left motor-related cortex, with cathodes positioned on the right dorsolateral supraorbital area. fNIRS data were collected from the right motor-related area at the same time. Functional connectivity (FC) between intracortical regions was calculated between fNIRS channels using a minimum variance distortion-less response magnitude squared coherence (MVDR-MSC) method. The levels of Oxy-HbO change and the FC between channels during the prestimulation, stimulation, and poststimulation stages were compared. Results showed no significant level difference, but the FC measured by MVDR-MSC significantly decreased during tDCS compared with pre-tDCS and post-tDCS, although the FC difference between pre-tDCS and post-tDCS was not significant. We conclude that coherence calculated from resting state fNIRS may be a useful tool for evaluating the effects of anodal tDCS and optimizing parameters for tDCS application.

  16. Comparison of near-infrared and Raman spectroscopy for on-line monitoring of etchant solutions directly through a Teflon tube

    International Nuclear Information System (INIS)

    Kim, Jaejin; Hwang, Jinyoung; Chung, Hoeil

    2008-01-01

    Both near-infrared (NIR) and Raman spectroscopy have been studied for the quantitative measurement of components (H 3 PO 4 , HNO 3 , and CH 3 COOH) in an etchant solution and the corresponding prediction robustness has been evaluated. Both measurements were accomplished by illuminating radiation directly through a Teflon tube. Raman spectral features of each component were much clearer and more selective than those observed in the NIR spectrum. Especially, NIR spectral variation pertinent to H 3 PO 4 and HNO 3 were mostly based on the displacement and perturbation of water bands rather than due solely to NIR absorption. Therefore, the resulting spectral variations were not highly specific. When the validation set contained minor spectral variations resulting from a slight instrumental change, NIR prediction performance for all three components degraded substantially by showing obvious prediction bias. However, the accuracies of Raman predictions were maintained. Since partial least squares (PLS) models for each component were built using NIR spectra of poor specificity with broadly overlapping features, even minor spectral differences introduced by instrumental variations sensitively influenced the prediction performance of the NIR models. Overall, the selectivity (specificity) of a targeting spectroscopic method should be considered critically to secure prediction robustness for monitoring components in an etchant solution

  17. Direct and simultaneous quantification of tannin mean degree of polymerization and percentage of galloylation in grape seeds using diffuse reflectance fourier transform-infrared spectroscopy.

    Science.gov (United States)

    Pappas, Christos; Kyraleou, Maria; Voskidi, Eleni; Kotseridis, Yorgos; Taranilis, Petros A; Kallithraka, Stamatina

    2015-02-01

    The direct and simultaneous quantitative determination of the mean degree of polymerization (mDP) and the degree of galloylation (%G) in grape seeds were quantified using diffuse reflectance infrared Fourier transform spectroscopy and partial least squares (PLS). The results were compared with those obtained using the conventional analysis employing phloroglucinolysis as pretreatment followed by high performance liquid chromatography-UV and mass spectrometry detection. Infrared spectra were recorded in solid state samples after freeze drying. The 2nd derivative of the 1832 to 1416 and 918 to 739 cm(-1) spectral regions for the quantification of mDP, the 2nd derivative of the 1813 to 607 cm(-1) spectral region for the degree of %G determination and PLS regression were used. The determination coefficients (R(2) ) of mDP and %G were 0.99 and 0.98, respectively. The corresponding values of the root-mean-square error of calibration were found 0.506 and 0.692, the root-mean-square error of cross validation 0.811 and 0.921, and the root-mean-square error of prediction 0.612 and 0.801. The proposed method in comparison with the conventional method is simpler, less time consuming, more economical, and requires reduced quantities of chemical reagents and fewer sample pretreatment steps. It could be a starting point for the design of more specific models according to the requirements of the wineries. © 2015 Institute of Food Technologists®

  18. Wearable functional Near Infrared Spectroscopy (fNIRS and transcranial Direct Current Stimulation (tDCS: Expanding Vistas for Neurocognitive Augmentation

    Directory of Open Access Journals (Sweden)

    Ryan eMcKendrick

    2015-03-01

    Full Text Available Contemporary studies with transcranial direct current stimulation (tDCS provide a growing base of evidence for enhancing cognition through the non-invasive delivery of weak electric currents to the brain. The main effect of tDCS is to modulate cortical excitability depending on the polarity of the applied current. However, the underlying mechanism of neuromodulation is not well understood. A new generation of functional near infrared spectroscopy (fNIRS systems is described that are miniaturized, portable, and include wearable sensors. These developments provide an opportunity to couple fNIRS with tDCS, consistent with a neuroergonomics approach for joint neuroimaging and neurostimulation investigations of cognition in complex tasks and in naturalistic conditions. The effects of tDCS on complex task performance and the use of fNIRS for monitoring cognitive workload during task performance are described. Also explained is how fNIRS + tDCS can be used simultaneously for assessing spatial working memory. Mobile optical brain imaging is a promising neuroimaging tool that has the potential to complement tDCS for realistic applications in natural settings.

  19. A differential optical absorption spectroscopy method for retrieval from ground-based Fourier transform spectrometers measurements of the direct solar beam

    Science.gov (United States)

    Huo, Yanfeng; Duan, Minzheng; Tian, Wenshou; Min, Qilong

    2015-08-01

    A differential optical absorption spectroscopy (DOAS)-like algorithm is developed to retrieve the column-averaged dryair mole fraction of carbon dioxide from ground-based hyper-spectral measurements of the direct solar beam. Different to the spectral fitting method, which minimizes the difference between the observed and simulated spectra, the ratios of multiple channel-pairs—one weak and one strong absorption channel—are used to retrieve from measurements of the shortwave infrared (SWIR) band. Based on sensitivity tests, a super channel-pair is carefully selected to reduce the effects of solar lines, water vapor, air temperature, pressure, instrument noise, and frequency shift on retrieval errors. The new algorithm reduces computational cost and the retrievals are less sensitive to temperature and H2O uncertainty than the spectral fitting method. Multi-day Total Carbon Column Observing Network (TCCON) measurements under clear-sky conditions at two sites (Tsukuba and Bremen) are used to derive xxxx for the algorithm evaluation and validation. The DOAS-like results agree very well with those of the TCCON algorithm after correction of an airmass-dependent bias.

  20. DEVELOPING ATMOSPHERIC RETRIEVAL METHODS FOR DIRECT IMAGING SPECTROSCOPY OF GAS GIANTS IN REFLECTED LIGHT. I. METHANE ABUNDANCES AND BASIC CLOUD PROPERTIES

    Energy Technology Data Exchange (ETDEWEB)

    Lupu, Roxana E. [BAER Institute/NASA Ames Research Center, Moffet Field, CA 94035 (United States); Marley, Mark S.; Zahnle, Kevin [NASA Ames Research Center, Moffet Field, CA 94035 (United States); Lewis, Nikole [Space Telescope Science Institute, 3700 San Martin Drive, Baltimore, MD 21218 (United States); Line, Michael [Univ. California at Santa Cruz, 1156 High Street, Santa Cruz, CA 95064 (United States); Traub, Wesley A., E-mail: Roxana.E.Lupu@nasa.gov [Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109 (United States)

    2016-12-01

    Upcoming space-based coronagraphic instruments in the next decade will perform reflected light spectroscopy and photometry of cool directly imaged extrasolar giant planets. We are developing a new atmospheric retrieval methodology to help assess the science return and inform the instrument design for such future missions, and ultimately interpret the resulting observations. Our retrieval technique employs a geometric albedo model coupled with both a Markov chain Monte Carlo Ensemble Sampler ( emcee ) and a multimodal nested sampling algorithm ( MultiNest ) to map the posterior distribution. This combination makes the global evidence calculation more robust for any given model and highlights possible discrepancies in the likelihood maps. As a proof of concept, our current atmospheric model contains one or two cloud layers, methane as a major absorber, and a H{sub 2}–He background gas. This 6-to-9 parameter model is appropriate for Jupiter-like planets and can be easily expanded in the future. In addition to deriving the marginal likelihood distribution and confidence intervals for the model parameters, we perform model selection to determine the significance of methane and cloud detection as a function of expected signal-to-noise ratio in the presence of spectral noise correlations. After internal validation, the method is applied to realistic spectra of Jupiter, Saturn, and HD 99492c, a model observing target. We find that the presence or absence of clouds and methane can be determined with high confidence, while parameter uncertainties are model dependent and correlated. Such general methods will also be applicable to the interpretation of direct imaging spectra of cloudy terrestrial planets.

  1. Quantitative analysis of the near-wall mixture formation process in a passenger car direct-injection diesel engine by using linear raman spectroscopy.

    Science.gov (United States)

    Taschek, Marco; Egermann, Jan; Schwarz, Sabrina; Leipertz, Alfred

    2005-11-01

    Optimum fuel preparation and mixture formation are core issues in the development of modern direct-injection (DI) Diesel engines, as these are crucial for defining the border conditions for the subsequent combustion and pollutant formation process. The local fuel/air ratio can be seen as one of the key parameters for this optimization process, as it allows the characterization and comparison of the mixture formation quality. For what is the first time to the best of our knowledge, linear Raman spectroscopy is used to detect the fuel/air ratio and its change along a line of a few millimeters directly and nonintrusively inside the combustion bowl of a DI Diesel engine. By a careful optimization of the measurement setup, the weak Raman signals could be separated successfully from disturbing interferences. A simultaneous measurement of the densities of air and fuel was possible along a line of about 10 mm length, allowing a time- and space-resolved measurement of the local fuel/air ratio. This could be performed in a nonreacting atmosphere as well as during fired operating conditions. The positioning of the measurement volume next to the interaction point of one of the spray jets with the wall of the combustion bowl allowed a near-wall analysis of the mixture formation process for a six-hole nozzle under varying injection and engine conditions. The results clearly show the influence of the nozzle geometry and preinjection on the mixing process. In contrast, modulation of the intake air temperature merely led to minor changes of the fuel concentration in the measurement volume.

  2. Room temperature redox reaction by oxide ion migration at carbon/Gd-doped CeO2 heterointerface probed by an in situ hard x-ray photoemission and soft x-ray absorption spectroscopies

    Directory of Open Access Journals (Sweden)

    Takashi Tsuchiya, Shogo Miyoshi, Yoshiyuki Yamashita, Hideki Yoshikawa, Kazuya Terabe, Keisuke Kobayashi and Shu Yamaguchi

    2013-01-01

    Full Text Available In situ hard x-ray photoemission spectroscopy (HX-PES and soft x-ray absorption spectroscopy (SX-XAS have been employed to investigate a local redox reaction at the carbon/Gd-doped CeO2 (GDC thin film heterointerface under applied dc bias. In HX-PES, Ce3d and O1s core levels show a parallel chemical shift as large as 3.2 eV, corresponding to the redox window where ionic conductivity is predominant. The window width is equal to the energy gap between donor and acceptor levels of the GDC electrolyte. The Ce M-edge SX-XAS spectra also show a considerable increase of Ce3+ satellite peak intensity, corresponding to electrochemical reduction by oxide ion migration. In addition to the reversible redox reaction, two distinct phenomena by the electrochemical transport of oxide ions are observed as an irreversible reduction of the entire oxide film by O2 evolution from the GDC film to the gas phase, as well as a vigorous precipitation of oxygen gas at the bottom electrode to lift off the GDC film. These in situ spectroscopic observations describe well the electrochemical polarization behavior of a metal/GDC/metal capacitor-like two-electrode cell at room temperature.

  3. Probing Metal Carbonation Reactions of CO2 in a Model System Containing Forsterite and H2O Using Si-29, C-13 Magic Angle Sample Spinning NMR Spectroscopy

    Science.gov (United States)

    Hu, J.; Kwak, J.; Hoyt, D. W.; Sears, J. A.; Rosso, K. M.; Felmy, A. R.

    2009-12-01

    Ex situ solid state NMR have been used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration using a model silicate mineral forsterite (Mg2SiO4)+scCO2 with and without H2O. Run conditions were 80C and 96 bar. Si-29 NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce Mg2+, and mono- and oligomeric hydroxylated silica species. The surface hydrolysis products contain only Q0 (Si(OH)4) and Q1 (Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to less than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. Si-29 NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. C-13 MAS NMR identified a possible reaction intermediates as (MgCO3)4*Mg(OH)2*5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed. This research is part of a broader effort at PNNL to develop experimental tools and fundamental insights into chemical transformations affecting subsurface CO2 reactive transport. Si-29 (left) and C-13 (right) MAS NMR spectra of Mg2SiO4 under various reaction conditions. Si-29 NMR reveals that in scCO2 without H2O, no reaction is

  4. Electron spectroscopy

    International Nuclear Information System (INIS)

    Hegde, M.S.

    1979-01-01

    An introduction to the various techniques in electron spectroscopy is presented. These techniques include: (1) UV Photoelectron spectroscopy, (2) X-ray Photoelectron spectroscopy, (3) Auger electron spectroscopy, (4) Electron energy loss spectroscopy, (5) Penning ionization spectroscopy and (6) Ion neutralization spectroscopy. The radiations used in each technique, the basis of the technique and the special information obtained in structure determination in atoms and molecules by each technique are summarised. (A.K.)

  5. Spectroscopic approaches to resolving ambiguities of hyper-polarized NMR signals from different reaction cascades

    DEFF Research Database (Denmark)

    Jensen, Pernille Rose; Meier, Sebastian

    2016-01-01

    The influx of exogenous substrates into cellular reaction cascades on the seconds time scale is directly observable by NMR spectroscopy when using nuclear spin polarization enhancement. Conventional NMR assignment spectra for the identification of reaction intermediates are not applicable...... in these experiments due to the non-equilibrium nature of the nuclear spin polarization enhancement. We show that ambiguities in the intracellular identification of transient reaction intermediates can be resolved by experimental schemes using site-specific isotope labelling, optimised referencing and response...

  6. Investigations of the mass and charge distribution of fission products from the 238U(n14,f) reaction by direct Ge(Li) method

    International Nuclear Information System (INIS)

    Daroczy, S.

    1979-01-01

    The fission yields can be measured by the well-known activation method if it is taken into account that the fission process results in 5-6 nuclides in an isobaric chain. The method which is based only on the gamma-spectrometric measurement of the irradiated fissioning sample is referred to as the direct Ge(Li) method for fission yield measurement. The thesis contains detailed description of the direct Ge(Li) method. The method was tested by the measurement of cumulative yields of 47 fission products and independent yields of 7 products in the reaction of 238 U(n 14 ,f). These are the members of 37 mass chains in the A=83-149 mass number region. The half-lives of the studied products are in the range of Tsub(1/2)=10 2 -10 9 s; the gamma spectrometric method was improved by extending its applicability to the measurement of short-lived products. Applying short irradiation time (5 min) the yields of 16 fission products with half-lives shorter than 1 hour could be measured. The lowest measured partial fission cross sections (yields) are in the order of 1 mb (0.1%). The accuracy of the yield measured by the direct Ge(Li) method is as high as or higher than that obtained radiochemically, especially for the products measured by many intensive gamma lines. (author)

  7. Study on HCl Driving Force for the Reaction of NaCl-Maleic Acid Mixing Single Droplet Using Micro-FTIR Spectroscopy

    Science.gov (United States)

    He, Xiang; Zhang, Yunhong

    2016-04-01

    Chemical aging is the one of the most important physicochemical process in atmospheric aerosols. Mixing of sea salt and water-soluble organic components has profound effects on the volatile characteristic and evolving chemical composition of the anthropogenic origin aerosols, which are poorly understood. In this study, the chemical reaction behavior of the mixture of NaCl and maleic acid (H2MA) micron-level single droplet was investigated using a gas-flow system combined with microscopic Fourier transform infrared (micro-FTIR) spectrometer over the range of relative humidity (63˜95% RH) for the first time. The results showed that the mixture of NaCl and H2MA single droplet could react to form monosodium maleate salt (NaHMA) at the constant RH from the characterization of the FTIR. The reaction is a result of an acid displacement reaction R1, which is driven by high volatility of the HCl product. NaCl(aq)+H2MA(aq)=NaHMA(aq)+HCl(aq,g) (R1) According to the change tendency of the absorbance values of 1579 cm-1 COO- stretching band of the NaHMA dependent upon reaction times at different RHs, the growth range of the trend which could lead to the faster reaction rate was obvious at lower RH. The water content of the droplet was also more likely to reduce rapidly with the loss of the RH from the absorbance changes of 3400 cm-1H2O stretching band dependent upon reaction times. These may be due to irreversible evaporation of HCl gas which is the main driving force for this type of reaction and the NaHMA is a less hygroscopic component compared to H2MA. And the HCl gas is more likely to evaporate faster from the single droplet and promote the reaction rate and the consumption of water content at lower RH. These results could help in understanding the chemical conversion processes of water-soluble dicarboxylic acids to dicarboxylate salts, as well as the consumption of Cl in sea salt aerosols by organic acids in the atmosphere.

  8. Experimental and modeling study of high performance direct carbon solid oxide fuel cell with in situ catalytic steam-carbon gasification reaction

    Science.gov (United States)

    Xu, Haoran; Chen, Bin; Zhang, Houcheng; Tan, Peng; Yang, Guangming; Irvine, John T. S.; Ni, Meng

    2018-04-01

    In this paper, 2D models for direct carbon solid oxide fuel cells (DC-SOFCs) with in situ catalytic steam-carbon gasification reaction are developed. The simulation results are found to be in good agreement with experimental data. The performance of DC-SOFCs with and without catalyst are compared at different operating potential, anode inlet gas flow rate and operating temperature. It is found that adding suitable catalyst can significantly speed up the in situ steam-carbon gasification reaction and improve the performance of DC-SOFC with H2O as gasification agent. The potential of syngas and electricity co-generation from the fuel cell is also evaluated, where the composition of H2 and CO in syngas can be adjusted by controlling the anode inlet gas flow rate. In addition, the performance DC-SOFCs and the percentage of fuel in the outlet gas are both increased with increasing operating temperature. At a reduced temperature (below 800 °C), good performance of DC-SOFC can still be obtained with in-situ catalytic carbon gasification by steam. The results of this study form a solid foundation to understand the important effect of catalyst and related operating conditions on H2O-assisted DC-SOFCs.

  9. Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

    Science.gov (United States)

    Bauer, Alex; Gyenge, Előd L.; Oloman, Colin W.

    Pressed graphite felt (thickness ∼350 μm) with electrodeposited PtRu (43 g m -2, 1.4:1 atomic ratio) or PtRuMo (52 g m -2, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m -2 with PtRuMo at 5500 A m -2 and 353 K while under the same conditions PtRu yielded 1925 W m -2. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation.

  10. Spillover effect induced Pt-TiO2/C as ethanol tolerant oxygen reduction reaction catalyst for direct ethanol fuel cells

    International Nuclear Information System (INIS)

    Meenakshi, S.; Nishanth, K.G.; Sridhar, P.; Pitchumani, S.

    2014-01-01

    Hypo-hyper-d-electronic interactive nature is used to develop a new carbon supported HT-Pt-TiO 2 composite catalyst comprising Pt and Ti in varying atomic ratio, namely 1:1, 2:1 and 3:1. The electro-catalysts are characterized by XRD, TEM, SEM-EDAX, Cyclic Voltammetry (CV) and Linear sweep voltammetry (LSV) techniques. HT-Pt-TiO 2 /C catalysts exhibit significant improvement in oxygen reduction reaction (ORR) over Pt/C. The effect of composition towards ORR with and without ethanol has been studied. The direct ethanol fuel cell (DEFC) with HT-Pt-TiO 2 /C cathode catalyst exhibits an enhanced peak power density of 41 mW cm −2 , whereas 21 mW cm −2 is obtained for the DEFCs with carbon-supported Pt catalyst operating under identical conditions

  11. Wafer-scale laser pantography: Fabrication of n-metal-oxide-semiconductor transistors and small-scale integrated circuits by direct-write laser-induced pyrolytic reactions

    International Nuclear Information System (INIS)

    McWilliams, B.M.; Herman, I.P.; Mitlitsky, F.; Hyde, R.A.; Wood, L.L.

    1983-01-01

    A complete set of processes sufficient for manufacture of n-metal-oxide-semiconductor (n-MOS) transistors by a laser-induced direct-write process has been demonstrated separately, and integrated to yield functional transistors. Gates and interconnects were fabricated of various combinations of n-doped and intrinsic polysilicon, tungsten, and tungsten silicide compounds. Both 0.1-μm and 1-μm-thick gate oxides were micromachined with and without etchant gas, and the exposed p-Si [100] substrate was cleaned and, at times, etched. Diffusion regions were doped by laser-induced pyrolytic decomposition of phosphine followed by laser annealing. Along with the successful manufacture of working n-MOS transistors and a set of elementary digital logic gates, this letter reports the successful use of several laser-induced surface reactions that have not been reported previously

  12. Fluorogenic organocatalytic reactions

    NARCIS (Netherlands)

    Raeisolsadati Oskouei, M.

    2017-01-01

    In this thesis, we introduce fluorescence spectroscopy as a new tool to gain insight into the interactions between the substrates and catalyst during organocatalytic reactions. The ultimate goal is to resolve the kinetics of the binding and reaction steps and obtain detailed understanding of the

  13. 57Fe-Mössbauer spectroscopy and electrochemical activities of graphitic layer encapsulated iron electrocatalysts for the oxygen reduction reaction

    DEFF Research Database (Denmark)

    Zhong, Lijie; Frandsen, Cathrine; Mørup, Steen

    2018-01-01

    Graphitic layer encapsulated iron based nanoparticles (G@FeNPs) have recently been disclosed as an interesting type of highly active electrocatalysts for the oxygen reduction reaction (ORR). However, the complex composition of the metal-containing components and their contributions in catalysis r...

  14. Measuring Heterogeneous Reaction Rates with ATR-FTIR Spectroscopy to Evaluate Chemical Fates in an Atmospheric Environment: A Physical Chemistry and Environmental Chemistry Laboratory Experiment

    Science.gov (United States)

    Roberts, Jason E.; Zeng, Guang; Maron, Marta K.; Mach, Mindy; Dwebi, Iman; Liu, Yong

    2016-01-01

    This paper reports an undergraduate laboratory experiment to measure heterogeneous liquid/gas reaction kinetics (ozone-oleic acid and ozone-phenothrin) using a flow reactor coupled to an attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometer. The experiment is specially designed for an upper-level undergraduate Physical…

  15. Monitoring and Control of a Continuous Grignard Reaction for the Synthesis of an Active Pharmaceutical Ingredient Intermediate Using Inline NIR spectroscopy

    DEFF Research Database (Denmark)

    Cervera Padrell, Albert Emili; Nielsen, Jesper; Jønch Pedersen, Michael

    2012-01-01

    to the stoichiometric ratio, leading the path to full process automation. The feedback control loop relies on NIR transmission measurements performed in a flow cell where, in contrast to labor-intensive offline HPLC analytical methods, the whole reaction product can be scanned in real time without sample dilution...

  16. Kinetics and thermochemistry of the reversible gas phase reaction HONO+NH3->3N-HONO studied by infrared diode laser spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, P.; Ratajczak, E.; Sillesen, A.

    1994-01-01

    The kinetics of the reversible reaction HONO+NH3 reversible H3N-HONO (1) was studied by monitoring trans-HONO relaxation kinetics. The rate of approach towards equilibrium was studied as a function of the ammonia concentration to obtain values of the rate constants for the forward and reverse rea...

  17. Hydrogen bonds in the vicinity of the special pair of the bacterial reaction center probed by hydrostatic high-pressure absorption spectroscopy.

    Science.gov (United States)

    Kangur, Liina; Jones, Michael R; Freiberg, Arvi

    2017-12-01

    Using the native bacteriochlorophyll a pigment cofactors as local probes, we investigated the response to external hydrostatic high pressure of reaction center membrane protein complexes from the photosynthetic bacterium Rhodobacter sphaeroides. Wild-type and engineered complexes were used with a varied number (0, 1 or 2) of hydrogen bonds that bind the reaction center primary donor bacteriochlorophyll cofactors to the surrounding protein scaffold. A pressure-induced breakage of hydrogen bonds was established for both detergent-purified and membrane-embedded reaction centers, but at rather different pressures: between 0.2 and 0.3GPa and at about 0.55GPa, respectively. The free energy change associated with the rupture of the single hydrogen bond present in wild-type reaction centers was estimated to be equal to 13-14kJ/mol. In the mutant with two symmetrical hydrogen bonds (FM197H) a single cooperative rupture of the two bonds was observed corresponding to an about twice stronger bond, rather than a sequential rupture of two individual bonds. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Astrophysical 3He(α ,γ )7Be and 3H(α ,γ )7Li direct capture reactions in a potential-model approach

    Science.gov (United States)

    Tursunov, E. M.; Turakulov, S. A.; Kadyrov, A. S.

    2018-03-01

    The astrophysical 3He(α ,γ )7Be and 3H(α ,γ )7Li direct capture processes are studied in the framework of the two-body model with potentials of a simple Gaussian form, which describe correctly the phase shifts in the s , p , d , and f waves, as well as the binding energy and the asymptotic normalization constant of the ground p3 /2 and the first excited p1 /2 bound states. It is shown that the E 1 transition from the initial s wave to the final p waves is strongly dominant in both capture reactions. On this basis the s -wave potential parameters are adjusted to reproduce the new data of the LUNA Collaboration around 100 keV and the newest data at the Gamov peak estimated with the help of the observed neutrino fluxes from the sun, S34(23-5+6keV ) =0.548 ±0.054 keV b for the astrophysical S factor of the capture process 3He(α ,γ )7Be . The resulting model describes well the astrophysical S factor in the low-energy big-bang nucleosynthesis region of 180-400 keV; however, it has a tendency to underestimate the data above 0.5 MeV. The energy dependence of the S factor is mostly consistent with the data and the results of the no-core shell model with continuum, but substantially different from the fermionic molecular dynamics model predictions. Two-body potentials, adjusted for the properties of the 7Be nucleus, 3He+α elastic scattering data, and the astrophysical S factor of the 3He(α ,γ )7Be direct capture reaction, are able to reproduce the properties of the 7Li nucleus, the binding energies of the ground 3 /2- and first excited 1 /2- states, and phase shifts of the 3H+α elastic scattering in partial waves. Most importantly, these potential models can successfully describe both absolute value and energy dependence of the existing experimental data for the mirror astrophysical 3H(α ,γ )7Li capture reaction without any additional adjustment of the parameters.

  19. Developing Atmospheric Retrieval Methods for Direct Imaging Spectroscopy of Gas Giants in Reflected Light I: Methane Abundances and Basic Cloud Properties

    Science.gov (United States)

    Lupu, R. E.; Marley, M. S.; Lewis, N.; Line, M.; Traub, W.; Zahnle, K.

    2016-01-01

    Reflected light spectroscopy and photometry of cool, directly imaged extrasolar giant planets are expected to be performed in the next decade by space-based telescopes equipped with optical wavelength coronagraphs and integral field spectrographs, such as the Wide-Field Infrared Survey Telescope (WFIRST). We are developing a new atmospheric retrieval methodology to help assess the science return and inform the instrument design for such future missions, and ultimately interpret the resulting observations. Our retrieval technique employs an albedo model coupled with both a Markov chain Monte Carlo Ensemble Sampler (emcee) and a multimodal nested sampling algorithm (MultiNest) to map the posterior distribution. This combination makes the global evidence calculation more robust for any given model, and highlights possible discrepancies in the likelihood maps. Here we apply this methodology to simulated spectra of cool giant planets. As a proof-of-concept, our current atmospheric model contains 1 or 2 cloud layers, methane as a major absorber, and a H2-He background gas. This 6-to-9 parameter model is appropriate for Jupiter-like planets and can be easily expanded in the future. In addition to deriving the marginal likelihood distribution and confidence intervals for the model parameters, we perform model selection to determine the significance of methane and cloud detection as a function of expected signal-to-noise, in the presence of spectral noise correlations. After internal validation, the method is applied to realistic reflected-light spectra of Jupiter, Saturn, and HD 99492 c, a likely observing target. We find that the presence or absence of clouds and methane can be determined with high accuracy, while parameters uncertainties are model-dependent.

  20. Gamma Spectroscopy

    NARCIS (Netherlands)

    Niemantsverdriet, J.W.; Butz, Tilman; Ertl, G.; Knözinger, H.; Schüth, F.

    2008-01-01

    No abstract. The sections in this article are 1 Introduction 2 Mössbauer Spectroscopy 3 Time-Differential Perturbed Angular Correlations (TDPAC) 4 Conclusions and Outlook Keywords: Mössbauer spectroscopy; gamma spectroscopy; perturbed angular correlation; TDPAC