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Sample records for reaction steps relevant

  1. An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

    Energy Technology Data Exchange (ETDEWEB)

    Svelle, Stian

    2004-07-01

    The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

  2. An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

    Energy Technology Data Exchange (ETDEWEB)

    Svelle, Stian

    2004-07-01

    The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

  3. 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

  4. 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

  5. A step-by-step guide to systematically identify all relevant animal studies

    Science.gov (United States)

    Leenaars, Marlies; Hooijmans, Carlijn R; van Veggel, Nieky; ter Riet, Gerben; Leeflang, Mariska; Hooft, Lotty; van der Wilt, Gert Jan; Tillema, Alice; Ritskes-Hoitinga, Merel

    2012-01-01

    Before starting a new animal experiment, thorough analysis of previously performed experiments is essential from a scientific as well as from an ethical point of view. The method that is most suitable to carry out such a thorough analysis of the literature is a systematic review (SR). An essential first step in an SR is to search and find all potentially relevant studies. It is important to include all available evidence in an SR to minimize bias and reduce hampered interpretation of experimental outcomes. Despite the recent development of search filters to find animal studies in PubMed and EMBASE, searching for all available animal studies remains a challenge. Available guidelines from the clinical field cannot be copied directly to the situation within animal research, and although there are plenty of books and courses on searching the literature, there is no compact guide available to search and find relevant animal studies. Therefore, in order to facilitate a structured, thorough and transparent search for animal studies (in both preclinical and fundamental science), an easy-to-use, step-by-step guide was prepared and optimized using feedback from scientists in the field of animal experimentation. The step-by-step guide will assist scientists in performing a comprehensive literature search and, consequently, improve the scientific quality of the resulting review and prevent unnecessary animal use in the future. PMID:22037056

  6. 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

  7. Two-Step Macrocycle Synthesis by Classical Ugi Reaction

    NARCIS (Netherlands)

    Abdelraheem, Eman M M; Khaksar, Samad; Kurpiewska, Katarzyna; Kalinowska-Tłuścik, Justyna; Shaabani, Shabnam; Dömling, Alexander

    2018-01-01

    The direct nonpeptidic macrocycle synthesis of α-isocyano-ω-amines via the classical Ugi four-component reaction (U-4CR) is introduced. Herein an efficient and flexible two-step procedure to complex macrocycles is reported. In the first step, the reaction between unprotected diamines and

  8. Analysis of reaction schemes using maximum rates of constituent steps

    Science.gov (United States)

    Motagamwala, Ali Hussain; Dumesic, James A.

    2016-01-01

    We show that the steady-state kinetics of a chemical reaction can be analyzed analytically in terms of proposed reaction schemes composed of series of steps with stoichiometric numbers equal to unity by calculating the maximum rates of the constituent steps, rmax,i, assuming that all of the remaining steps are quasi-equilibrated. Analytical expressions can be derived in terms of rmax,i to calculate degrees of rate control for each step to determine the extent to which each step controls the rate of the overall stoichiometric reaction. The values of rmax,i can be used to predict the rate of the overall stoichiometric reaction, making it possible to estimate the observed reaction kinetics. This approach can be used for catalytic reactions to identify transition states and adsorbed species that are important in controlling catalyst performance, such that detailed calculations using electronic structure calculations (e.g., density functional theory) can be carried out for these species, whereas more approximate methods (e.g., scaling relations) are used for the remaining species. This approach to assess the feasibility of proposed reaction schemes is exact for reaction schemes where the stoichiometric coefficients of the constituent steps are equal to unity and the most abundant adsorbed species are in quasi-equilibrium with the gas phase and can be used in an approximate manner to probe the performance of more general reaction schemes, followed by more detailed analyses using full microkinetic models to determine the surface coverages by adsorbed species and the degrees of rate control of the elementary steps. PMID:27162366

  9. Relevance of positive patch-test reactions to fragrance mix.

    Science.gov (United States)

    Devos, Steven A; Constandt, Lieve; Tupker, Ron A; Noz, Kathy C; Lucker, Georges P H; Bruynzeel, Derk P; Schuttelaar, Marie-Louise A; Kruyswijk, Mente R J; van Zuuren, Esther J; Vink, Jaqueline; Coenraads, Pieter-Jan; Kiemeney, Lambertus A L M; van der Valk, Pieter G M

    2008-01-01

    Fragrances are an important cause of allergic contact dermatitis. We presume that the traditional fragrance mix (FM) detects 70 to 80% of fragrance-allergic patients. FM has an irritant potential. Weak positive reactions may have a greater chance of being irrelevant than strong reactions. To improve the appraisal of FM patch-test reactions, we studied the relevance of reactions of different strength. We also studied the predictive value of the following on the relevance of the initial FM patch-test results: patch-test results of a repeated FM test; results of patch tests with balsam of Peru, colophony, and ingredients of the mix; and (history of) atopic dermatitis. One hundred thirty-eight patients who had doubtful positive (?+) or positive (+ to +++) reactions were included in the study. We determined relevance by history taking, location and course of the dermatitis, and additional patch testing. Patients were retested with FM and with each ingredient separately. The relevance of reactions to FM increases with the strength of the reactions. Predictors of relevance are the results of retesting with FM, the results of tests with the ingredients, and a history and/or present symptoms of atopic dermatitis. Retesting with FM and its ingredients may add to the benefit of patch testing.

  10. Nonequilibrium thermodynamics and a fluctuation theorem for individual reaction steps in a chemical reaction network

    International Nuclear Information System (INIS)

    Pal, Krishnendu; Das, Biswajit; Banerjee, Kinshuk; Gangopadhyay, Gautam

    2015-01-01

    We have introduced an approach to nonequilibrium thermodynamics of an open chemical reaction network in terms of the propensities of the individual elementary reactions and the corresponding reverse reactions. The method is a microscopic formulation of the dissipation function in terms of the relative entropy or Kullback-Leibler distance which is based on the analogy of phase space trajectory with the path of elementary reactions in a network of chemical process. We have introduced here a fluctuation theorem valid for each opposite pair of elementary reactions which is useful in determining the contribution of each sub-reaction on the nonequilibrium thermodynamics of overall reaction. The methodology is applied to an oligomeric enzyme kinetics at a chemiostatic condition that leads the reaction to a nonequilibrium steady state for which we have estimated how each step of the reaction is energy driven or entropy driven to contribute to the overall reaction. (paper)

  11. 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

  12. 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

  13. Step-by-Step Simulation of Radiation Chemistry Using Green Functions for Diffusion-Influenced Reactions

    Science.gov (United States)

    Plante, Ianik; Cucinotta, Francis A.

    2011-01-01

    Radiolytic species are formed approximately 1 ps after the passage of ionizing radiation through matter. After their formation, they diffuse and chemically react with other radiolytic species and neighboring biological molecules, leading to various oxidative damage. Therefore, the simulation of radiation chemistry is of considerable importance to understand how radiolytic species damage biological molecules [1]. The step-by-step simulation of chemical reactions is difficult, because the radiolytic species are distributed non-homogeneously in the medium. Consequently, computational approaches based on Green functions for diffusion-influenced reactions should be used [2]. Recently, Green functions for more complex type of reactions have been published [3-4]. We have developed exact random variate generators of these Green functions [5], which will allow us to use them in radiation chemistry codes. Moreover, simulating chemistry using the Green functions is which is computationally very demanding, because the probabilities of reactions between each pair of particles should be evaluated at each timestep [2]. This kind of problem is well adapted for General Purpose Graphic Processing Units (GPGPU), which can handle a large number of similar calculations simultaneously. These new developments will allow us to include more complex reactions in chemistry codes, and to improve the calculation time. This code should be of importance to link radiation track structure simulations and DNA damage models.

  14. Considerations for the independent reaction times and step-by-step methods for radiation chemistry simulations

    Science.gov (United States)

    Plante, Ianik; Devroye, Luc

    2017-10-01

    Ionizing radiation interacts with the water molecules of the tissues mostly by ionizations and excitations, which result in the formation of the radiation track structure and the creation of radiolytic species such as H.,.OH, H2, H2O2, and e-aq. After their creation, these species diffuse and may chemically react with the neighboring species and with the molecules of the medium. Therefore radiation chemistry is of great importance in radiation biology. As the chemical species are not distributed homogeneously, the use of conventional models of homogeneous reactions cannot completely describe the reaction kinetics of the particles. Actually, many simulations of radiation chemistry are done using the Independent Reaction Time (IRT) method, which is a very fast technique to calculate radiochemical yields but which do not calculate the positions of the radiolytic species as a function of time. Step-by-step (SBS) methods, which are able to provide such information, have been used only sparsely because these are time-consuming in terms of calculation. Recent improvements in computer performance now allow the regular use of the SBS method in radiation chemistry. The SBS and IRT methods are both based on the Green's functions of the diffusion equation (GFDE). In this paper, several sampling algorithms of the GFDE and for the IRT method are presented. We show that the IRT and SBS methods are exactly equivalent for 2-particles systems for diffusion and partially diffusion-controlled reactions between non-interacting particles. We also show that the results obtained with the SBS simulation method with periodic boundary conditions are in agreement with the predictions by classical reaction kinetics theory, which is an important step towards using this method for modelling of biochemical networks and metabolic pathways involved in oxidative stress. Finally, the first simulation results obtained with the code RITRACKS (Relativistic Ion Tracks) are presented.

  15. Site selectivity of specific reaction steps important for catalysis

    DEFF Research Database (Denmark)

    Nielsen, Kenneth

    ) overlayer system. In the STM study of the structure sensitivity of the CO dissociation reaction on the Ru(0 1 54) sample, it was determined that after cooling the sample from 700K to 400K in 10-8Torr of CO or in the CO that was left after a TPD, the sample displayed periodic decorations on every other...... site, is the most stable conguration after dissociation. Preliminary results where the sample was exposed to high doses of CO, at a CO pressure of 10-5 Torr and a temperature of 550K (dissociation conditions) indicated that especially every other step had a very rough appearance after 7 min exposure...

  16. Positive patch test reactions to oxidized limonene: exposure and relevance.

    Science.gov (United States)

    Bråred Christensson, Johanna; Andersen, Klaus E; Bruze, Magnus; Johansen, Jeanne D; Garcia-Bravo, Begoña; Gimenez Arnau, Ana; Goh, Chee-Leok; Nixon, Rosemary; White, Ian R

    2014-11-01

    R-Limonene is a common fragrance terpene found in domestic and industrial products. R-Limonene autoxidizes on air exposure, and the oxidation products can cause contact allergy. In a recent multicentre study, 5.2% (range 2.3-12.1%) of 2900 patients showed a positive patch test reaction to oxidized R-limonene. To study the exposure to limonene among consecutive dermatitis patients reacting to oxidized R-limonene in an international setting, and to assess the relevance of the exposure for the patients' dermatitis. Oxidized R-limonene 3.0% (containing limonene hydroperoxides at 0.33%) in petrolatum was tested in 2900 consecutive dermatitis patients in Australia, Denmark, the United Kingdom, Singapore, Spain, and Sweden. A questionnaire assessing exposure to limonene-containing products was completed. Overall, exposure to products containing limonene was found and assessed as being probably relevant for the patients' dermatitis in 36% of the limonene-allergic patients. In Barcelona and Copenhagen, > 70% of the patients were judged to have had an exposure to limonene assessed as relevant. Oxidized R-limonene is a common fragrance allergen, and limonene was frequently found in the labelling on the patients' products, and assessed as relevant for the patients' dermatitis. A large number of domestic and occupational sources for contact with R-limonene were identified. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  17. 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

  18. Step-to-step spatiotemporal variables and ground reaction forces of intra-individual fastest sprinting in a single session.

    Science.gov (United States)

    Nagahara, Ryu; Mizutani, Mirai; Matsuo, Akifumi; Kanehisa, Hiroaki; Fukunaga, Tetsuo

    2018-06-01

    We aimed to investigate the step-to-step spatiotemporal variables and ground reaction forces during the acceleration phase for characterising intra-individual fastest sprinting within a single session. Step-to-step spatiotemporal variables and ground reaction forces produced by 15 male athletes were measured over a 50-m distance during repeated (three to five) 60-m sprints using a long force platform system. Differences in measured variables between the fastest and slowest trials were examined at each step until the 22nd step using a magnitude-based inferences approach. There were possibly-most likely higher running speed and step frequency (2nd to 22nd steps) and shorter support time (all steps) in the fastest trial than in the slowest trial. Moreover, for the fastest trial there were likely-very likely greater mean propulsive force during the initial four steps and possibly-very likely larger mean net anterior-posterior force until the 17th step. The current results demonstrate that better sprinting performance within a single session is probably achieved by 1) a high step frequency (except the initial step) with short support time at all steps, 2) exerting a greater mean propulsive force during initial acceleration, and 3) producing a greater mean net anterior-posterior force during initial and middle acceleration.

  19. 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

  20. RKC time-stepping for advection-diffusion-reaction problems

    International Nuclear Information System (INIS)

    Verwer, J.G.; Sommeijer, B.P.; Hundsdorfer, W.

    2004-01-01

    The original explicit Runge-Kutta-Chebyshev (RKC) method is a stabilized second-order integration method for pure diffusion problems. Recently, it has been extended in an implicit-explicit manner to also incorporate highly stiff reaction terms. This implicit-explicit RKC method thus treats diffusion terms explicitly and the highly stiff reaction terms implicitly. The current paper deals with the incorporation of advection terms for the explicit method, thus aiming at the implicit-explicit RKC integration of advection-diffusion-reaction equations in a manner that advection and diffusion terms are treated simultaneously and explicitly and the highly stiff reaction terms implicitly

  1. Anaphylactic reaction to iodinated contrast media. Review the relevant loterature

    International Nuclear Information System (INIS)

    Kuwashima, Shigeko; Kitajima, Kazuhiro; Kohno, Tatsuo; Kaji, Yasushi; Takahashi, Tetuya; Seki, Masaya; Sakamoto, Tomoyuki

    2007-01-01

    Recently, iodinated contrast media are necessary for CT examinations and they occupy an important position in the radiological diagnosis. Nonionic contrast media significantly reduce the prevalence of all degree of adverse reaction to contrast media rather than ionic contrast media. So, generally, iodinated contrast media are safe and widely used, but adverse reaction after intravenous iodinated contrast media are not uncommon. Severe and potentially life-threatening reaction occur by using the iodinated contrast media practically. Patients at risk must be identified before the contrast media study, and all possible measures must be taken to deal effectively with spontaneous anaphylactic reactions. We report three cases of anaphylactic reactions by iodinated contrast media on CT. (author)

  2. 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.

  3. Relevance of positive patch-test reactions to fragrance mix.

    NARCIS (Netherlands)

    Devos, S.A.; Constandt, L.; Tupker, R.A.; Noz, K.C.; Lucker, G.P.H.; Bruynzeel, D.P.; Schuttelaar, M.L.; Kruyswijk, M.R.; Zuuren, E.J. van; Vink, J.; Coenraads, P.J.; Kiemeney, L.A.L.M.; Valk, P.G.M. van der

    2008-01-01

    BACKGROUND: Fragrances are an important cause of allergic contact dermatitis. We presume that the traditional fragrance mix (FM) detects 70 to 80% of fragrance-allergic patients. FM has an irritant potential. Weak positive reactions may have a greater chance of being irrelevant than strong

  4. Relevance of positive patch-test reactions to fragrance mix

    NARCIS (Netherlands)

    Devos, S.A.; Constandt, L.; Tupker, R.A.; Noz, K.C.; Lucker, G.P.H.; Bruynzeel, D.P.; Schuttelaar, M.L.A.; Kruyswijk, M.R.J.; van Zuuren, E.J.; Vink, J.; Coenraads, P.J.; Kiemeney, L.A.L.M.; van der Valk, P.G.M.

    2008-01-01

    BACKGROUND: Fragrances are an important cause of allergic contact dermatitis. We presume that the traditional fragrance mix (FM) detects 70 to 80% of fragrance-allergic patients. FM has an irritant potential. Weak positive reactions may have a greater chance of being irrelevant than strong

  5. Determining two-step control in heterogeneous catalytic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Chakrabarty, T; Silveston, P L; Hudgins, R R

    1979-10-01

    The data by Thaller and Thodos on the sec.-butanol dehydrogenation to methyl ethyl ketone on brass catalyst indicated that a dual site surface reaction was rate-controlling below 575/sup 0/K and hydrogen desorption was rate-controlling above 616/sup 0/K (Vertical BarAIChE J.

  6. Consumer adverse drug reaction reporting - A new step in pharmacovigilance?

    NARCIS (Netherlands)

    van Grootheest, K; de Graaf, L; de Jong-van den Berg, LTW

    2003-01-01

    The direct reporting of adverse drug reactions by patients is becoming an increasingly important topic for discussion in the world of pharmacovigilance. At this time, few countries accept consumer reports. We present an overview of experiences with consumer reporting in various countries of the

  7. Molecular dynamics simulation of the first electron transfer step in the oxygen reduction reaction

    NARCIS (Netherlands)

    Hartnig, C.B.; Koper, M.T.M.

    2002-01-01

    We present a molecular dynamics simulation of solvent reorganization in the first electron transfer step in the oxygen reduction reaction, i.e. O2+e-¿O2-, modeled as taking place in the outer Helmholtz plane. The first electron transfer step is usually considered the rate-determining step from many

  8. Performance monitoring and response conflict resolution associated with choice stepping reaction tasks.

    Science.gov (United States)

    Watanabe, Tatsunori; Tsutou, Kotaro; Saito, Kotaro; Ishida, Kazuto; Tanabe, Shigeo; Nojima, Ippei

    2016-11-01

    Choice reaction requires response conflict resolution, and the resolution processes that occur during a choice stepping reaction task undertaken in a standing position, which requires maintenance of balance, may be different to those processes occurring during a choice reaction task performed in a seated position. The study purpose was to investigate the resolution processes during a choice stepping reaction task at the cortical level using electroencephalography and compare the results with a control task involving ankle dorsiflexion responses. Twelve young adults either stepped forward or dorsiflexed the ankle in response to a visual imperative stimulus presented on a computer screen. We used the Simon task and examined the error-related negativity (ERN) that follows an incorrect response and the correct-response negativity (CRN) that follows a correct response. Error was defined as an incorrect initial weight transfer for the stepping task and as an incorrect initial tibialis anterior activation for the control task. Results revealed that ERN and CRN amplitudes were similar in size for the stepping task, whereas the amplitude of ERN was larger than that of CRN for the control task. The ERN amplitude was also larger in the stepping task than the control task. These observations suggest that a choice stepping reaction task involves a strategy emphasizing post-response conflict and general performance monitoring of actual and required responses and also requires greater cognitive load than a choice dorsiflexion reaction. The response conflict resolution processes appear to be different for stepping tasks and reaction tasks performed in a seated position.

  9. Heterogeneous reaction mechanisms and kinetics relevant to the CVD of semiconductor materials

    Energy Technology Data Exchange (ETDEWEB)

    Creighton, J.R.; Coltrin, M.E.

    1994-03-01

    This report documents the state of the art in experimental and theoretical techniques for determining reaction mechanisms and chemical kinetics of heterogeneous reactions relevant to the chemical vapor deposition of semiconductor materials. It summarizes the most common ultra-high vacuum experimental techniques that are used and the types of rate information available from each. Several case studies of specific chemical systems relevant to the microelectronics industry are described. Theoretical methods for calculating heterogeneous reaction rate constants are also summarized.

  10. Reactions of Ground State Nitrogen Atoms N(4S) with Astrochemically-Relevant Molecules on Interstellar Dusts

    Science.gov (United States)

    Krim, Lahouari; Nourry, Sendres

    2015-06-01

    In the last few years, ambitious programs were launched to probe the interstellar medium always more accurately. One of the major challenges of these missions remains the detection of prebiotic compounds and the understanding of reaction pathways leading to their formation. These complex heterogeneous reactions mainly occur on icy dust grains, and their studies require the coupling of laboratory experiments mimicking the extreme conditions of extreme cold and dilute media. For that purpose, we have developed an original experimental approach that combine the study of heterogeneous reactions (by exposing neutral molecules adsorbed on ice to non-energetic radicals H, OH, N...) and a neon matrix isolation study at very low temperatures, which is of paramount importance to isolate and characterize highly reactive reaction intermediates. Such experimental approach has already provided answers to many questions raised about some astrochemically-relevant reactions occurring in the ground state on the surface of dust grain ices in dense molecular clouds. The aim of this new present work is to show the implication of ground state atomic nitrogen on hydrogen atom abstraction reactions from some astrochemically-relevant species, at very low temperatures (3K-20K), without providing any external energy. Under cryogenic temperatures and with high barrier heights, such reactions involving N(4S) nitrogen atoms should not occur spontaneously and require an initiating energy. However, the detection of some radicals species as byproducts, in our solid samples left in the dark for hours at 10K, proves that hydrogen abstraction reactions involving ground state N(4S) nitrogen atoms may occur in solid phase at cryogenic temperatures. Our results show the efficiency of radical species formation stemming from non-energetic N-atoms and astrochemically-relevant molecules. We will then discuss how such reactions, involving nitrogen atoms in their ground states, might be the first key step

  11. 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.)

  12. Errors in Postural Preparation Lead to Increased Choice Reaction Times for Step Initiation in Older Adults

    Science.gov (United States)

    Nutt, John G.; Horak, Fay B.

    2011-01-01

    Background. This study asked whether older adults were more likely than younger adults to err in the initial direction of their anticipatory postural adjustment (APA) prior to a step (indicating a motor program error), whether initial motor program errors accounted for reaction time differences for step initiation, and whether initial motor program errors were linked to inhibitory failure. Methods. In a stepping task with choice reaction time and simple reaction time conditions, we measured forces under the feet to quantify APA onset and step latency and we used body kinematics to quantify forward movement of center of mass and length of first step. Results. Trials with APA errors were almost three times as common for older adults as for younger adults, and they were nine times more likely in choice reaction time trials than in simple reaction time trials. In trials with APA errors, step latency was delayed, correlation between APA onset and step latency was diminished, and forward motion of the center of mass prior to the step was increased. Participants with more APA errors tended to have worse Stroop interference scores, regardless of age. Conclusions. The results support the hypothesis that findings of slow choice reaction time step initiation in older adults are attributable to inclusion of trials with incorrect initial motor preparation and that these errors are caused by deficits in response inhibition. By extension, the results also suggest that mixing of trials with correct and incorrect initial motor preparation might explain apparent choice reaction time slowing with age in upper limb tasks. PMID:21498431

  13. Photochemical reactions of nucleic acids and their constituents of photobiological relevance

    International Nuclear Information System (INIS)

    Saito, I.; Sugiyama, H.; Matsuura, T.

    1983-01-01

    A review is given of the papers published from 1977 to May 1983 on the UV-induced photochemical reactions of nucleic acids and their constituents of photobiological relevance where the structures of photoproducts have been fully characterized. Among the topics discussed are photoadditions relevant to nucleic acid-protein photocrosslinking, photoreactions with psoralens and nucleic acids and photochemical reactions of polynucleotides. (U.K.)

  14. Biomarkers for AAA: Encouraging steps but clinical relevance still to be delivered.

    Science.gov (United States)

    Htun, Nay Min; Peter, Karlheinz

    2014-10-01

    Potential biomarkers have been investigated using proteomic studies in a variety of diseases. Some biomarkers have central roles in both diagnosis and monitoring of various disorders in clinical medicine, such as troponins, brain natriuretic peptide, and C-reactive protein. Although several biomarkers have been suggested in human abdominal aortic aneurysm (AAA), reliable markers have been lacking. In this issue, Moxon et al. [Proteomics Clin Appl. 2014, 8, 762-772] undertook a broad and systematic proteomic approach toward identification of biomarkers in a commonly used AAA mouse model (AAA created by angiotensin-II infusion). In this mouse model, apolipoprotein C1 and matrix metalloproteinase-9 were identified as novel biomarkers of stable AAA. This finding represents an important step forward, toward a clinically relevant role of biomarkers in AAA. This also encourages for further studies toward the identification of biomarkers (or their combinations) that can predict AAA progression and rupture, which would represent a major progress in AAA management and would establish an AAA biomarker as a much anticipated clinical tool. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Effects of self-schema elaboration on affective and cognitive reactions to self-relevant information.

    Science.gov (United States)

    Petersen, L E; Stahlberg, D; Dauenheimer, D

    2000-02-01

    The basic assumption of the integrative self-schema model (ISSM; L.-E. Petersen, 1994; L.-E. Petersen, D. Stahlberg, & D. Dauenheimer, 1996; D. Stahlberg, L.-E. Petersen, & D. Dauenheimer, 1994, 1999) is that self-schema elaboration (schematic vs. aschematic) affects reactions to self-relevant information. This assumption is based on the idea that schematic dimensions occupy a more central position in the cognitive system than aschematic dimensions. In the first study, this basic prediction could be clearly confirmed: The results showed that schematic dimensions possessed stronger cognitive associations with other self-relevant cognitions as well as a higher resistance to change than aschematic dimensions did. In the second study, the main assumptions of the ISSM concerning the affective and cognitive reactions to self-relevant feedback were tested: The ISSM proposes that, on schematic dimensions, reactions to self-relevant feedback will most likely follow principles of self-consistency theory, whereas on aschematic dimensions positive feedback should elicit the most positive reactions that self-enhancement theory would predict. The experimental results clearly confirmed the hypotheses derived from the ISSM for affective reactions. Cognitive reactions, however, were in line with self-consistency principles and were not modified by the elaboration of the self-schema dimension involved.

  16. GAS-PHASE REACTIONS OF POLYCYCLIC AROMATIC HYDROCARBON ANIONS WITH MOLECULES OF INTERSTELLAR RELEVANCE

    International Nuclear Information System (INIS)

    Demarais, Nicholas J.; Yang Zhibo; Martinez, Oscar; Wehres, Nadine; Bierbaum, Veronica M.; Snow, Theodore P.

    2012-01-01

    We have studied reactions of small dehydrogenated polycyclic aromatic hydrocarbon anions with neutral species of interstellar relevance. Reaction rate constants are measured at 300 K for the reactions of phenide (C 6 H – 5 ), naphthalenide (C 10 H – 7 ), and anthracenide (C 14 H – 9 ) with atomic H, H 2 , and D 2 using a flowing afterglow-selected ion flow tube instrument. Reaction rate constants of phenide with neutral molecules (CO, O 2 , CO 2 , N 2 O, C 2 H 2 , CH 3 OH, CH 3 CN, (CH 3 ) 2 CO, CH 3 CHO, CH 3 Cl, and (CH 3 CH 2 ) 2 O) are also measured under the same conditions. Experimental measurements are accompanied by ab initio calculations to provide insight into reaction pathways and enthalpies. Our measured reaction rate constants should prove useful in the modeling of astrophysical environments, particularly when applied to dense regions of the interstellar and circumstellar medium.

  17. Gas-phase Reactions of Polycyclic Aromatic Hydrocarbon Anions with Molecules of Interstellar Relevance

    Science.gov (United States)

    Demarais, Nicholas J.; Yang, Zhibo; Martinez, Oscar; Wehres, Nadine; Snow, Theodore P.; Bierbaum, Veronica M.

    2012-02-01

    We have studied reactions of small dehydrogenated polycyclic aromatic hydrocarbon anions with neutral species of interstellar relevance. Reaction rate constants are measured at 300 K for the reactions of phenide (C6H- 5), naphthalenide (C10H- 7), and anthracenide (C14H- 9) with atomic H, H2, and D2 using a flowing afterglow-selected ion flow tube instrument. Reaction rate constants of phenide with neutral molecules (CO, O2, CO2, N2O, C2H2, CH3OH, CH3CN, (CH3)2CO, CH3CHO, CH3Cl, and (CH3CH2)2O) are also measured under the same conditions. Experimental measurements are accompanied by ab initio calculations to provide insight into reaction pathways and enthalpies. Our measured reaction rate constants should prove useful in the modeling of astrophysical environments, particularly when applied to dense regions of the interstellar and circumstellar medium.

  18. Age differences in emotional reactions: arousal and age-relevance count.

    Science.gov (United States)

    Streubel, Berit; Kunzmann, Ute

    2011-12-01

    Recent findings suggest positivity effects in older adults' attention and memory, but few studies have examined such effects on the level of emotional reactivity. In this study, 52 young and 52 older adults rated 172 pictures of the International Affective Picture System, differing in arousal and age-relevance, in terms of valence and discrete emotions. Age differences in the ratio of pleasantness reactions to pleasant pictures vs. unpleasantness reactions to unpleasant pictures as well as age differences in absolute levels of unpleasantness and pleasantness reactions suggest that positivity effects in older adults' subjective emotional reactions are reduced under high arousal. There is also evidence that positivity effects may be restricted to stimuli with low relevance in old age.

  19. Probing the Rate-Determining Step of the Claisen-Schmidt Condensation by Competition Reactions

    Science.gov (United States)

    Mak, Kendrew K. W.; Chan, Wing-Fat; Lung, Ka-Ying; Lam, Wai-Yee; Ng, Weng-Cheong; Lee, Siu-Fung

    2007-01-01

    Competition experiments are a useful tool for preliminary study of the linear free energy relationship of organic reactions. This article describes a physical organic experiment for upper-level undergraduates to identify the rate-determining step of the Claisen-Schmidt condensation of benzaldehyde and acetophenone by studying the linear free…

  20. Densities of accessible final states for multi-step compound reactions

    International Nuclear Information System (INIS)

    Maoming De; Guo Hua

    1993-01-01

    The densities of accessible final states for calculations of multi-step compound reactions are derived. The Pauli exclusion principle is taken into account in the calculations. The results are compared with a previous author's results and the effect of the Pauli exclusion principle is investigated. (Author)

  1. Fast-ion energy resolution by one-step reaction gamma-ray spectrometry

    DEFF Research Database (Denmark)

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

    2016-01-01

    The spectral broadening of γ-rays from fusion plasmas can be measured in high-resolution gamma-ray spectrometry (GRS). We derive weight functions that determine the observable velocity space and quantify the velocity-space sensitivity of one-step reaction high-resolution GRS measurements in magne...

  2. A cascade reaction network mimicking the basic functional steps of acquired immune response

    Science.gov (United States)

    Han, Da; Wu, Cuichen; You, Mingxu; Zhang, Tao; Wan, Shuo; Chen, Tao; Qiu, Liping; Zheng, Zheng; Liang, Hao; Tan, Weihong

    2015-01-01

    Biological systems use complex ‘information processing cores’ composed of molecular networks to coordinate their external environment and internal states. An example of this is the acquired, or adaptive, immune system (AIS), which is composed of both humoral and cell-mediated components. Here we report the step-by-step construction of a prototype mimic of the AIS which we call Adaptive Immune Response Simulator (AIRS). DNA and enzymes are used as simple artificial analogues of the components of the AIS to create a system which responds to specific molecular stimuli in vitro. We show that this network of reactions can function in a manner which is superficially similar to the most basic responses of the vertebrate acquired immune system, including reaction sequences that mimic both humoral and cellular responses. As such, AIRS provides guidelines for the design and engineering of artificial reaction networks and molecular devices. PMID:26391084

  3. A cascade reaction network mimicking the basic functional steps of adaptive immune response.

    Science.gov (United States)

    Han, Da; Wu, Cuichen; You, Mingxu; Zhang, Tao; Wan, Shuo; Chen, Tao; Qiu, Liping; Zheng, Zheng; Liang, Hao; Tan, Weihong

    2015-10-01

    Biological systems use complex 'information-processing cores' composed of molecular networks to coordinate their external environment and internal states. An example of this is the acquired, or adaptive, immune system (AIS), which is composed of both humoral and cell-mediated components. Here we report the step-by-step construction of a prototype mimic of the AIS that we call an adaptive immune response simulator (AIRS). DNA and enzymes are used as simple artificial analogues of the components of the AIS to create a system that responds to specific molecular stimuli in vitro. We show that this network of reactions can function in a manner that is superficially similar to the most basic responses of the vertebrate AIS, including reaction sequences that mimic both humoral and cellular responses. As such, AIRS provides guidelines for the design and engineering of artificial reaction networks and molecular devices.

  4. A proposed abiotic reaction scheme for hydroxylamine and monochloramine under chloramination relevant drinking water conditions.

    Science.gov (United States)

    Wahman, David G; Speitel, Gerald E; Machavaram, Madhav V

    2014-09-01

    Drinking water monochloramine (NH2Cl) use may promote ammonia-oxidizing bacteria (AOB). AOB use (i) ammonia monooxygenase for biological ammonia (NH3) oxidation to hydroxylamine (NH2OH) and (ii) hydroxylamine oxidoreductase for NH2OH oxidation to nitrite. NH2Cl and NH2OH may react, providing AOB potential benefits and detriments. The NH2Cl/NH2OH reaction would benefit AOB by removing the disinfectant (NH2Cl) and releasing their growth substrate (NH3), but the NH2Cl/NH2OH reaction would also provide a possible additional inactivation mechanism besides direct NH2Cl reaction with cells. Because biological NH2OH oxidation supplies the electrons required for biological NH3 oxidation, the NH2Cl/NH2OH reaction provides a direct mechanism for NH2Cl to inhibit NH3 oxidation, starving the cell of reductant by preventing biological NH2OH oxidation. To investigate possible NH2Cl/NH2OH reaction implications on AOB, an understanding of the underlying abiotic reaction is first required. The present study conducted a detailed literature review and proposed an abiotic NH2Cl/NH2OH reaction scheme (RS) for chloramination relevant drinking water conditions (μM concentrations, air saturation, and pH 7-9). Next, RS literature based kinetics and end-products were evaluated experimentally between pHs 7.7 and 8.3, representing (i) the pH range for future experiments with AOB and (ii) mid-range pHs typically found in chloraminated drinking water. In addition, a (15)N stable isotope experiment was conducted to verify nitrous oxide and nitrogen gas production and their nitrogen source. Finally, the RS was slightly refined using the experimental data and an AQUASIM implemented kinetic model. A chloraminated drinking water relevant RS is proposed and provides the abiotic reaction foundation for future AOB biotic experiments. Published by Elsevier Ltd.

  5. Field theoretical approach to proton-nucleus reactions. I - One step inelastic scattering

    International Nuclear Information System (INIS)

    Eiras, A.; Kodama, T.; Nemes, M.C.

    1988-01-01

    In this work we obtain a closed form expression to the double differential cross section for one step proton-nucleus reaction within a field theoretical framework. Energy and momentum conservation as well as nuclear structure effects are consistently taken into account within the field theoretical eikonal approximation. In our formulation the kinematics of such reaction is not dominated by the free nucleon-nucleon cross section but a new factor which we call relativistic differential cross section in a Born Approximation. (author) [pt

  6. Particle-hole state densities for statistical multi-step compound reactions

    International Nuclear Information System (INIS)

    Oblozinsky, P.

    1986-01-01

    An analytical relation is derived for the density of particle-hole bound states applying the equidistant-spacing approximation and the Darwin-Fowler statistical method. The Pauli exclusion principle as well as the finite depth of the potential well are taken into account. The set of densities needed for calculations of multi-step compound reactions is completed by deriving the densities of accessible final states for escape and damping. (orig.)

  7. Elderly fallers enhance dynamic stability through anticipatory postural adjustments during a choice stepping reaction time

    Directory of Open Access Journals (Sweden)

    Romain Tisserand

    2016-11-01

    Full Text Available In the case of disequilibrium, the capacity to step quickly is critical to avoid falling for elderly. This capacity can be simply assessed through the choice stepping reaction time test (CSRT, where elderly fallers (F take longer to step than elderly non-fallers (NF. However, reasons why elderly F elongate their stepping time remain unclear. The purpose of this study is to assess the characteristics of anticipated postural adjustments (APA that elderly F develop in a stepping context and their consequences on the dynamic stability. 44 community-dwelling elderly subjects (20 F and 22 NF performed a CSRT where kinematics and ground reaction forces were collected. Variables were analyzed using two-way repeated measures ANOVAs. Results for F compared to NF showed that stepping time is elongated, due to a longer APA phase. During APA, they seem to use two distinct balance strategies, depending on the axis: in the anteroposterior direction, we measured a smaller backward movement and slower peak velocity of the center of pressure (CoP; in the mediolateral direction, the CoP movement was similar in amplitude and peak velocity between groups but lasted longer. The biomechanical consequence of both strategies was an increased margin of stability (MoS at foot-off, in the respective direction. By elongating their APA, elderly F use a safer balance strategy that prioritizes dynamic stability conditions instead of the objective of the task. Such a choice in balance strategy probably comes from muscular limitations and/or a higher fear of falling and paradoxically indicates an increased risk of fall.

  8. The asymmetric hetero-Diels-Alder reaction in the syntheses of biologically relevant compounds.

    Science.gov (United States)

    Eschenbrenner-Lux, Vincent; Kumar, Kamal; Waldmann, Herbert

    2014-10-13

    The hetero-Diels-Alder reaction is one of the most powerful transformations in the chemistry toolbox for the synthesis of aza- and oxa-heterocycles embodying multiple stereogenic centers. However, as compared to other cycloadditions, in particular the dipolar cycloadditions and the Diels-Alder reaction, the hetero-Diels-Alder reaction has been much less explored and exploited in organic synthesis. Nevertheless, this powerful transformation has opened up efficient and creative routes to biologically relevant small molecules and different natural products which contain six-membered oxygen or nitrogen ring systems. Recent developments in this field, in particular in the establishment of enantioselectively catalyzed hetero-Diels-Alder cycloadditions steered by a plethora of different catalysts and the application of the resulting small molecules in chemical biology and medicinal chemistry research, are highlighted in this Minireview. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Cross section measurements of proton capture reactions on Se isotopes relevant to the astrophysical p process

    Science.gov (United States)

    Foteinou, V.; Harissopulos, S.; Axiotis, M.; Lagoyannis, A.; Provatas, G.; Spyrou, A.; Perdikakis, G.; Zarkadas, Ch.; Demetriou, P.

    2018-03-01

    Cross sections of proton capture reactions on 74Se, 78Se, and 80Se have been measured at incident beam energies from 2 to 6 MeV, 1.7 to 3 MeV, and 1.5 to 3.5 MeV, respectively. In the case of Se,8078, cross sections were obtained from in-beam γ -angular distribution measurements, whereas for the 74Se isotope they were derived from off-beam activity measurements. The measured cross sections were compared with calculations performed with the nuclear reaction code talys (version 1.6). A good agreement between theory and experiment was found. Astrophysical S factors and reaction rates deduced from the experimental and calculated cross sections were also compared and the impact of different nuclear ingredients in the calculations on the reaction rates was investigated. It was found that, for certain combinations of nuclear input models, the reaction rates obtained at temperatures relevant to p -process nucleosynthesis differ by a factor 2 at the most, differences that are well within the acceptable deviations of calculated p -nuclei abundances and observations.

  10. Growth of Fullerene Fragments Using the Diels-Alder Cycloaddition Reaction: First Step towards a C60 Synthesis by Dimerization

    Directory of Open Access Journals (Sweden)

    Julio A. Alonso

    2013-02-01

    Full Text Available Density Functional Theory has been used to model the Diels-Alder reactions of the fullerene fragments triindenetriphenilene and pentacyclopentacorannulene with ethylene and 1,3-butadiene. The purpose is to prove the feasibility of using Diels-Alder cycloaddition reactions to grow fullerene fragments step by step, and to dimerize fullerene fragments, as a way to obtain C60. The dienophile character of the fullerene fragments is dominant, and the reaction of butadiene with pentacyclopentacorannulene is favored.

  11. Roles of multi-step transfer in fusion process induced by heavy-ion reactions

    International Nuclear Information System (INIS)

    Imanishi, B.; Oertzen, W. von.

    1993-06-01

    In nucleus-nucleus collisions of the systems, 12 C+ 13 C and 13 C+ 16 O- 12 C+ 17 O, the effects of the multi-step transfers and inelastic excitations on the fusion cross sections are investigated in the framework of the coupled-reaction-channel (CRC) method. Strong CRC effects of the multi-step processes are observed. Namely, the valence neutron in 13 C or 17 O plays an important role in the enhancement of the fusion. The potential barrier is effectively lowered with the formation of the covalent molecule of the configuration, 12 C+n+ 12 C or 12 C+n+ 16 O. In the analyses of the system 12 C+ 13 C, however, it is still required to introduce core-core optical potential of lower barrier height in the state of the positive total parity. This could be due to the neck formation with the nucleons contained in two core nuclei. (author)

  12. Neutron-induced reactions relevant for Inertial-Cofinement Fusion Experiments

    Science.gov (United States)

    Boswell, Melissa; Devlin, Mathew; Fotiadis, Nikolaos; Merrill, Frank; Nelson, Ronald; Tonchev, Anton

    2014-09-01

    The typical ignition experiment at the National Ignition Facility ablatively implodes a plastic capsule filled with DT fuel, generating a high flux of 14-MeV neutrons from the d(t,n) α reaction. There is some spread in the energy of these primary 14-MeV neutrons, which is mainly attributable to Doppler shifting from the relative thermal motion of the burning DT fuel. Neutrons created during this reaction have 5--10% chance of scattering before escaping the fuel assembly, losing some fraction of their energy in the scattering process. Neutrons emerging with an energy greater than the reaction energy are generated by a two-step process where neutrons first transfer momentum to a deuteron or tritium ion, these enhanced energy ions then fuse in flight to produce higher energy neutrons; some of these neutrons have energies in excess of 30 MeV. Measuring the fluencies of both the low- and high-energy neutrons is a powerful mechanism for studying the properties of the fuel assembly, and the various parameters important to inertial confinement fusion. We have developed a number of tools to measure the spectral characteristics of the NIF neutron spectrum. Most of these methods rely on exploiting the energy dependence of (n, γ), (n,2n), (n,3n) and (n,p) reactions on a variety o.

  13. Spiro annulation of cage polycycles via Grignard reaction and ring-closing metathesis as key steps

    Directory of Open Access Journals (Sweden)

    Sambasivarao Kotha

    2015-08-01

    Full Text Available A simple synthetic strategy to C2-symmetric bis-spiro-pyrano cage compound 7 involving ring-closing metathesis is reported. The hexacyclic dione 10 was prepared from simple and readily available starting materials such as 1,4-naphthoquinone and cyclopentadiene. The synthesis of an unprecedented octacyclic cage compound through intramolecular Diels–Alder (DA reaction as a key step is described. The structures of three new cage compounds 7, 12 and 18 were confirmed by single crystal X-ray diffraction studies.

  14. Evaluating the fall risk among elderly population by choice step reaction test

    Directory of Open Access Journals (Sweden)

    Wang D

    2016-08-01

    Full Text Available Donghai Wang,1 Jian Zhang,1 Yuliang Sun,2 Wenfei Zhu,2 Shiliu Tian,1 Yu Liu1 1Key Laboratory of Exercise and Health Sciences of the Ministry of Education, Shanghai University of Sport, Shanghai, People’s Republic of China; 2School of Physical Education, Shaanxi Normal University, Xian, People’s Republic of China Abstract: Falls during daily activities are often associated with injuries and physical disabilities, thereby affecting quality of life among elder adults. Balance control, which is crucial in avoiding falls, is composed of two elements: muscle strength and central nervous system (CNS control. A number of studies have reported that reduced muscle strength raises the risk of falling. However, to date there has been only limited research focused on the relationship between fall risk and the CNS. This study aimed to investigate the relationship between CNS and risk of falling among the elderly. A total of 140 elderly people (92 females and 48 males were divided into faller and nonfaller groups based on questionnaire responses concerning falls in their daily life. Participants undertook a choice step reaction test in which they were required to respond to random visual stimuli using foot movements as fast as possible in the left or right directions. Response time was quantified as premotor time (PMT and motor time (MT. In addition, the participants’ electromyography data were recorded during the choice step reaction test. A maximal isokinetic torque test was also performed. PMT was greater in the fallers than in the nonfallers group. There was a significant difference between fall status and direction on PMT. PMT of the left limb in nonfallers was faster than the right, but in fallers there was no difference between left and right limbs. A similar phenomenon was also observed for MT. There were significant differences between fallers and nonfallers in maximum isokinetic torque at knee and ankle joints. The correct rate of PMT was

  15. Intraindividual Stepping Reaction Time Variability Predicts Falls in Older Adults With Mild Cognitive Impairment.

    Science.gov (United States)

    Bunce, David; Haynes, Becky I; Lord, Stephen R; Gschwind, Yves J; Kochan, Nicole A; Reppermund, Simone; Brodaty, Henry; Sachdev, Perminder S; Delbaere, Kim

    2017-06-01

    Reaction time measures have considerable potential to aid neuropsychological assessment in a variety of health care settings. One such measure, the intraindividual reaction time variability (IIV), is of particular interest as it is thought to reflect neurobiological disturbance. IIV is associated with a variety of age-related neurological disorders, as well as gait impairment and future falls in older adults. However, although persons diagnosed with Mild Cognitive Impairment (MCI) are at high risk of falling, the association between IIV and prospective falls is unknown. We conducted a longitudinal cohort study in cognitively intact (n = 271) and MCI (n = 154) community-dwelling adults aged 70-90 years. IIV was assessed through a variety of measures including simple and choice hand reaction time and choice stepping reaction time tasks (CSRT), the latter administered as a single task and also with a secondary working memory task. Logistic regression did not show an association between IIV on the hand-held tasks and falls. Greater IIV in both CSRT tasks, however, did significantly increase the risk of future falls. This effect was specific to the MCI group, with a stronger effect in persons exhibiting gait, posture, or physiological impairment. The findings suggest that increased stepping IIV may indicate compromised neural circuitry involved in executive function, gait, and posture in persons with MCI increasing their risk of falling. IIV measures have potential to assess neurobiological disturbance underlying physical and cognitive dysfunction in old age, and aid fall risk assessment and routine care in community and health care settings. © The Author 2016. Published by Oxford University Press on behalf of The Gerontological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  16. Bilateral ground reaction forces and joint moments for lateral sidestepping and crossover stepping tasks

    Science.gov (United States)

    Kuntze, Gregor; Sellers, William I.; Mansfield, Neil

    2009-01-01

    Racquet sports have high levels of joint injuries suggesting the joint loads during play may be excessive. Sports such as badminton employ lateral sidestepping (SS) and crossover stepping (XS) movements which so far have not been described in terms of biomechanics. This study examined bilateral ground reaction forces and three dimensional joint kinetics for both these gaits in order to determine the demands of the movements on the leading and trailing limb and predict the contribution of these movements to the occurrence of overuse injury of the lower limbs. A force platform and motion-analysis system were used to record ground reaction forces and track marker trajectories of 9 experienced male badminton players performing lateral SS, XS and forward running tasks at a controlled speed of 3 m·s-1 using their normal technique. Ground reaction force and kinetic data for the hip, knee and ankle were analyzed, averaged across the group and the biomechanical variables compared. In all cases the ground reaction forces and joint moments were less than those experienced during moderate running suggesting that in normal play SS and XS gaits do not lead to high forces that could contribute to increased injury risk. Ground reaction forces during SS and XS do not appear to contribute to the development of overuse injury. The distinct roles of the leading and trailing limb, acting as a generator of vertical force and shock absorber respectively, during the SS and XS may however contribute to the development of muscular imbalances which may ultimately contribute to the development of overuse injury. However it is still possible that faulty use of these gaits might lead to high loads and this should be the subject of future work. Key pointsGround reaction forces and joint moments during lateral stepping are smaller in magnitude than those experienced during moderate running.Force exposure in SS and XS gaits in normal play does not appear to contribute to the development of

  17. BILATERAL GROUND REACTION FORCES AND JOINT MOMENTS FOR LATERAL SIDESTEPPING AND CROSSOVER STEPPING TASKS

    Directory of Open Access Journals (Sweden)

    William I. Sellers

    2009-03-01

    Full Text Available Racquet sports have high levels of joint injuries suggesting the joint loads during play may be excessive. Sports such as badminton employ lateral sidestepping (SS and crossover stepping (XS movements which so far have not been described in terms of biomechanics. This study examined bilateral ground reaction forces and three dimensional joint kinetics for both these gaits in order to determine the demands of the movements on the leading and trailing limb and predict the contribution of these movements to the occurrence of overuse injury of the lower limbs. A force platform and motion-analysis system were used to record ground reaction forces and track marker trajectories of 9 experienced male badminton players performing lateral SS, XS and forward running tasks at a controlled speed of 3 m·s-1 using their normal technique. Ground reaction force and kinetic data for the hip, knee and ankle were analyzed, averaged across the group and the biomechanical variables compared. In all cases the ground reaction forces and joint moments were less than those experienced during moderate running suggesting that in normal play SS and XS gaits do not lead to high forces that could contribute to increased injury risk. Ground reaction forces during SS and XS do not appear to contribute to the development of overuse injury. The distinct roles of the leading and trailing limb, acting as a generator of vertical force and shock absorber respectively, during the SS and XS may however contribute to the development of muscular imbalances which may ultimately contribute to the development of overuse injury. However it is still possible that faulty use of these gaits might lead to high loads and this should be the subject of future work

  18. Benzoylformate analogues exhibit differential rate-determining steps in the benzoylformate decarboxylase reaction

    International Nuclear Information System (INIS)

    Garcia, G.A.; Weiss, P.M.; Cook, P.F.; Kenyon, G.L.; Cleland, W.W.

    1987-01-01

    Benzoylformate decarboxylase from Pseudomonas putida is a thiamine pyrophosphate (TPP)-dependent enzyme which converts benzoylformate to benzaldehyde and CO 2 . The rate-determining step(s) in the benzoylformate decarboxylase reaction for a series of substituted benzoylformates (p-CH 3 O, p-CH 3 , p-Cl, and m-F) were studied using solvent deuterium and 13 C kinetic isotope effects. The normal substrate was found to have two partially rate-determining steps; initial tetrahedral adduct formation (D 2 O-sensitive) and decarboxylation ( 13 C-sensitive). D 2 O and 13 C isotope effects indicate that electron-withdrawing substituents (p-Cl and m-F) remove the rate dependence upon decarboxylation such that only a D 2 O effect on (V/K) is observed. Conversely, electron-donating substituents increase the rate-dependence upon decarboxylation such that a larger 13 (V/K) is seen while the D 2 O effects on (V) and (V/K) are not dramatically different from those for benzoylformate. All of the data are consistent with substituent stabilization or destabilization of the carbanionic intermediate formed upon decarboxylation

  19. Assessment of PDF Micromixing Models Using DNS Data for a Two-Step Reaction

    Science.gov (United States)

    Tsai, Kuochen; Chakrabarti, Mitali; Fox, Rodney O.; Hill, James C.

    1996-11-01

    Although the probability density function (PDF) method is known to treat the chemical reaction terms exactly, its application to turbulent reacting flows have been overshadowed by the ability to model the molecular mixing terms satisfactorily. In this study, two PDF molecular mixing models, the linear-mean-square-estimation (LMSE or IEM) model and the generalized interaction-by-exchange-with-the-mean (GIEM) model, are compared with the DNS data in decaying turbulence with a two-step parallel-consecutive reaction and two segregated initial conditions: ``slabs" and ``blobs". Since the molecular mixing model is expected to have a strong effect on the mean values of chemical species under such initial conditions, the model evaluation is intended to answer the following questions: Can the PDF models predict the mean values of chemical species correctly with completely segregated initial conditions? (2) Is a single molecular mixing timescale sufficient for the PDF models to predict the mean values with different initial conditions? (3) Will the chemical reactions change the molecular mixing timescales of the reacting species enough to affect the accuracy of the model's prediction for the mean values of chemical species?

  20. One step gold (bio)functionalisation based on CS{sub 2}-amine reaction

    Energy Technology Data Exchange (ETDEWEB)

    Almeida, Ines [Centro de Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, Ed. C8, Campo Grande, 1749-016 Lisboa (Portugal); Cascalheira, Antonio C. [Lumisense, Lda, Campus Faculdade de Ciencias da Universidade de Lisboa, Ed. ICAT, Campo Grande, 1749-016 Lisboa (Portugal); Viana, Ana S., E-mail: anaviana@fc.ul.p [Centro de Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, Ed. C8, Campo Grande, 1749-016 Lisboa (Portugal)

    2010-12-01

    Dithiocarbamates have been regarded as alternative anchor groups to thiols on gold surfaces, and claimed to be formed in situ through the reaction between secondary amines and carbon disulphide. In this paper, we further exploit this methodology for a convenient one step biomolecule immobilisation onto gold surfaces. First, the reactivity between CS{sub 2} and electroactive compounds containing amines, primary (dopamine), secondary (epinephrine), and an amino acid (tryptophan) has been investigated by electrochemical methods. Cyclic voltammetric characterisation of the modified electrodes confirmed the immobilisation of all the target compounds, allowing the estimation of their surface concentration. The best result was obtained with epinephrine, a secondary amine, for which a typical quasi-reversible behaviour of surface confined electroactive species could be clearly depicted. Electrochemical reductive desorption studies enabled to infer on the extent of the reaction and on the relative stability of the generated monolayers. Bio-functionalisation studies have been accomplished through the reaction of CS{sub 2} with glucose oxidase in aqueous medium, and the catalytic activity of the immobilised enzyme was evaluated towards glucose, by electrochemical methods in the presence of a redox mediator. Scanning tunnelling microscopy (STM) and Atomic force microscopy (AFM) were used respectively, to characterize the gold electrodes and Glucose Oxidase coverage and distribution on the modified surfaces.

  1. One step synthesis of chlorine-free Pt/Nitrogen-doped graphene composite for oxygen reduction reaction

    KAUST Repository

    Varga, Tamá s; Varga, Á gnes Tí mea; Ballai, Gergő; Haspel, Henrik; Kukovecz, Á kos; Kó nya, Z.

    2018-01-01

    Chlorine-free Platinum/nitrogen-doped graphene oxygen reduction reaction catalysts were synthesized by a one step method of annealing a mixture of platinum acetylacetonate and graphene oxide under ammonia atmosphere. Nanoparticles with close

  2. The reaction rate for dissociative adsorption of N-2 on stepped Ru(0001): Six-dimensional quantum calculations

    DEFF Research Database (Denmark)

    van Harrevelt, Rob; Honkala, Johanna Karoliina; Nørskov, Jens Kehlet

    2005-01-01

    Quantum-mechanical calculations of the reaction rate for dissociative adsorption of N-2 on stepped Ru(0001) are presented. Converged six-dimensional quantum calculations for this heavy-atom reaction have been performed using the multiconfiguration time-dependent Hartree method. A potential...

  3. 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...

  4. A trifunctional mesoporous silica-based, highly active catalyst for one-pot, three-step cascade reactions.

    Science.gov (United States)

    Biradar, Ankush V; Patil, Vijayshinha S; Chandra, Prakash; Doke, Dhananjay S; Asefa, Tewodros

    2015-05-18

    We report the synthesis of a trifunctional catalyst containing amine, sulphonic acid and Pd nanoparticle catalytic groups anchored on the pore walls of SBA-15. The catalyst efficiently catalyzes one-pot three-step cascade reactions comprising deacetylation, Henry reaction and hydrogenation, giving up to ∼100% conversion and 92% selectivity to the final product.

  5. Effect of one step KOH activation and CaO modified carbon in transesterification reaction

    Science.gov (United States)

    Yacob, Abd Rahim; Zaki, Muhammad Azam Muhammad

    2017-11-01

    In this work, one step activation was introduced using potassium hydroxide (KOH) and calcium oxide (CaO) modified palm kernel shells. Various concentration of calcium oxide was used as catalyst while maintaining the same concentration of potassium hydroxide to activate and impregnate the palm kernel shell before calcined at 500°C for 5 hours. All the prepared samples were characterized using Fourier Transform Infrared (FTIR) and Field Emission Scanning Electron Microscope (FESEM). FTIR analysis of raw palm kernel shell showed the presence of various functional groups. However, after activation, most of the functional groups were eliminated. The basic strength of the prepared samples were determined using back titration method. The samples were then used as base heterogeneous catalyst for the transesterification reaction of rice bran oil with methanol. Analysis of the products were performed using Gas Chromatography Flame Ionization Detector (GC-FID) to calculate the percentage conversion of the biodiesel products. This study shows, as the percentage of one step activation potassium and calcium oxide doped carbon increases thus, the basic strength also increases followed by the increase in biodiesel production. Optimization study shows that the optimum biodiesel production was at 8 wt% catalyst loading, 9:1 methanol: oil molar ratio at 65°C and 6 hours which gives a conversion up to 95%.

  6. Elementary Steps of Syngas Reactions on Mo2C(001): Adsorption Thermochemistry and Bond Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Medford, Andrew

    2012-02-16

    Density functional theory (DFT) and ab initio thermodynamics are applied in order to investigate the most stable surface and subsurface terminations of Mo{sub 2}C(001) as a function of chemical potential and in the presence of syngas. The Mo-terminated (001) surface is then used as a model surface to evaluate the thermochemistry and energetic barriers for key elementary steps in syngas reactions. Adsorption energy scaling relations and Broensted-Evans-Polanyi relationships are established and used to place Mo{sub 2}C into the context of transition metal surfaces. The results indicate that the surface termination is a complex function of reaction conditions and kinetics. It is predicted that the surface will be covered by either C{sub 2}H{sub 2} or O depending on conditions. Comparisons to transition metals indicate that the Mo-terminated Mo{sub 2}C(001) surface exhibits carbon reactivity similar to transition metals such as Ru and Ir, but is significantly more reactive towards oxygen.

  7. Investigation of some biologically relevant redox reactions using electrochemical mass spectrometry interfaced by desorption electrospray ionization.

    Science.gov (United States)

    Lu, Mei; Wolff, Chloe; Cui, Weidong; Chen, Hao

    2012-04-01

    Recently we have shown that, as a versatile ionization technique, desorption electrospray ionization (DESI) can serve as a useful interface to combine electrochemistry (EC) with mass spectrometry (MS). In this study, the EC/DESI-MS method has been further applied to investigate some aqueous phase redox reactions of biological significance, including the reduction of peptide disulfide bonds and nitroaromatics as well as the oxidation of phenothiazines. It was found that knotted/enclosed disulfide bonds in the peptides apamin and endothelin could be electrochemically cleaved. Subsequent tandem MS analysis of the resulting reduced peptide ions using collision-induced dissociation (CID) and electron-capture dissociation (ECD) gave rise to extensive fragment ions, providing a fast protocol for sequencing peptides with complicated disulfide bond linkages. Flunitrazepam and clonazepam, a class of nitroaromatic drugs, are known to undergo reduction into amines which was proposed to involve nitroso and N-hydroxyl intermediates. Now in this study, these corresponding intermediate ions were successfully intercepted and their structures were confirmed by CID. This provides mass spectrometric evidence for the mechanism of the nitro to amine conversion process during nitroreduction, an important redox reaction involved in carcinogenesis. In addition, the well-known oxidation reaction of chlorpromazine was also examined. The putative transient one-electron transfer product, the chlorpromazine radical cation (m/z 318), was captured by MS, for the first time, and its structure was also verified by CID. In addition to these observations, some features of the DESI-interfaced electrochemical mass spectrometry were discussed, such as simple instrumentation and the lack of background signal. These results further demonstrate the feasibility of EC/DESI-MS for the study of the biology-relevant redox chemistry and would find applications in proteomics and drug development research.

  8. One-step versus two-step mechanism of Diels-Alder reaction of 1-chloro-1-nitroethene with cyclopentadiene and furan.

    Science.gov (United States)

    Jasiński, Radomir

    2017-08-01

    DFT computational study shows that Diels-Alder (DA) reactions of 1-chloro-1-nitroethene with cyclopentadiene and furan have polar nature. However, their mechanism is substantially different. In particular, 1-chloro-1-nitroethene react with cyclopentadiene according to one-step mechanism. In the same time, more favourable channel associated with the P-DA reaction between furan and 1-chloro-1-nitroethene is a domino process, that comprises an initial hetero-Diels-Alder reaction yielding a [2+4] cycloadduct, which experiences a subsequent [3,3] sigmatropic shift to yield the expected formal [4+2] cycloadduct. This is a consequence of more polar nature of reaction, due to higher nucleophilicity of furan in comparison to cyclopentadiene. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Step-by-Step Simulation of Radiation of Radiation Chemistry Using Green Functions for Diffusion-Influenced Reactions

    Science.gov (United States)

    Plante, Ianik; Cucinotta, Francis A.

    2011-01-01

    The irradiation of biological systems leads to the formation of radiolytic species such as H(raised dot), (raised dot)OH, H2, H2O2, e(sup -)(sub aq), etc.[1]. These species react with neighboring molecules, which result in damage in biological molecules such as DNA. Radiation chemistry is there for every important to understand the radiobiological consequences of radiation[2]. In this work, we discuss an approach based on the exact Green Functions for diffusion-influenced reactions which may be used to simulate radiation chemistry and eventually extended to study more complex systems, including DNA.

  10. Revisiting the relevance of using a constant voltage step to improve electrochemical performances of Li-rich lamellar oxides

    Science.gov (United States)

    Pradon, A.; Caldes, M. T.; Petit, P.-E.; La Fontaine, C.; Elkaim, E.; Tessier, C.; Ouvrard, G.; Dumont, E.

    2018-03-01

    A Li-rich lamellar oxide was cycled at high potential and the relevance of using a constant voltage step (CVS) at the end of the charge, needed for industrial application, was investigated by electrochemical performance, X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). Electrochemical studies at 4.7 and 4.5 V with and without CVS showed that capacity and voltage fading occurred mostly when cells operated at high potential. After cycling, 3D-type defects involving transition metals trapped in lithium layer were observed by HRTEM into the electrode bulk. These defects are responsible for the voltage fading. XRD microstrain parameter was used to evaluate defects rate in aged materials subjected to a CVS, showing more 3D-type defects when cycled at 4.7 V than at 4.5 V. The time spent at high potential at the end of the charge as well as the value of the upper potential limit, are both relevant parameters to voltage decay. The use of a CVS at the end of the charge needs at the same time, a reduced upper potential window in order to minimize 3D-type defects occurrence. Unfortunately, this approach is still not sufficient to prevent voltage fading.

  11. The coordination chemistry of nitrosyl in cyanoferrates. An exhibit of bioinorganic relevant reactions.

    Science.gov (United States)

    Olabe, José A

    2008-07-28

    Sodium nitroprusside (SNP, Na(2)[Fe(CN)(5)(NO)].2H(2)O) is a widely used NO-donor hypotensive agent, containing the formally described nitrosonium (NO(+)) ligand, which may be redox-interconverted to the corresponding one-electron (NO) and two-electron (NO(-)/HNO) reduced bound species. Thus, the chemistry of the three nitrosyl ligands may be explored with adequate, biologically relevant substrates. The nitrosonium complex, [Fe(CN)(5)(NO)](2-), is formed through a reductive nitrosylation reaction of [Fe(III)(CN)(5)(H(2)O)](2-) with NO, or, alternatively, through the coordination of NO(2)(-) to [Fe(II)(CN)(5)(H(2)O)](3-) and further proton-assisted dehydration. It is extremely inert toward NO(+)-dissociation, and behaves as an electrophile toward different bases: OH(-), amines, thiolates, etc. Also, SNP releases NO upon UV-vis photo-activation, with formation of [Fe(III)(CN)(5)(H(2)O)](2-). The more electron rich [Fe(CN)(5)(NO)](3-) may be prepared from [Fe(II)(CN)(5)(H(2)O)](3-) and NO, and is also highly inert toward the dissociation of NO (k = 1.6 x 10(-5) s(-1), 25.0 degrees C, pH 10.2). It reacts with O(2) leading to SNP, with the intermediacy of a peroxynitrite adduct. The [Fe(CN)(5)(NO)](3-) ion is labile toward the release of trans-cyanide, forming the [Fe(CN)(4)(NO)](2-) ion. Both complexes exist in a pH-dependent equilibrium, and decompose thermally in the hours time scale, releasing cyanides and NO. The latter may further bind to [Fe(CN)(4)(NO)](2-) with formation of a singlet dinitrosyl species, [Fe(CN)(4)(NO)(2)](2-), which in turn is unstable toward disproportionation into SNP and N(2)O, and toward the parallel formation of a tetrahedral paramagnetic dinitrosyl compound, [Fe(CN)(2)(NO)(2)]. Emerging studies with the putative nitroxyl complex, [Fe(CN)(5)(HNO)](3-), should allow for a complete picture of the three nitrosyl ligands in the same pentacyano fragment. The present Perspective, based on an adequate characterization of structural and

  12. Mass transfer with complex chemical reactions in gas–liquid systems : two-step reversible reactions with unit stoichiometric and kinetic orders

    NARCIS (Netherlands)

    Vas Bhat, R.D.; Kuipers, J.A.M.; Versteeg, G.F.

    2000-01-01

    An absorption model to study gas–liquid mass transfer accompanied by reversible two-step reactions in the liquid phase has been presented. This model has been used to determine mass transfer rates, enhancement factors and concentration profiles over a wide range of process conditions. Although

  13. Mass transfer with complex chemical reactions in gas-liquid systems: two-step reversible reactions with unit stoichiometric and kinetic orders

    NARCIS (Netherlands)

    Vas bhat, R.D.; Kuipers, J.A.M.; Versteeg, Geert

    2000-01-01

    An absorption model to study gas¿liquid mass transfer accompanied by reversible two-step reactions in the liquid phase has been presented. This model has been used to determine mass transfer rates, enhancement factors and concentration profiles over a wide range of process conditions. Although

  14. Estimating reaction rate constants from a two-step reaction: a comparison between two-way and three-way methods

    NARCIS (Netherlands)

    Bijlsma, S.; Smilde, A. K.

    2000-01-01

    In this paper, two different spectral datasets are used in order to estimate reaction rate constants using different algorithms. Dataset 1 consists of short-wavelength near-infrared (SW NIR) spectra taken in time of the two-step epoxidation of 2,5-di-tert-butyl-1,4-benzoquinone using tert-butyl

  15. Stepping reaction time and gait adaptability are significantly impaired in people with Parkinson's disease: Implications for fall risk.

    Science.gov (United States)

    Caetano, Maria Joana D; Lord, Stephen R; Allen, Natalie E; Brodie, Matthew A; Song, Jooeun; Paul, Serene S; Canning, Colleen G; Menant, Jasmine C

    2018-02-01

    Decline in the ability to take effective steps and to adapt gait, particularly under challenging conditions, may be important reasons why people with Parkinson's disease (PD) have an increased risk of falling. This study aimed to determine the extent of stepping and gait adaptability impairments in PD individuals as well as their associations with PD symptoms, cognitive function and previous falls. Thirty-three older people with PD and 33 controls were assessed in choice stepping reaction time, Stroop stepping and gait adaptability tests; measurements identified as fall risk factors in older adults. People with PD had similar mean choice stepping reaction times to healthy controls, but had significantly greater intra-individual variability. In the Stroop stepping test, the PD participants were more likely to make an error (48 vs 18%), took 715 ms longer to react (2312 vs 1517 ms) and had significantly greater response variability (536 vs 329 ms) than the healthy controls. People with PD also had more difficulties adapting their gait in response to targets (poorer stepping accuracy) and obstacles (increased number of steps) appearing at short notice on a walkway. Within the PD group, higher disease severity, reduced cognition and previous falls were associated with poorer stepping and gait adaptability performances. People with PD have reduced ability to adapt gait to unexpected targets and obstacles and exhibit poorer stepping responses, particularly in a test condition involving conflict resolution. Such impaired stepping responses in Parkinson's disease are associated with disease severity, cognitive impairment and falls. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. An Ugi Reaction Incorporating a Redox-Neutral Amine C-H Functionalization Step.

    Science.gov (United States)

    Zhu, Zhengbo; Seidel, Daniel

    2016-02-19

    Pyrrolidine and 1,2,3,4-tetrahydroisoquinoline (THIQ) undergo redox-neutral α-amidation with concurrent N-alkylation upon reaction with aromatic aldehydes and isocyanides. Reactions are promoted by acetic acid and represent a new variant of the Ugi reaction.

  17. The association between choice stepping reaction time and falls in older adults--a path analysis model

    NARCIS (Netherlands)

    Pijnappels, M.A.G.M.; Delbaere, K.; Sturnieks, D.L.; Lord, S.R.

    2010-01-01

    Background: choice stepping reaction time (CSRT) is a functional measure that has been shown to significantly discriminate older fallers from non-fallers. Objective: to investigate how physiological and cognitive factors mediate the association between CSRT performance and multiple falls by use of

  18. A Convergent Enantioselective Total Synthesis of (-)-Perhydrohistrionicotoxin with an Intramolecular Imino Ene-type Reaction as a Key Step

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Hagberg, Lars

    1998-01-01

    A convergent enantioselective total synthesis of the neurotoxic spirocyclic alkaloid (-)-perhydrohistrionicotoxin (2) is described. A Lewis acid-mediated intramolecular imine ene-type reaction was used for the key spirocyclisation step (14 to 3, with 3 being obtained as a single diastereoisomer...

  19. Cintichem modified process - {sup 99}Mo precipitation step: application of statistical analysis tools over the reaction parameters

    Energy Technology Data Exchange (ETDEWEB)

    Teodoro, Rodrigo; Dias, Carla R.B.R.; Osso Junior, Joao A., E-mail: jaosso@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Fernandez Nunez, Eutimio Gustavo [Universidade de Sao Paulo (EP/USP), SP (Brazil). Escola Politecnica. Dept. de Engenharia Quimica

    2011-07-01

    Precipitation of {sup 99}Mo by {alpha}-benzoin oxime ({alpha}-Bz) is a standard precipitation method for molybdenum due the high selectivity of this agent. Nowadays, statistical analysis tools have been employed in analytical systems to prove its efficiency and feasibility. IPEN has a project aiming the production of {sup 99}Mo by the fission of {sup 235}U route. The processing uses as the first step the precipitation of {sup 99}Mo with {alpha}-Bz. This precipitation step involves many key reaction parameters. The aim of this work is based on the development of the already known acidic route to produce {sup 99}Mo as well as the optimization of the reactional parameters applying statistical tools. In order to simulate {sup 99}Mo precipitation, the study was conducted in acidic media using HNO{sub 3}, {alpha}Bz as precipitant agent and NaOH /1%H{sub 2}O{sub 2} as dissolver solution. Then, a Mo carrier, KMnO{sub 4} solutions and {sup 99}Mo tracer were added to the reaction flask. The reactional parameters ({alpha}-Bz/Mo ratio, Mo carrier, reaction time and temperature, and cooling reaction time before filtration) were evaluated under a fractional factorial design of resolution V. The best values of each reactional parameter were determined by a response surface statistical planning. The precipitation and recovery yields of {sup 99}Mo were measured using HPGe detector. Statistical analysis from experimental data suggested that the reactional parameters {alpha}-Bz/Mo ratio, reaction time and temperature have a significant impact on {sup 99}Mo precipitation. Optimization statistical planning showed that higher {alpha}Bz/Mo ratios, room temperature, and lower reaction time lead to higher {sup 99}Mo yields. (author)

  20. Automatized Assessment of Protective Group Reactivity: A Step Toward Big Reaction Data Analysis.

    Science.gov (United States)

    Lin, Arkadii I; Madzhidov, Timur I; Klimchuk, Olga; Nugmanov, Ramil I; Antipin, Igor S; Varnek, Alexandre

    2016-11-28

    We report a new method to assess protective groups (PGs) reactivity as a function of reaction conditions (catalyst, solvent) using raw reaction data. It is based on an intuitive similarity principle for chemical reactions: similar reactions proceed under similar conditions. Technically, reaction similarity can be assessed using the Condensed Graph of Reaction (CGR) approach representing an ensemble of reactants and products as a single molecular graph, i.e., as a pseudomolecule for which molecular descriptors or fingerprints can be calculated. CGR-based in-house tools were used to process data for 142,111 catalytic hydrogenation reactions extracted from the Reaxys database. Our results reveal some contradictions with famous Greene's Reactivity Charts based on manual expert analysis. Models developed in this study show high accuracy (ca. 90%) for predicting optimal experimental conditions of protective group deprotection.

  1. [Academic discussion of adverse reaction of clinical trials of new traditional Chinese medicines and relevant influencing factors].

    Science.gov (United States)

    Wang, Wen-ping; Yu, Ming; Wang, Li; Jiang, Xi-ren; Li, Xiao-bin; Wang, Hua-wei; Cao, Ying; Liu, Kai; Huang, Lu-qi

    2015-01-01

    Data of clinical trial projects involved by clinical trial institutions certified by the State Food and Drug Administration from 2002 to November 2012 were collected to summarize adverse reactions in project summary/statistical reports, analyze the rate of adverse reactions of clinical trials of new traditional Chinese medicines and relevant influencing factors, and increase the awareness of the safety of new traditional Chinese medicines. A total of 73 050 cases in 209 projects of 14 specialties were collected, including 49 689 cases in the new traditional Chinese medicine group and 271 adverse reaction cases, with an incidence rate of adverse reactions at 0.55%. The adverse reaction rate in 3 months 0.63% for injection > 0.50% for oral. In the administration of only the test drug, the adverse reaction rate of patches was the highest (2.68%), whereas that of aerosols and suppositories was lowest (0). In the combined administration of the test drug and the simulation agent, the adverse reaction rate of external test patch + capsule was the highest (3.38%), whereas that of capsule + oral liquid, pills + granules, tablets + oral liquid, tablets + pills, tablet + capsule was the lowest (0). In the administration of only the test drug, the adverse reaction rate was 0.47%; In the combined administration with simulation agent (drug volume increase), the adverse reaction rate was 0.74%. Different doses caused adverse reaction different rates; The adverse reaction rate of drugs with whole-course dose between 1 100-1 200 g was the highest (3.36%), that for whole-course doses of 500-600, 900-1 000, 1 400-1 500, 1 600-1 700, 1 800-1 900 g was the lowest (0). In conclusion, the adverse reaction rate of new traditional Chinese medicines was still up to 0.55%, with the adverse reaction rate between 0.47% and 0.72% over the 11 years, without significant difference in each year. The adverse reaction rate was closely related to course of treatment, approach of administration

  2. Analytical total reaction cross-section calculations via Fermi-type functions. I. Fermi-step nuclear densities

    International Nuclear Information System (INIS)

    Abul-Magd, A.Y.; Talib aly al Hinai, M.

    2000-01-01

    In the framework of Glauber's multiple scattering theory we propose a closed form expression for the total nucleus-nucleus reaction cross-section. We adopt the Gaussian and the two-parameter Fermi step radial shapes to describe the nuclear density distributions of the projectile and the target, respectively. The present formula is used to study different systems over a wide energy range including low energy reactions, where the role of the Coulomb repulsion is taken into account. The present predictions reasonably reproduce experiment

  3. On correctness of some processing operations for two-step cascade intensities data from the (nth, 2γ) reaction

    International Nuclear Information System (INIS)

    Sukhovoj, A.M.; Khitrov, V.A.; Chol, Li

    2004-01-01

    An influence of some incorrectness of analysis on the level densities and radiative strength functions derived from the experimental γ spectra is considered. It was shown that the obtaining of reliable data from the reaction (n, 2γ) requires deriving dependence of the two-step cascade intensities on their primary transition energy. The influence of some conditions of an analysis of the experimental γ-spectra from the reaction ( 3 He, α) on the expected value of both level density and radiative strength functions was estimated. The ways to decrease these uncertainties are suggested

  4. Possible self-complexity and affective reactions to goal-relevant evaluation.

    Science.gov (United States)

    Niedenthal, P M; Setterlund, M B; Wherry, M B

    1992-07-01

    The complexity of people's self-concept appears to be inversely related to the intensity of their reactions to evaluative feedback about present goals and abilities (Linville, 1985, 1987). The idea that the complexity of individuals' possible self-concept similarly mediates reactions to feedback regarding future goals was investigated. Two preliminary studies suggested that complexity of the actual self only explains 20% to 30% of the variance in possible self-complexity. Three studies were conducted. Support was found for the idea that possible self-complexity mediates affective reactions to evaluative feedback about future goals and actual self-complexity mediates affective reactions to evaluative feedback about present goals. The findings underscore the independent roles of the organization of actual and possible self-concepts in affective processes.

  5. Experimental and theoretical data on ion-molecule-reactions relevant for plasma modelling

    International Nuclear Information System (INIS)

    Hansel, A.; Praxmarer, C.; Lindinger, W.

    1995-01-01

    Despite the fact that the rate coefficients of hundreds of ion-molecule-reactions have been published in the literature, much more data are required for the purpose of plasma modelling. Many ion molecule reactions have rate coefficients, k, as large as the collisional limiting value, k c , i.e. the rate coefficients k c at which ion-neutral collision complexes are formed are close to the actual rate coefficients observed. In the case of the interaction of an ion with a non polar molecule, k c , is determined by the Langevin limiting value k L being typically 10 -9 cm 3 s -1 . However, when ions react with polar molecules k c is predicted by the average dipole orientation (ADO) theory. These classical theories yield accurate rate coefficients at thermal and elevated temperatures for practically all proton transfer as well as for many charge transfer and hydrogen abstraction reactions. The agreement between experimental and calculated values is usually better than ±20% and in the case of proton transfer reactions the agreement seems to be even better as recent investigations have shown. Even the interaction of the permanent ion dipole with non polar and polar neutrals can be taken into account to predict reaction rate coefficients as has been shown very recently in reactions of the highly polar ion ArH 3 + with various neutrals

  6. A clinical decision support system algorithm for intravenous to oral antibiotic switch therapy: validity, clinical relevance and usefulness in a three-step evaluation study.

    Science.gov (United States)

    Akhloufi, H; Hulscher, M; van der Hoeven, C P; Prins, J M; van der Sijs, H; Melles, D C; Verbon, A

    2018-04-26

    To evaluate a clinical decision support system (CDSS) based on consensus-based intravenous to oral switch criteria, which identifies intravenous to oral switch candidates. A three-step evaluation study of a stand-alone CDSS with electronic health record interoperability was performed at the Erasmus University Medical Centre in the Netherlands. During the first step, we performed a technical validation. During the second step, we determined the sensitivity, specificity, negative predictive value and positive predictive value in a retrospective cohort of all hospitalized adult patients starting at least one therapeutic antibacterial drug between 1 and 16 May 2013. ICU, paediatric and psychiatric wards were excluded. During the last step the clinical relevance and usefulness was prospectively assessed by reports to infectious disease specialists. An alert was considered clinically relevant if antibiotics could be discontinued or switched to oral therapy at the time of the alert. During the first step, one technical error was found. The second step yielded a positive predictive value of 76.6% and a negative predictive value of 99.1%. The third step showed that alerts were clinically relevant in 53.5% of patients. For 43.4% it had already been decided to discontinue or switch the intravenous antibiotics by the treating physician. In 10.1%, the alert resulted in advice to change antibiotic policy and was considered useful. This prospective cohort study shows that the alerts were clinically relevant in >50% (n = 449) and useful in 10% (n = 85). The CDSS needs to be evaluated in hospitals with varying activity of infectious disease consultancy services as this probably influences usefulness.

  7. Intraindividual Stepping Reaction Time Variability Predicts Falls in Older Adults With Mild Cognitive Impairment

    OpenAIRE

    Bunce, D; Haynes, BI; Lord, SR; Gschwind, YJ; Kochan, NA; Reppermund, S; Brodaty, H; Sachdev, PS; Delbaere, K

    2017-01-01

    Background: Reaction time measures have considerable potential to aid neuropsychological assessment in a variety of health care settings. One such measure, the intraindividual reaction time variability (IIV), is of particular interest as it is thought to reflect neurobiological disturbance. IIV is associated with a variety of age-related neurological disorders, as well as gait impairment and future falls in older adults. However, although persons diagnosed with Mild Cognitive Impairment (MCI)...

  8. Design and synthesis of polycyclic sulfones via Diels-Alder reaction and ring-rearrangement metathesis as key steps.

    Science.gov (United States)

    Kotha, Sambasivarao; Gunta, Rama

    2015-01-01

    Here, we describe a new and simple synthetic strategy to various polycyclic sulfones via Diels-Alder reaction and ring-rearrangement metathesis (RRM) as the key steps. This approach delivers tri- and tetracyclic sulfones with six (n = 1), seven (n = 2) or eight-membered (n = 3) fused-ring systems containing trans-ring junctions unlike the conventional all cis-ring junctions generally obtained during the RRM sequence. Interestingly the starting materials used are simple and commercially available.

  9. A 11-Steps Total Synthesis of Magellanine through a Gold(I)-Catalyzed Dehydro Diels-Alder Reaction.

    Science.gov (United States)

    McGee, Philippe; Bétournay, Geneviève; Barabé, Francis; Barriault, Louis

    2017-05-22

    We have developed an innovative strategy for the formation of angular carbocycles via a gold(I)-catalyzed dehydro Diels-Alder reaction. This transformation provides rapid access to a variety of complex angular cores in excellent diastereoselectivities and high yields. The usefulness of this Au I -catalyzed cycloaddition was further demonstrated by accomplishing a 11-steps total synthesis of (±)-magellanine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. A comparison of ground reaction force components according to the foothold heights in 16-t truck during downward step.

    Science.gov (United States)

    Hyun, Seung-Hyun; Ryew, Che-Cheong

    2017-12-01

    The aim of this study is to compare and analyze the components of ground reaction force (GRF) relative to the foothold heights during downward step of 16-t truck. Adult males (n= 10) jumped downward from each 1st, 2nd, 3rd foothold step and driver's seat orderly using hand rail. Sampling rate of force components of 3 axis (medial-lateral [ML] GRF, anterior-posterior [AP] GRF, peak vertical force [PVF]), variables (COPx, COPy, COP area) of center of pressure (COP), loading rate, and stability index (ML, AP, vertical, and dynamic postural stability index [DPSI]) processed from GRF system was cut off at 1,000 Hz. and variables was processed with repeated one-way analysis of variance. AP GRF, PVF and loading rate showed higher value in case of not used hand rail than that used hand rail in all 1st, 2nd, and 3rd of foothold step. DPSI showed more lowered stability in order of 2nd, 3rd step than 1st foothold step used with hand rail, of which showed lowest stability from driver's seat. COPx, COPy, and COP area showed higher value in case of 2nd and 3rd than that of 1st of foothold step, and showed lowest stability from driver's seat. It is more desirable for cargo truck driver to utilize an available hand rail in order of 3rd, 2nd, and 1st of foothold step than downward stepping directly, thus by which may results in decrease of falling injuries and minimization of impulsive force transferring to muscular-skeletal system.

  11. Two-step nuclear reactions: The Surrogate Method, the Trojan Horse Method and their common foundations

    Energy Technology Data Exchange (ETDEWEB)

    Hussein, Mahir S. [DCTA, Instituto Tecnologico de Aeronautica, Sao Jose dos Campos, SP (Brazil); Universidade de Sao Paulo, Instituto de Estudos Avancados, C. P. 72012, Sao Paulo, SP (Brazil); Universidade de Sao Paulo, Instituto de Fisica, C. P. 66318, Sao Paulo, SP (Brazil)

    2017-05-15

    In this Letter I argue that the Surrogate Method, used to extract the fast neutron capture cross section on actinide target nuclei, which has important practical application for the next generation of breeder reactors, and the Trojan Horse Method employed to extract reactions of importance to nuclear astrophysics, have a common foundation, the Inclusive Non-Elastic Breakup (INEB) Theory. Whereas the Surrogate Method relies on the premise that the extracted neutron cross section in a (d, p) reaction is predominantly a compound-nucleus one, the Trojan Horse Method assumes a predominantly direct process for the secondary reaction induced by the surrogate fragment. In general, both methods contain both direct and compound contributions, and I show how these seemingly distinct methods are in fact the same but at different energies and different kinematic regions. The unifying theory is the rather well developed INEB theory. (orig.)

  12. Two-step nuclear reactions: The Surrogate Method, the Trojan Horse Method and their common foundations

    International Nuclear Information System (INIS)

    Hussein, Mahir S.

    2017-01-01

    In this Letter I argue that the Surrogate Method, used to extract the fast neutron capture cross section on actinide target nuclei, which has important practical application for the next generation of breeder reactors, and the Trojan Horse Method employed to extract reactions of importance to nuclear astrophysics, have a common foundation, the Inclusive Non-Elastic Breakup (INEB) Theory. Whereas the Surrogate Method relies on the premise that the extracted neutron cross section in a (d, p) reaction is predominantly a compound-nucleus one, the Trojan Horse Method assumes a predominantly direct process for the secondary reaction induced by the surrogate fragment. In general, both methods contain both direct and compound contributions, and I show how these seemingly distinct methods are in fact the same but at different energies and different kinematic regions. The unifying theory is the rather well developed INEB theory. (orig.)

  13. Confidence-increasing elements in user instructions: Seniors' reactions to verification steps and personal stories

    NARCIS (Netherlands)

    Loorbach, N.R.; Karreman, Joyce; Steehouder, M.F.

    2013-01-01

    Purpose: Research shows that confidence-increasing elements in user instructions positively influence senior users' task performance and motivation. We added verification steps and personal stories to user instructions for a cell phone, to find out how seniors (between 60 and 70 years) perceive

  14. Nuclear reactions in AGB nucleosynthesis: the 19F(α, p22Ne at energies of astrophysical relevance

    Directory of Open Access Journals (Sweden)

    D’Agata G.

    2017-01-01

    Full Text Available The abundance of 19F in the universe is strictly related to standard and extra-mixing processes taking place inside AGB-stars, that are considered to be the most important sites for its production. Nevertheless the way in which it is destroyed is far from being well understood. For this reason we studied the 19F(α,p22Ne reaction, that is supposed to be the main destruction channel in the Helium-rich part of the star. In this experiment, the reaction has been studied in the energy range of relevance for astrophysics (0÷1 MeV via the Trojan Horse Method (THM, using the three-body reaction 6Li(19F,p22Ned.

  15. Genome-wide mapping for clinically relevant predictors of lamotrigine- and phenytoin-induced hypersensitivity reactions.

    LENUS (Irish Health Repository)

    McCormack, Mark

    2012-03-01

    An association between carbamazepine-induced hypersensitivity and HLA-A*3101 has been reported in populations of both European and Asian descent. We aimed to investigate HLA-A*3101 and other common variants across the genome as markers for cutaneous adverse drug reactions (cADRs) attributed to lamotrigine and phenytoin.

  16. Stability of Transition-metal Carbides in Liquid Phase Reactions Relevant for Biomass-Based Conversion

    NARCIS (Netherlands)

    Souza Macêdo, L.; Stellwagen, D.R.; Teixeira da Silva, V.; Bitter, J.H.

    2015-01-01

    Transition-metal carbides have been employed for biobased conversions aiming to replace the rare noble metals. However, when reactions are in liquid phase, many authors have observed catalyst deactivation. The main routes of deactivation in liquid phase biobased conversions are coke deposition,

  17. Solvents in Organic Synthesis: Replacement and Multi-step Reaction Systems

    DEFF Research Database (Denmark)

    Gani, Rafiqul; Gómez, Paola Arenas; Folic, Milica

    2008-01-01

    Solvents are widely used as reaction media in the chemical, fine chemical and pharmaceutical industries, but they present numerous environmental, health and safety (EHS) challenges that need to be managed and are subject to increasing regulatory scrutiny. The above issues, together with the princ...

  18. Field theoretical approach to proton-nucleus reactions: II-Multiple-step excitation process

    International Nuclear Information System (INIS)

    Eiras, A.; Kodama, T.; Nemes, M.

    1989-01-01

    A field theoretical formulation to multiple step excitation process in proton-nucleus collision within the context of a relativistic eikonal approach is presented. A closed form expression for the double differential cross section can be obtained whose structure is very simple and makes the physics transparent. Glauber's formulation of the same process is obtained as a limit of ours and the necessary approximations are studied and discussed. (author) [pt

  19. A Pilot Study of Ion - Molecule Reactions at Temperatures Relevant to the Atmosphere of Titan

    Czech Academy of Sciences Publication Activity Database

    Zymak, Illia; Žabka, Ján; Polášek, Miroslav; Španěl, Patrik; Smith, D.

    2016-01-01

    Roč. 46, č. 4 (2016), s. 533-538 ISSN 0169-6149 R&D Projects: GA ČR(CZ) GA14-19693S Grant - others:COST(XE) TD1308 Institutional support: RVO:61388955 Keywords : titan ionosphere * variable temperature selected ions flow tube * ion-molecule reactions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.000, year: 2016

  20. Elementary steps and reaction pathways in the aqueous phase alkylation of phenol with ethanol

    Energy Technology Data Exchange (ETDEWEB)

    Eckstein, Sebastian; Hintermeier, Peter H.; Olarte, Mariefel V.; Liu, Yue; Baráth, Eszter; Lercher, Johannes A.

    2017-08-01

    The hydronium ion normalized reaction rate in aqueous phase alkylation of phenol with ethanol on H-MFI zeolites increases with decreasing concentration of acid sites. Higher rates are caused by higher concentrations of phenol in the zeolite pores, as the concentration of hydronium ions generated by zeolite Brønsted acid sites decreases. Considering the different concentrations of reacting species it is shown that the intrinsic rate constant for alkylation is independent of the concentration of hydronium ions in the zeolite pores. Alkylation at the aromatic ring of phenol and of toluene as well as O-alkylation of phenol have the same activation energy, 104 ± 5 kJ/mol. This is energetic barrier to form the ethyl carbenium ion from ethanol associated to the hydronium ion. Thus, in both the reaction pathways the catalyst involves a carbenium ion, which forms a bond to a nucleophilic oxygen (ether formation) or carbon (alkylation).

  1. Biomimicry Promotes the Efficiency of a 10-Step Sequential Enzymatic Reaction on Nanoparticles, Converting Glucose to Lactate.

    Science.gov (United States)

    Mukai, Chinatsu; Gao, Lizeng; Nelson, Jacquelyn L; Lata, James P; Cohen, Roy; Wu, Lauren; Hinchman, Meleana M; Bergkvist, Magnus; Sherwood, Robert W; Zhang, Sheng; Travis, Alexander J

    2017-01-02

    For nanobiotechnology to achieve its potential, complex organic-inorganic systems must grow to utilize the sequential functions of multiple biological components. Critical challenges exist: immobilizing enzymes can block substrate-binding sites or prohibit conformational changes, substrate composition can interfere with activity, and multistep reactions risk diffusion of intermediates. As a result, the most complex tethered reaction reported involves only 3 enzymes. Inspired by the oriented immobilization of glycolytic enzymes on the fibrous sheath of mammalian sperm, here we show a complex reaction of 10 enzymes tethered to nanoparticles. Although individual enzyme efficiency was higher in solution, the efficacy of the 10-step pathway measured by conversion of glucose to lactate was significantly higher when tethered. To our knowledge, this is the most complex organic-inorganic system described, and it shows that tethered, multi-step biological pathways can be reconstituted in hybrid systems to carry out functions such as energy production or delivery of molecular cargo. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

    Science.gov (United States)

    Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

    2015-04-01

    Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

  3. Bottom–up protein identifications from microliter quantities of individual human tear samples. Important steps towards clinical relevance.

    Directory of Open Access Journals (Sweden)

    Peter Raus

    2015-12-01

    With 375 confidently identified proteins in the healthy adult tear, the obtained results are comprehensive and in large agreement with previously published observations on pooled samples of multiple patients. We conclude that, to a limited extent, bottom–up tear protein identifications from individual patients may have clinical relevance.

  4. Capture reactions at astrophysically relevant energies: extended gas target experiments and GEANT simulations

    CERN Document Server

    Kölle, V; Braitmayer, S E; Mohr, P J; Wilmes, S; Staudt, G; Hammer, J W; Jäger, M; Knee, H; Kunz, R; Mayer, A

    1999-01-01

    Several resonances of the capture reaction sup 2 sup 0 Ne(alpha, gamma) sup 2 sup 4 Mg were measured using an extended windowless gas target system. Detailed GEANT simulations were performed to derive the strength and the total width of the resonances from the measured yield curve. The crucial experimental parameters, which are mainly the density profile in the gas target and the efficiency of the gamma-ray detector, were analyzed by a comparison between the measured data and the corresponding simulation calculations. The excellent agreement between the experimental data and the simulations gives detailed insight into these parameters. (author)

  5. [The relevance of junctional rhythm during neurocardiogenic reaction provoked by tilt testing].

    Science.gov (United States)

    Zyśko, Dorota; Gajek, Jacek; Agrawal, Anil Kumar; Rudnicki, Jerzy

    2012-01-01

    During neurocardiogenic reaction provoked by tilt testing (TT), different arrhythmias such as sinus bradycardia, sinus arrest, atrioventricular block or junctional rhythm or beats (JR) may occur. The characteristics of the JR during neurocardiogenic reaction have not yet been systematically assessed. It is not known whether the presence of JR during neurocardiogenic reaction is related to clinical characteristics of syncopal patients or the outcome of TT. To assess whether clinical outcome of TT and clinical data are related to the presence of JR during TT. The study group consisted of 532 patients aged 43.3 ± 18.2 years with positive TT, divided into four groups on the basis of the presence of JR and/or a ventricular pause (VP) during neurocardiogenic reaction: group VP(-)/JR(+) - JR present and VP absent, group VP(+)/JR(+) - both JR and VP present, group VP(+)/JR(-) - JR absent and VP present, and group VP(-)/JR(-) - both JR and VP absent. The control group consisted of 53 patients with no history of syncope or presyncope, including 46 patients with negative TT and seven patients with false positive TT. Total loss of consciousness during TT occurred in group VP(-)/JR(+) less frequently than in groups VP(+)/JR(+) and VP(+)/JR(-), and more frequently than in group VP(-)/JR(-) (80% vs 96% vs 94% vs 62%; p 〈 0.05 for both comparisons). Group VP(-)/JR(+) was significantly younger than group VP(-)/JR(-) (37.3 ± 16.3 years vs 45.8 ± 18.9 years; p 〈 0.05) and had a lower number of syncopal events than group VP(+)/JR(+) and VP(+)/JR(-) (median [IQ]: 2.5 (1-6) vs 4 (2-12) and 4 (2-10), respectively; p 〈 0.05) and lower rate of traumatic injuries than group VP(+)/JR(+) and VP(+)/JR(-) (22% vs 45% and 39%, respectively; p 〈 0.05). Logistic regression analysis revealed that the presence of JR was associated with younger age, male gender, history of blood-instrumentation-injection phobia and higher number of syncopal spells in medical history. The ROC curve analysis

  6. It just doesn't speak to me: mid-aged men's reactions to '10,000 Steps a Day'.

    Science.gov (United States)

    Burton, Nicola W; Walsh, Anthony; Brown, Wendy J

    2008-04-01

    The evaluation of an earlier 10,000 Steps community-based intervention program indicated that men were less likely than women to have used a pedometer or increased their physical activity (PA). This study aimed to explore men's reactions to the 10,000 Steps a Day message, the use of pedometers, and other strategies for increasing PA. Five focus groups were conducted with 39 men aged 45-65 years. Although many were familiar with the 10,000 Steps message, the majority of men did not like it. Pedometers were seen as useful for assessing PA in the short term, but not for ongoing use. Participants were generally aware of PA recommendations. Walking was considered a good option for this age group, but there was varying interest in this type of activity. Weight and stress management were commonly identified benefits of PA. Common barriers to PA were lack of time and motivation, health and weight restrictions, cost, and disinterest. Suggestions of how to promote PA to mid-aged men included workplace initiatives, making PA "fun", and creating opportunities for men to do PA with their family or same-aged peers. PA promotion using the 10,000 Steps message, walking, and pedometers may not appeal to mid-aged men.

  7. Exponential growth for self-reproduction in a catalytic reaction network: relevance of a minority molecular species and crowdedness

    Science.gov (United States)

    Kamimura, Atsushi; Kaneko, Kunihiko

    2018-03-01

    Explanation of exponential growth in self-reproduction is an important step toward elucidation of the origins of life because optimization of the growth potential across rounds of selection is necessary for Darwinian evolution. To produce another copy with approximately the same composition, the exponential growth rates for all components have to be equal. How such balanced growth is achieved, however, is not a trivial question, because this kind of growth requires orchestrated replication of the components in stochastic and nonlinear catalytic reactions. By considering a mutually catalyzing reaction in two- and three-dimensional lattices, as represented by a cellular automaton model, we show that self-reproduction with exponential growth is possible only when the replication and degradation of one molecular species is much slower than those of the others, i.e., when there is a minority molecule. Here, the synergetic effect of molecular discreteness and crowding is necessary to produce the exponential growth. Otherwise, the growth curves show superexponential growth because of nonlinearity of the catalytic reactions or subexponential growth due to replication inhibition by overcrowding of molecules. Our study emphasizes that the minority molecular species in a catalytic reaction network is necessary for exponential growth at the primitive stage of life.

  8. Underground structure pattern and multi AO reaction with step feed concept for upgrading an large wastewater treatment plant

    Science.gov (United States)

    Peng, Yi; Zhang, Jie; Li, Dong

    2018-03-01

    A large wastewater treatment plant (WWTP) could not meet the new demand of urban environment and the need of reclaimed water in China, using a US treatment technology. Thus a multi AO reaction process (Anaerobic/oxic/anoxic/oxic/anoxic/oxic) WWTP with underground structure was proposed to carry out the upgrade project. Four main new technologies were applied: (1) multi AO reaction with step feed technology; (2) deodorization; (3) new energy-saving technology such as water resource heat pump and optical fiber lighting system; (4) dependable old WWTP’s water quality support measurement during new WWTP’s construction. After construction, upgrading WWTP had saved two thirds land occupation, increased 80% treatment capacity and improved effluent standard by more than two times. Moreover, it had become a benchmark of an ecological negative capital changing to a positive capital.

  9. High-yield production of pure tagatose from fructose by a three-step enzymatic cascade reaction.

    Science.gov (United States)

    Lee, Seon-Hwa; Hong, Seung-Hye; Kim, Kyoung-Rok; Oh, Deok-Kun

    2017-08-01

    To produce tagatose from fructose with a high conversion rate and to establish a high-yield purification method of tagatose from the reaction mixture. Fructose at 1 M (180 g l -1 ) was converted to 0.8 M (144 g l -1 ) tagatose by a three-step enzymatic cascade reaction, involving hexokinase, plus ATP, fructose-1,6-biphosphate aldolase, phytase, over 16 h with a productivity of 9 g l -1 h -1 . No byproducts were detected. Tagatose was recrystallized from ethanol to a purity of 99.9% and a yield of 96.3%. Overall, tagatose at 99.9% purity was obtained from fructose with a yield of 77%. This is the first biotechnological production of tagatose from fructose and the first application of solvent recrystallization for the purification of rare sugars.

  10. Rapid Synthesis of Lead Oxide Nanorods by One-step Solid-state Chemical Reaction at Room Temperature

    Institute of Scientific and Technical Information of China (English)

    CAO, Ya-Li(曹亚丽); JIA, Dian-Zeng(贾殿赠); LIU, Lang(刘浪); LUO, Jian-Min(骆建敏)

    2004-01-01

    A simple and facile method was reported to synthesize lead oxide nanorods. Nanorods of lead oxide were obtained directly from grinding solid metal salt and sodium hydroxide in agate mortar with the assistance of a suitable nonionic surfactant in only one step, which is different from the result of hydroxide in solution. The product has been characterized by XRD, TEM and SEM. The formation mechanism of rod-like morphology is discussed and the surfactant plays an important soft-template role in modifying the interface of solid-state reaction and according process of rod-formation.

  11. The initial step of silicate versus aluminosilicate formation in zeolite synthesis: a reaction mechanism in water with a tetrapropylammonium template

    KAUST Repository

    Trinh, Thuat T.

    2012-01-01

    The initial step for silicate and aluminosilicate condensation is studied in water in the presence of a realistic tetrapropylammonium template under basic conditions. The model corresponds to the synthesis conditions of ZSM5. The free energy profile for the dimer formation ((OH) 3Si-O-Si-(OH) 2O - or [(OH) 3Al-O-Si-(OH) 3] -) is calculated with ab initio molecular dynamics and thermodynamic integration. The Si-O-Si dimer formation occurs in a two-step manner with an overall free energy barrier of 75 kJ mol -1. The first step is associated with the Si-O bond formation and results in an intermediate with a five-coordinated Si, and the second one concerns the removal of the water molecule. The template is displaced away from the Si centres upon dimer formation, and a shell of water molecules is inserted between the silicate and the template. The main effect of the template is to slow down the backward hydrolysis reaction with respect to the condensation one. The Al-O-Si dimer formation first requires the formation of a metastable precursor state by proton transfer from Si(OH) 4 to Al(OH) 4 - mediated by a solvent molecule. It then proceeds through a single step with an overall barrier of 70 kJ mol -1. The model with water molecules explicitly included is then compared to a simple calculation using an implicit continuum model for the solvent. The results underline the importance of an explicit and dynamical treatment of the water solvent, which plays a key role in assisting the reaction. © the Owner Societies 2012.

  12. Production of ethyl ester from crude palm oil by two-step reaction using continuous microwave system

    Directory of Open Access Journals (Sweden)

    Sukritthira Ratanawilai

    2011-02-01

    Full Text Available The esterification of free fatty acids (FFA in vegetable oils with alcohol using an acid catalyst is a promising methodto convert FFA into valuable ester and obtain a FFA-free oil that can be further transesterified using alkali bases. In thiswork, the direct esterification reaction of FFA in crude palm oil to ethyl ester by continuous microwave was studied and theeffects of the main variables involved in the process, amount of catalyst, reaction time and the molar ratio oil/ alcohol, wereanalyzed. The optimum condition for the continuous esterification process was carried out with a molar ratio of oil to ethanol1:6, using 1.25%wt of H2SO4/oil as a catalyst, microwave power of 78 W and a reaction time 90 min. This esterification processshows that the amount of FFA was reduced from 7.5%wt to values around 1.4 %wt. Similar results were obtained followingconventional heating at 70°C, but only after a reaction time of 240 min. The esterified crude palm oil is suitable to perform thetransesterification process. Transesterification of the esterified palm oil has been accomplished with a molar ratio of oil toethanol of 1:8.5, 2.5%wt of KOH as a catalyst, a microwave power of 78 W, and a reaction time of 7 min. In addition, theproblem of glycerin separation was solved by mixing 10%wt of pure glycerin into the ethyl ester to induce the glycerin fromthe reaction to separated. This two-step esterification and transesterification process provided a yield of 78%wt with anester content of 97.4%wt. The final ethyl ester product met with the specifications stipulated by ASTM D6751-02.

  13. Predictors of cognitive impairment assessed by Mini Mental State Examination in community-dwelling older adults: relevance of the step test.

    Science.gov (United States)

    Muscari, Antonio; Spiller, Ilaria; Bianchi, Giampaolo; Fabbri, Elisa; Forti, Paola; Magalotti, Donatella; Pandolfi, Paolo; Zoli, Marco

    2018-07-15

    Several predictors of cognitive impairment assessed by Mini Mental State Examination (MMSE) have previously been identified. However, which predictors are the most relevant and what is their effect on MMSE categories remains unclear. Cross-sectional and longitudinal study using data from 1116 older adults (72.6 ± 5.6 years, 579 female), 350 of whom were followed for 7 years. At baseline, the following variables were collected: personal data, marital status, occupation, anthropometric measures, risk factors, previous cardiovascular events, self-rated health and physical activity during the last week. Furthermore, routine laboratory tests, abdominal echography and a step test (with measurement of the time needed to ascend and descend two steps 20 times) were performed. The associations of these variables with cross-sectional cognitive deficit (MMSE cognitive decline (decrease of MMSE score over 7 years of follow-up) were investigated using logistic regression models. Cross-sectional cognitive deficit was independently associated with school education ≤ 5 years, prolonged step test duration, having been blue collar or housewife (P ≤ 0.0001 for all) and, with lower significance, with advanced age, previous stroke and poor recent physical activity (P cognitive decline was mainly associated with step test duration (P = 0.0001) and diastolic blood pressure (P = 0.0002). The MMSE categories mostly associated with step test duration were orientation, attention, calculation and language, while memory appeared to be poorly or not affected. In our cohort of older adults, step test duration was the most relevant predictor of cognitive impairment. Copyright © 2018 Elsevier Inc. All rights reserved.

  14. A simple test of choice stepping reaction time for assessing fall risk in people with multiple sclerosis.

    Science.gov (United States)

    Tijsma, Mylou; Vister, Eva; Hoang, Phu; Lord, Stephen R

    2017-03-01

    Purpose To determine (a) the discriminant validity for established fall risk factors and (b) the predictive validity for falls of a simple test of choice stepping reaction time (CSRT) in people with multiple sclerosis (MS). Method People with MS (n = 210, 21-74y) performed the CSRT, sensorimotor, balance and neuropsychological tests in a single session. They were then followed up for falls using monthly fall diaries for 6 months. Results The CSRT test had excellent discriminant validity with respect to established fall risk factors. Frequent fallers (≥3 falls) performed significantly worse in the CSRT test than non-frequent fallers (0-2 falls). With the odds of suffering frequent falls increasing 69% with each SD increase in CSRT (OR = 1.69, 95% CI: 1.27-2.26, p = falls in people with MS. This test may prove useful in documenting longitudinal changes in fall risk in relation to MS disease progression and effects of interventions. Implications for rehabilitation Good choice stepping reaction time (CSRT) is required for maintaining balance. A simple low-tech CSRT test has excellent discriminative and predictive validity in relation to falls in people with MS. This test may prove useful documenting longitudinal changes in fall risk in relation to MS disease progression and effects of interventions.

  15. Double-step processes in the 12C(p,d)11C reaction at 45 MeV

    International Nuclear Information System (INIS)

    Couvert, Pierre.

    1974-01-01

    12 C(p,d) 11 C pick-up reaction was performed with a 45 MeV proton beam. A 130keV energy resolution was obtained and angular distributions of nine of the ten first levels of 11 C have been extracted within a large angular range. Assuming only neutron direct transfert, the strong relative excitation of high spin levels cannot be reproduced by a DWBA analysis. The double-step process assumption seems to be verified by a systematical analysis of the (p,d) reaction mechanisms. This analysis is done in the coupled-channel formalism for the five first negative parity states of 11 C. The 3/2 - ground state is essentially populated by the direct transfer of a Psub(3/2) neutron. The contribution of a double-step process, via the 2 + inelastic excitation of 12 C, is important for the four other states. A mechanism which assumes a deuteron inelastic scattering on the 11 C final nucleus after the neutron transfer cannot be neglected and improves the fits when it is taken into account [fr

  16. Compositional change of some first wall materials by considering multiple step nuclear reaction

    Energy Technology Data Exchange (ETDEWEB)

    Noda, Tetsuji; Utsumi, Misako; Fujita, Mitsutane [National Research Inst. for Metals, Tsukuba, Ibaraki (Japan)

    1997-03-01

    The conceptual system for nuclear material design is considered and some trials on WWW server with functions of the easily accessible simulation of nuclear reactions are introduced. Moreover, as an example of the simulation on the system using nuclear data, transmutation calculation was made for candidate first wall materials such as 9Cr-2W steel, V-5Cr-5Ti and SiC in SUS316/Li{sub 2}O/H{sub 2}O(SUS), 9Cr-2WLi{sub 2}O/H{sub 2}O(RAF), V alloy/Li/Be(V), and SiC/Li{sub 2}ZrO{sub 3}/He(SiC) blanket/shield systems based on ITER design model. Neutron spectrum varies with different blanket/shield compositions. The flux of low energy neutrons decreases in order of V-SiC-RAF-SUS blanket/shield systems. Fair amounts of W depletion in 9Cr-2W steel and the increase of Cr content in V-5Cr-5Ti were predicted in SUS or RAF systems. Concentration change in W and Cr is estimated to be suppressed if Li coolant is used in place of water. Helium and hydrogen production are not strongly affected by the different blanket/shield compositions. (author)

  17. Aldimine Formation Reaction, the First Step of the Maillard Early-phase Reaction, Might be Enhanced in Variant Hemoglobin, Hb Himeji.

    Science.gov (United States)

    Koga, Masafumi; Inada, Shinya; Shimizu, Sayoko; Hatazaki, Masahiro; Umayahara, Yutaka; Nishihara, Eijun

    2015-01-01

    Hb Himeji (β140Ala→Asp) is known as a variant hemoglobin in which glycation is enhanced and HbA1c measured by immunoassay shows a high value. The phenomenon of enhanced glycation in Hb Himeji is based on the fact that the glycation product of variant hemoglobin (HbX1c) shows a higher value than HbA1c. In this study, we investigated whether aldimine formation reaction, the first step of the Maillard early-phase reaction, is enhanced in Hb Himeji in vitro. Three non-diabetic subjects with Hb Himeji and four non-diabetic subjects without variant hemoglobin were enrolled. In order to examine aldimine formation reaction, whole blood cells were incubated with 500 mg/dl of glucose at 37°C for 1 hour and were analyzed by high-performance liquid chromatography. Both HbA1c and HbX1c were not increased in this condition. After incubation with glucose, labile HbA1c (LA1c) fraction increased in the controls (1.1±0.3%). In subjects with Hb Himeji increases in the labile HbX1c (LX1c) fraction as well as the LA1c fraction were observed, and the degree of increase in the LX1c fraction was significantly higher than that of the LA1c fraction (1.8±0.1% vs. 0.5±0.2%, Preaction might be enhanced in Hb Himeji in vitro. The 140th amino acid in β chain of hemoglobin is suggested to be involved in aldimine formation reaction. © 2015 by the Association of Clinical Scientists, Inc.

  18. Flavourzyme, an Enzyme Preparation with Industrial Relevance: Automated Nine-Step Purification and Partial Characterization of Eight Enzymes.

    Science.gov (United States)

    Merz, Michael; Eisele, Thomas; Berends, Pieter; Appel, Daniel; Rabe, Swen; Blank, Imre; Stressler, Timo; Fischer, Lutz

    2015-06-17

    Flavourzyme is sold as a peptidase preparation from Aspergillus oryzae. The enzyme preparation is widely and diversely used for protein hydrolysis in industrial and research applications. However, detailed information about the composition of this mixture is still missing due to the complexity. The present study identified eight key enzymes by mass spectrometry and partially by activity staining on native polyacrylamide gels or gel zymography. The eight enzymes identified were two aminopeptidases, two dipeptidyl peptidases, three endopeptidases, and one α-amylase from the A. oryzae strain ATCC 42149/RIB 40 (yellow koji mold). Various specific marker substrates for these Flavourzyme enzymes were ascertained. An automated, time-saving nine-step protocol for the purification of all eight enzymes within 7 h was designed. Finally, the purified Flavourzyme enzymes were biochemically characterized with regard to pH and temperature profiles and molecular sizes.

  19. Systematic literature review of integrated community case management and the private sector in Africa: Relevant experiences and potential next steps.

    Science.gov (United States)

    Awor, Phyllis; Miller, Jane; Peterson, Stefan

    2014-12-01

    Despite substantial investments made over the past 40 years in low income countries, governments cannot be viewed as the principal health care provider in many countries. Evidence on the role of the private sector in the delivery of health services is becoming increasingly available. In this study, we set out to determine the extent to which the private sector has been utilized in providing integrated care for sick children under 5 years of age with community-acquired malaria, pneumonia or diarrhoea. We reviewed the published literature for integrated community case management (iCCM) related experiences within both the public and private sector. We searched PubMed and Google/Google Scholar for all relevant literature until July 2014. The search terms used were "malaria", "pneumonia", "diarrhoea", "private sector" and "community case management". A total of 383 articles referred to malaria, pneumonia or diarrhoea in the private sector. The large majority of these studies (290) were only malaria related. Most of the iCCM-related studies evaluated introduction of only malaria drugs and/or diagnostics into the private sector. Only one study evaluated the introduction of drugs and diagnostics for malaria, pneumonia and diarrhoea in the private sector. In contrast, most iCCM-related studies in the public sector directly reported on community case management of 2 or more of the illnesses. While the private sector is an important source of care for children in low income countries, little has been done to harness the potential of this sector in improving access to care for non-malaria-associated fever in children within the community. It would be logical for iCCM programs to expand their activities to include the private sector to achieve higher population coverage. An implementation research agenda for private sector integrated care of febrile childhood illness needs to be developed and implemented in conjunction with private sector intervention programs.

  20. Detection of Listeria monocytogenes in ready-to-eat food by Step One real-time polymerase chain reaction.

    Science.gov (United States)

    Pochop, Jaroslav; Kačániová, Miroslava; Hleba, Lukáš; Lopasovský, L'ubomír; Bobková, Alica; Zeleňáková, Lucia; Stričík, Michal

    2012-01-01

    The aim of this study was to follow contamination of ready-to-eat food with Listeria monocytogenes by using the Step One real time polymerase chain reaction (PCR). We used the PrepSEQ Rapid Spin Sample Preparation Kit for isolation of DNA and MicroSEQ® Listeria monocytogenes Detection Kit for the real-time PCR performance. In 30 samples of ready-to-eat milk and meat products without incubation we detected strains of Listeria monocytogenes in five samples (swabs). Internal positive control (IPC) was positive in all samples. Our results indicated that the real-time PCR assay developed in this study could sensitively detect Listeria monocytogenes in ready-to-eat food without incubation.

  1. Compact Ag@Fe3O4 Core-shell Nanoparticles by Means of Single-step Thermal Decomposition Reaction

    Science.gov (United States)

    Brollo, Maria Eugênia F.; López-Ruiz, Román; Muraca, Diego; Figueroa, Santiago J. A.; Pirota, Kleber R.; Knobel, Marcelo

    2014-10-01

    A temperature pause introduced in a simple single-step thermal decomposition of iron, with the presence of silver seeds formed in the same reaction mixture, gives rise to novel compact heterostructures: brick-like Ag@Fe3O4 core-shell nanoparticles. This novel method is relatively easy to implement, and could contribute to overcome the challenge of obtaining a multifunctional heteroparticle in which a noble metal is surrounded by magnetite. Structural analyses of the samples show 4 nm silver nanoparticles wrapped within compact cubic external structures of Fe oxide, with curious rectangular shape. The magnetic properties indicate a near superparamagnetic like behavior with a weak hysteresis at room temperature. The value of the anisotropy involved makes these particles candidates to potential applications in nanomedicine.

  2. Synthesis of monoclinic Celsian from Coal Fly Ash by using a one-step solid-state reaction process

    Energy Technology Data Exchange (ETDEWEB)

    Long-Gonzalez, D.; Lopez-Cuevas, J.; Gutierrez-Chavarria, C.A.; Pena, P.; Baudin, C.; Turrillas, X. [CINVESTAV, Coahuila (Mexico)

    2010-03-15

    Monoclinic (Celsian) and hexagonal (Hexacelsian) Ba1-xSrxAl{sub 2}Si2O8 solid solutions, where x=0, 0.25, 0.375, 0.5, 0.75 or 1, were synthesized by using Coal Fly Ash (CFA) as main raw material, employing a simple one-step solid-state reaction process involving thermal treatment for 5 h at 850-1300{sup o}C. Fully monoclinic Celsian was obtained at 1200{sup o} C/5 h, for SrO contents of 0.25 {<=} x {<=} 0.75. However, an optimum SrO level of 0.25 {<=} x {<=} 0.375 was recommended for the stabilization of Celsian. These synthesis conditions represent a significant improvement over the higher temperatures, longer times and/or multi-step processes needed to obtain fully monoclinic Celsian, when other raw materials are used for this purpose, according to previous literature. These results were attributed to the role of the chemical and phase constitution of CFA as well as to a likely mineralizing effect of CaO and TiO{sub 2} present in it, which enhanced the Hexacelsian to Celsian conversion.

  3. One step synthesis of chlorine-free Pt/Nitrogen-doped graphene composite for oxygen reduction reaction

    KAUST Repository

    Varga, Tamás

    2018-03-14

    Chlorine-free Platinum/nitrogen-doped graphene oxygen reduction reaction catalysts were synthesized by a one step method of annealing a mixture of platinum acetylacetonate and graphene oxide under ammonia atmosphere. Nanoparticles with close to the ideal particle size for oxygen reduction reaction (ORR) were formed, i.e., with diameter of 3–4 nm (500 and 600 °C) and 6 nm (700 °C). X-ray photoelectron spectroscopy confirmed the successful introduction of both pyridinic and pyrrolic type nitrogen moieties into the graphene layers, which indicates a strong interaction between the nanoparticles and the graphene layers. The electrocatalytic activity of glassy carbon electrodes (GCE) modified with the synthesized Pt/NG samples for oxygen reduction was compared to that of a platinum/carbon black catalyst modified electrode in acidic and alkaline media. Based on the measured limiting current densities and calculated electron transfer number, the highest activity was measured in acidic and alkaline media on the samples annealed at 600 and 700 °C, respectively.

  4. New Improved Indirect Measurement of the {sup 19}F( p , α ){sup 16}O Reaction at Energies of Astrophysical Relevance

    Energy Technology Data Exchange (ETDEWEB)

    Indelicato, I.; La Cognata, M.; Spitaleri, C.; Cherubini, S.; Gulino, M.; Lamia, L.; Pizzone, R. G.; Romano, S.; Tumino, A. [INFN, Laboratori Nazionali del Sud, Catania (Italy); Burjan, V.; Hons, Z.; Kroha, V.; Mrazek, J. [Nuclear Physics Institute of ASCR, Rez near Prague (Czech Republic); Hayakawa, S. [RIKEN, CNS, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Mazzocco, M.; Strano, E.; Torresi, D., E-mail: indelicato@lns.infn.it [INFN, Sezione di Padova, Padova (Italy)

    2017-08-10

    Fluorine abundance determination is of great importance in stellar physics to understand s-elements production and mixing processes in asymptotic giant branch (AGB) stars. Up to now, theoretical models overproduce F abundances in AGB stars with respect to the observed values, thus calling for further investigation of the reactions involving fluorine. In particular, the {sup 19}F( p , α ){sup 16}O reaction is the main destruction channel of fluorine at the bottom of the convective envelope in AGB stars, an H-rich environment where it can experience temperatures high enough to determine its destruction, owing to additional mixing processes. In this paper the Trojan horse method (THM) was used to extract the {sup 19}F( p , α {sub 0}){sup 16}O S-factor in the energy range of astrophysical interest ( E {sub cm} ≈ 0–1 MeV). This is the most relevant channel at the low temperatures (few 10{sup 7} K) characterizing the bottom of the convective envelope, according to current knowledge. A previous indirect experiment using the THM has observed three resonances in the energy regions below E {sub cm} ≈ 450 keV. These energies correspond to typical AGB temperatures, thus implying a significant increase in the reaction rate. Statistics are scarce for performing an accurate separation between resonances, preventing one from drawing a quantitative conclusion about their total widths and spin parities. Before THM measurement, only extrapolations were available below about 500 keV, showing a non-resonant behavior that sharply contradicts the trend of the astrophysical factor at higher energies. A new experiment has been performed to verify the measured TH astrophysical factor and to perform more accurate spectroscopy of the involved resonances.

  5. Reaction mechanisms in zeolite catalysis

    NARCIS (Netherlands)

    Rozanska, X.; Santen, van R.A.; Auerbach, S.C.; Carrado, K.A.; Dutta, P.D.

    2003-01-01

    A review; described are the most basic mechanistic reaction steps that are induced by zeolite catalysts. Details on the zeolitic properties that are relevant to mol. reactivity are also provided. The theor. methods and models at hand to allow the investigation of these reaction steps and that have

  6. Use of the challenge point framework to guide motor learning of stepping reactions for improved balance control in people with stroke: a case series.

    Science.gov (United States)

    Pollock, Courtney L; Boyd, Lara A; Hunt, Michael A; Garland, S Jayne

    2014-04-01

    Stepping reactions are important for walking balance and community-level mobility. Stepping reactions of people with stroke are characterized by slow reaction times, poor coordination of motor responses, and low amplitude of movements, which may contribute to their decreased ability to recover their balance when challenged. An important aspect of rehabilitation of mobility after stroke is optimizing the motor learning associated with retraining effective stepping reactions. The Challenge Point Framework (CPF) is a model that can be used to promote motor learning through manipulation of conditions of practice to modify task difficulty, that is, the interaction of the skill of the learner and the difficulty of the task to be learned. This case series illustrates how the retraining of multidirectional stepping reactions may be informed by the CPF to improve balance function in people with stroke. Four people (53-68 years of age) with chronic stroke (>1 year) and mild to moderate motor recovery received 4 weeks of multidirectional stepping reaction retraining. Important tenets of motor learning were optimized for each person during retraining in accordance with the CPF. Participants demonstrated improved community-level walking balance, as determined with the Community Balance and Mobility Scale. These improvements were evident 1 year later. Aspects of balance-related self-efficacy and movement kinematics also showed improvements during the course of the intervention. The application of CPF motor learning principles in the retraining of stepping reactions to improve community-level walking balance in people with chronic stroke appears to be promising. The CPF provides a plausible theoretical framework for the progression of functional task training in neurorehabilitation.

  7. Effect of a perturbation-based balance training program on compensatory stepping and grasping reactions in older adults: a randomized controlled trial.

    Science.gov (United States)

    Mansfield, Avril; Peters, Amy L; Liu, Barbara A; Maki, Brian E

    2010-04-01

    Compensatory stepping and grasping reactions are prevalent responses to sudden loss of balance and play a critical role in preventing falls. The ability to execute these reactions effectively is impaired in older adults. The purpose of this study was to evaluate a perturbation-based balance training program designed to target specific age-related impairments in compensatory stepping and grasping balance recovery reactions. This was a double-blind randomized controlled trial. The study was conducted at research laboratories in a large urban hospital. Thirty community-dwelling older adults (aged 64-80 years) with a recent history of falls or self-reported instability participated in the study. Participants were randomly assigned to receive either a 6-week perturbation-based (motion platform) balance training program or a 6-week control program involving flexibility and relaxation training. Features of balance reactions targeted by the perturbation-based program were: (1) multi-step reactions, (2) extra lateral steps following anteroposterior perturbations, (3) foot collisions following lateral perturbations, and (4) time to complete grasping reactions. The reactions were evoked during testing by highly unpredictable surface translation and cable pull perturbations, both of which differed from the perturbations used during training. /b> Compared with the control program, the perturbation-based training led to greater reductions in frequency of multi-step reactions and foot collisions that were statistically significant for surface translations but not cable pulls. The perturbation group also showed significantly greater reduction in handrail contact time compared with the control group for cable pulls and a possible trend in this direction for surface translations. Further work is needed to determine whether a maintenance program is needed to retain the training benefits and to assess whether these benefits reduce fall risk in daily life. Perturbation-based training

  8. Descent with Modification: Thermal Reactions of Subsurface H2O2 of Relevance to Icy Satellites and Other Small Bodies

    Science.gov (United States)

    Hudson, Reggie L.; Loefler, Mark J.

    2012-01-01

    Laboratory experiments have demonstrated that magnetospheric radiation in the Jovian system drives reaction chemistry in ices at temperatures relevant to Europa and other icy satellites. Similarly, cosmic radiation (mainly protons) acting on cometary and interstellar ices can promote extensive chemical change. Among the products that have been identified in irradiated H20-ice is hydrogen peroxide (H202), which has been observed on Europa and is suspected on other worlds. Although the infrared spectra and radiation chemistry of H2O2-containing ices are well documented, the thermally-induced solid-phase chemistry of H2O2 is largely unknown. Therefore, in this presentation we report new laboratory results on reactions at 50 - 130 K in ices containing H2O2 and other molecules, both in the presence and absence of H2O. As an example of our results, we find that warming H2O + H2O2 + SO2 ices promotes SO2 oxidation to SO4(2-). We suspect that such redox chemistry may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto. If other molecules prove to be just as reactive with frozen H2O2 then it may explain why H2O2 has been absent from surfaces of many of the small icy bodies that are known to be exposed to ionizing radiation. Our results also have implications for the survival of H2O2 as it descends towards a subsurface ocean on Europa.

  9. Neutron-capture reactions by stable and unstable neutron-rich nuclei and their relevance for nucleosynthesis in hot and explosive astrophysical scenarios

    International Nuclear Information System (INIS)

    Hofinger, R.

    1997-10-01

    This thesis deals on the one hand with neutron-capture reactions by carbon-, nitrogen-, oxygen- and sulfur-isotopes, and on the other hand with the two-step processes 4 He(2n, γ) 6 He and 9 Li(2n, γ) 11 Li. Some of the involved carbon-, nitrogen- and oxygen-isotopes possess neutron-halos characterized by the unexpected large radial extension of the nuclear matter density distribution. Special attention is paid to the halo properties in the calculation of the direct neutron capture cross section. For the determination of the nuclear structure, models are used, when no experimental information is available. The results for the reaction rates are compared to previously used rates. The rates obtained in this work are partly orders of magnitude higher than the previously used reaction rates. The reaction rates for the two-step processes are on the one hand calculated assuming a two-step process, on the other hand from genuine three-body models for the process of photodisintegration of the nuclei 6 He and 11 Li. It turns out that the calculations assuming a trio-step process underestimate the reaction rates by orders of magnitude. The influence of the reaction rate for the reaction 4 He(2n, γ) 6 He and the formation of 12 C is examined in a nuclear reaction network under conditions which are typical for the α- process in supernovae of type II. It turns out that under these conditions the influence of the reaction 4 He(2n, γ) 6 He is negligible on the formation of 12 C. (author)

  10. One-pot, two-step synthesis of imidazo[1,2-a]benzimidazoles via a multicomponent [4 + 1] cycloaddition reaction.

    Science.gov (United States)

    Hsiao, Ya-Shan; Narhe, Bharat D; Chang, Ying-Sheng; Sun, Chung-Ming

    2013-10-14

    A one-pot, two-step synthesis of imidazo[1,2-a]benzimidazoles has been achieved by a three-component reaction of 2-aminobenzimidazoles with an aromatic aldehyde and an isocyanide. The reaction involving condensation of 2-aminobenzimidazole with an aldehyde is run under microwave activation to generate an imine intermediate under basic conditions which then undergoes [4 + 1] cycloaddition with an isocyanide.

  11. Step training improves reaction time, gait and balance and reduces falls in older people: a systematic review and meta-analysis.

    Science.gov (United States)

    Okubo, Yoshiro; Schoene, Daniel; Lord, Stephen R

    2017-04-01

    To examine the effects of stepping interventions on fall risk factors and fall incidence in older people. Electronic databases (PubMed, EMBASE, CINAHL, Cochrane, CENTRAL) and reference lists of included articles from inception to March 2015. Randomised (RCT) or clinical controlled trials (CCT) of volitional and reactive stepping interventions that included older (minimum age 60) people providing data on falls or fall risk factors. Meta-analyses of seven RCTs (n=660) showed that the stepping interventions significantly reduced the rate of falls (rate ratio=0.48, 95% CI 0.36 to 0.65, prisk ratio=0.51, 95% CI 0.38 to 0.68, pfalls and proportion of fallers. A meta-analysis of two RCTs (n=62) showed that stepping interventions significantly reduced laboratory-induced falls, and meta-analysis findings of up to five RCTs and CCTs (n=36-416) revealed that stepping interventions significantly improved simple and choice stepping reaction time, single leg stance, timed up and go performance (pfalls among older adults by approximately 50%. This clinically significant reduction may be due to improvements in reaction time, gait, balance and balance recovery but not in strength. Further high-quality studies aimed at maximising the effectiveness and feasibility of stepping interventions are required. CRD42015017357. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

  12. One-step Conversion of Levulinic Acid to Succinic Acid Using I2/t-BuOK System: The Iodoform Reaction Revisited.

    Science.gov (United States)

    Kawasumi, Ryosuke; Narita, Shodai; Miyamoto, Kazunori; Tominaga, Ken-Ichi; Takita, Ryo; Uchiyama, Masanobu

    2017-12-21

    The iodoform reaction has long been used as a qualitative test for acetyl and/or ethanol units in organic molecules. However, its synthetic applications are quite limited. Here, we describe a tuned iodoform reaction for oxidative demethylation reaction with I 2 and t-BuOK in t-BuOH, in which in situ-generated t-BuOI serves as the chemoselective iodinating agent. This system enables one-step conversion of levulinic acid to succinic acid, a major four-carbon chemical feedstock. This oxidative demethylation is also applicable to other compounds containing an acetyl group/ethanol unit, affording the corresponding carboxylic acids in a selective manner.

  13. Physiological and cognitive mediators for the association between self-reported depressed mood and impaired choice stepping reaction time in older people.

    NARCIS (Netherlands)

    Kvelde, T.; Pijnappels, M.A.G.M.; Delbaere, K.; Close, J.C.; Lord, S.R.

    2010-01-01

    Background. The aim of the study was to use path analysis to test a theoretical model proposing that the relationship between self-reported depressed mood and choice stepping reaction time (CSRT) is mediated by psychoactive medication use, physiological performance, and cognitive ability.A total of

  14. Multi-step processes in the (d, t) and (d, 3He) reactions on 116Sn and 208Pb targets at Ed = 200 MeV

    International Nuclear Information System (INIS)

    Langevin-Joliot, H.; Van de Wiele, J.; Guillot, J.; Koning, A.J.

    2000-01-01

    The role of multi-step processes in the reactions 116 Sn(d,t), 208 Pb(d,t) and 116 Sn(d, 3 He), previously studied at E d = 200 MeV at forward angles and for relatively low energy transfers, has been investigated. We have performed for the first time multi-step calculations taking into account systematically collective excitations in the second and higher order step inelastic transitions. A calculation code based on the Feshbach, Kerman and Koonin model has been modified to handle explicitly these collective excitations, most important in the forward angle domain. One step double differential pick-up cross sections were built from finite range distorted wave results spread in energy using known or estimated hole state characteristics. It is shown that two-step cross sections calculated using the above method compare rather well with those deduced via coupled channel calculations for the same collective excitations. The multi-step calculations performed up to 6 steps reproduce reasonably well the 115 Sn, 207 Pb and 115 In experimental spectra measured up to E x ∼- 40 MeV and 15 deg. The relative contributions of steps of increasing order to pick-up cross sections at E d = 200 MeV and 150 MeV are discussed. (authors)

  15. Detection of Mycobacterium tuberculosis in clinical samples by two-step polymerase chain reaction and nonisotopic hybridization methods.

    OpenAIRE

    Shawar, R M; el-Zaatari, F A; Nataraj, A; Clarridge, J E

    1993-01-01

    Detection of Mycobacterium tuberculosis in clinical specimens by the polymerase chain reaction (PCR) was compared with detection by culture. A 317-bp segment within the M. tuberculosis-specific insertion sequence IS6110 was amplified. The detection limit of the PCR assay for cultured mycobacteria was 50 cells per reaction by ethidium bromide-stained agarose gel electrophoresis and 5 cells per reaction by hybridization with an oligonucleotide probe conjugated with either digoxigenin or alkalin...

  16. Design and synthesis of fused polycycles via Diels-Alder reaction and ring-rearrangement metathesis as key steps.

    Science.gov (United States)

    Kotha, Sambasivarao; Ravikumar, Ongolu

    2015-01-01

    Atom efficient processes such as the Diels-Alder reaction (DA) and the ring-rearrangement metathesis (RRM) have been used to design new polycycles. In this regard, ruthenium alkylidene catalysts are effective in realizing the RRM of bis-norbornene derivatives prepared by DA reaction and Grignard addition. Here, fused polycycles are assembled which are difficult to produce by conventional synthetic routes.

  17. Reorientation of the Methyl Group in MAs(III) is the Rate-Limiting Step in the ArsM As(III) S-Adenosylmethionine Methyltransferase Reaction.

    Science.gov (United States)

    Packianathan, Charles; Li, Jiaojiao; Kandavelu, Palani; Sankaran, Banumathi; Rosen, Barry P

    2018-03-01

    The most common biotransformation of trivalent inorganic arsenic (As(III)) is methylation to mono-, di-, and trimethylated species. Methylation is catalyzed by As(III) S -adenosylmethionine (SAM) methyltransferase (termed ArsM in microbes and AS3MT in animals). Methylarsenite (MAs(III)) is both the product of the first methylation step and the substrate of the second methylation step. When the rate of the overall methylation reaction was determined with As(III) as the substrate, the first methylation step was rapid, whereas the second methylation step was slow. In contrast, when MAs(III) was used as the substrate, the rate of methylation was as fast as the first methylation step when As(III) was used as the substrate. These results indicate that there is a slow conformational change between the first and second methylation steps. The structure of CmArsM from the thermophilic alga Cyanidioschyzon merolae sp. 5508 was determined with bound MAs(III) at 2.27 Å resolution. The methyl group is facing the solvent, as would be expected when MAs(III) is bound as the substrate rather than facing the SAM-binding site, as would be expected for MAs(III) as a product. We propose that the rate-limiting step in arsenic methylation is slow reorientation of the methyl group from the SAM-binding site to the solvent, which is linked to the conformation of the side chain of a conserved residue Tyr70.

  18. Step-scan Fourier transform infrared (FTIR) spectrometer for investigating chemical reactions of energy-related materials. Final report, April 1, 1995--March 31, 1997

    Energy Technology Data Exchange (ETDEWEB)

    Eyring, E.M.

    1997-11-04

    Two step-scan Fourier transform infrared (FTIR) spectrometers were purchased with URI-DOE funds by the University of Utah. These infrared spectrometers have been used to carry out the following investigations: the determination of strength of adsorption of organic molecules at the liquid-solid interface of coated attenuated total reflectance (ATR) elements, the kinetic study of the photoinitiated polymerization of a dental resin, the exploration of the kinetics of photochemical reactions of organic molecules in solution, and the development of a stopped-flow FTIR interface for measuring rates and mechanisms of reactions in solution that are not photoinitiated and do not have convenient ultraviolet-visible spectral features.

  19. Experimental studies of keV energy neutron-induced reactions relevant to astrophysics and nuclear physics

    Energy Technology Data Exchange (ETDEWEB)

    Shima, T.; Kii, T.; Kikuchi, T.; Okazaki, F.; Kobayashi, T.; Baba, T.; Nagai, Y. [Tokyo Inst. of Tech. (Japan). Faculty of Science; Igashira, M.

    1997-03-01

    Nuclear reactions induced by keV energy neutrons provide a plenty of informations for studies of both astrophysics and nuclear physics. In this paper we will show our experimental studies of neutron- induced reactions of light nuclei in the keV energy region by means of a pulsed keV neutron beam and high-sensitivity detectors. Also we will discuss astrophysical and nuclear-physical consequences by using the obtained results. (author)

  20. A theoretical study of the mechanism of the atmospherically relevant reaction of chlorine atoms with methyl nitrate, and calculation of the reaction rate coefficients at temperatures relevant to the troposphere.

    Science.gov (United States)

    Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

    2015-03-21

    The reaction between atomic chlorine (Cl) and methyl nitrate (CH3ONO2) is significant in the atmosphere, as Cl is a key oxidant, especially in the marine boundary layer, and alkyl nitrates are important nitrogen-containing organic compounds, which are temporary reservoirs of the reactive nitrogen oxides NO, NO2 and NO3 (NOx). Four reaction channels HCl + CH2ONO2, CH3OCl + NO2, CH3Cl + NO3 and CH3O + ClNO2 were considered. The major channel is found to be the H abstraction channel, to give the products HCl + CH2ONO2. For all channels, geometry optimization and frequency calculations were carried out at the M06-2X/6-31+G** level, while relative electronic energies were improved to the UCCSD(T*)-F12/CBS level. The reaction barrier (ΔE(‡)0K) and reaction enthalpy (ΔH(RX)298K) of the H abstraction channel were computed to be 0.61 and -2.30 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS//M06-2X/6-31+G** level. Reaction barriers (ΔE(‡)0K) for the other channels are more positive and these pathways do not contribute to the overall reaction rate coefficient in the temperature range considered (200-400 K). Rate coefficients were calculated for the H-abstraction channel at various levels of variational transition state theory (VTST) including tunnelling. Recommended ICVT/SCT rate coefficients in the temperature range 200-400 K are presented for the first time for this reaction. The values obtained in the 200-300 K region are particularly important as they will be valuable for atmospheric modelling calculations involving reactions with methyl nitrate. The implications of the results to atmospheric chemistry are discussed. Also, the enthalpies of formation, ΔHf,298K, of CH3ONO2 and CH2ONO2 were computed to be -29.7 and 19.3 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS level.

  1. Parameters for calculation of nuclear reactions of relevance to non-energy nuclear applications (Reference Input Parameter Library: Phase III). Summary report of the first research coordination meeting

    International Nuclear Information System (INIS)

    Capote Noy, R.

    2004-08-01

    A summary is given of the First Research Coordination Meeting on Parameters for Calculation of Nuclear Reactions of Relevance to Non-Energy Nuclear Applications (Reference Input Parameter Library: Phase III), including a critical review of the RIPL-2 file. The new library should serve as input for theoretical calculations of nuclear reaction data at incident energies up to 200 MeV, as needed for energy and non-energy modern applications of nuclear data. Technical discussions and the resulting work plan of the Coordinated Research Programme are summarized, along with actions and deadlines. Participants' contributions to the RCM are also attached. (author)

  2. Design and synthesis of fused polycycles via Diels–Alder reaction and ring-rearrangement metathesis as key steps

    Directory of Open Access Journals (Sweden)

    Sambasivarao Kotha

    2015-07-01

    Full Text Available Atom efficient processes such as the Diels–Alder reaction (DA and the ring-rearrangement metathesis (RRM have been used to design new polycycles. In this regard, ruthenium alkylidene catalysts are effective in realizing the RRM of bis-norbornene derivatives prepared by DA reaction and Grignard addition. Here, fused polycycles are assembled which are difficult to produce by conventional synthetic routes.

  3. One-step fabrication of PEGylated fluorescent nanodiamonds through the thiol-ene click reaction and their potential for biological imaging

    Science.gov (United States)

    Huang, Hongye; Liu, Meiying; Tuo, Xun; Chen, Junyu; Mao, Liucheng; Wen, Yuanqing; Tian, Jianwen; Zhou, Naigen; Zhang, Xiaoyong; Wei, Yen

    2018-05-01

    Over the past years, fluorescent carbon nanoparticles have got growing interest for biological imaging. Fluorescent nanodiamonds (FNDs) are novel fluorescent carbon nanoparticles with multitudinous useful properties, including remarkable fluorescence properties, extremely low toxicity and high refractive index. However, facile preparation of FNDs with designable properties and functions from non-fluorescent detonation nanodiamonds (DNDs) has demonstrated to be challengeable. In this work, we reported for the first time that preparation of Polyethylene glycol (PEG) functionalized FNDs through a one-step thiol-ene click reaction using thiol containing PEG (PEG-SH) as the coating agent. Based on the characterization results, we demonstrated that PEG-SH could be efficiently introduced on DNDs to obtain FNDs through the thiol-ene click chemistry. The resultant FND-PEG composites showed high water dispersibility, strong fluorescence and low cytotoxicity. Moreover, FND-PEG composites could be internalized by cells and displayed good cell dyeing performance. All of these features implied that FND-PEG composites are of great potential for biological imaging. Taken together, a facile one-step strategy based on the one-step thiol-ene click reaction has been developed for efficient preparation of FND-PEG composites from non-fluorescent DNDs. The strategy should be also useful for fabrication of many other functional FNDs via using different thiol containing compounds for the universality of thiol-ene click reaction.

  4. Synthesis of the AB ring system of clifednamide utilizing Claisen rearrangement and Diels-Alder reaction as key steps.

    Science.gov (United States)

    Loke, Inga; Bentzinger, Guillaume; Holz, Julia; Raja, Aruna; Bhasin, Aman; Sasse, Florenz; Köhn, Andreas; Schobert, Rainer; Laschat, Sabine

    2016-01-21

    In order to construct the functionalized AB ring system of clifednamide, member of the class of macrocyclic tetramic acid lactams, a synthesis was developed which utilized an Ireland-Claisen rearrangement and an intramolecular Diels-Alder reaction. Starting from di-O-isopropylidene-d-mannitol the allyl carboxylate precursor for the sigmatropic rearrangement was prepared. This rearrangement proceeded diastereoselectively only in the presence of an allyl silyl ether instead of the parent enone in the side chain, as suggested by deuteration experiments. A subsequent Diels-Alder reaction yielded the target ethyl hexahydro-1H-indene-carboxylate with high diastereoselectivity. Quantum-chemical investigations of this intramolecular Diels-Alder reaction support the proposed configuration of the final product.

  5. Measurement of the $^{44}$Ti($\\alpha$,p)$^{47}$V reaction cross section, of relevance to $\\gamma$-ray observation of core collapse supernovae, using reclaimed $^{44}$Ti

    CERN Multimedia

    Despite decades of research, fundamental uncertainties remain in the underlying explosion mechanism of core collapse supernovae. One of the most direct methods that might help resolve this problem is a comparison of the predicted to the observed flux of $\\gamma$-rays due to decay of $^{44}$Ti produced in the explosion, as it is believed this could reveal the location of the mass cut, a key hydrodynamical property of the explosion. Such a study is at present limited by the uncertainty in the $^{44}$Ti($\\alpha$,p)$^{47}$V reaction rate. In this experiment we propose to measure the cross section for this reaction at astrophysically relevant energies. The single previous measurement of this reaction was limited to higher energies due to low beam intensities. Here, a more intense beam will be employed, generated from $^{44}$Ti reclaimed as part of the ERAWAST project at PSI.

  6. The B-10((p)over-right-arrow, gamma)C-11 reaction at astrophysically relevant energies

    NARCIS (Netherlands)

    Tonchev, AP; Nelson, SO; Sabourov, K; Crowley, BT; Joshi, K; Weller, HR; Kelley, JH; Prior, RM; Spraker, M; Kalantar-Nayestanaki, N

    2003-01-01

    The B-10(, gamma)C-11 reaction was studied by detecting the gamma-rays produced when 100, 130-, and 160-keV polarized protons were stopped in a thick B-10 target. Polarized and unpolarized incident beams were used to measure the cross section and vector analyzing power as a function of angle and

  7. New Improved Indirect Measurement of the F-19(p, alpha)O-16 Reaction at Energies of Astrophysical Relevance

    Czech Academy of Sciences Publication Activity Database

    Indelicato, I.; La Cognata, M.; Spitaleri, C.; Burjan, Václav; Cherubini, S.; Gulino, M.; Hayakawa, S.; Hons, Zdeněk; Kroha, Václav; Lamia, L.; Mazzocco, M.; Mrázek, Jaromír; Pizzone, R. G.; Romano, S.; Strano, E.; Torresi, D.; Tumino, A.

    2017-01-01

    Roč. 845, č. 1 (2017), č. článku 19. ISSN 0004-637X Institutional support: RVO:61389005 Keywords : nuclear reactions * nucleosynthesis * abundances Subject RIV: BN - Astronomy, Celestial Mechanics, Astrophysics OBOR OECD: Astronomy (including astrophysics,space science) Impact factor: 5.533, year: 2016

  8. The initial step of silicate versus aluminosilicate formation in zeolite synthesis: a reaction mechanism in water with a tetrapropylammonium template

    KAUST Repository

    Trinh, Thuat T.; Rozanska, Xavier; Delbecq, Franç oise; Sautet, Philippe

    2012-01-01

    is then compared to a simple calculation using an implicit continuum model for the solvent. The results underline the importance of an explicit and dynamical treatment of the water solvent, which plays a key role in assisting the reaction. © the Owner Societies

  9. Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.

    Science.gov (United States)

    Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J

    2015-02-17

    CONSPECTUS: Reactions on water and ice surfaces and in other aqueous media are ubiquitous in the atmosphere, but the microscopic mechanisms of most of these processes are as yet unknown. This Account examines recent progress in atomistic simulations of such reactions and the insights provided into mechanisms and interpretation of experiments. Illustrative examples are discussed. The main computational approaches employed are classical trajectory simulations using interaction potentials derived from quantum chemical methods. This comprises both ab initio molecular dynamics (AIMD) and semiempirical molecular dynamics (SEMD), the latter referring to semiempirical quantum chemical methods. Presented examples are as follows: (i) Reaction of the (NO(+))(NO3(-)) ion pair with a water cluster to produce the atmospherically important HONO and HNO3. The simulations show that a cluster with four water molecules describes the reaction. This provides a hydrogen-bonding network supporting the transition state. The reaction is triggered by thermal structural fluctuations, and ultrafast changes in atomic partial charges play a key role. This is an example where a reaction in a small cluster can provide a model for a corresponding bulk process. The results support the proposed mechanism for production of HONO by hydrolysis of NO2 (N2O4). (ii) The reactions of gaseous HCl with N2O4 and N2O5 on liquid water surfaces. Ionization of HCl at the water/air interface is followed by nucleophilic attack of Cl(-) on N2O4 or N2O5. Both reactions proceed by an SN2 mechanism. The products are ClNO and ClNO2, precursors of atmospheric atomic chlorine. Because this mechanism cannot result from a cluster too small for HCl ionization, an extended water film model was simulated. The results explain ClNO formation experiments. Predicted ClNO2 formation is less efficient. (iii) Ionization of acids at ice surfaces. No ionization is found on ideal crystalline surfaces, but the process is efficient on

  10. Outpatient rapid 4-step desensitization for gynecologic oncology patients with mild to low-risk, moderate hypersensitivity reactions to carboplatin/cisplatin.

    Science.gov (United States)

    Li, Quan; Cohn, David; Waller, Allyson; Backes, Floor; Copeland, Larry; Fowler, Jeffrey; Salani, Ritu; O'Malley, David

    2014-10-01

    The primary objective of this study is to assess the efficacy and safety of an outpatient, 4-step, one-solution desensitization protocol in gynecologic oncology patients with history of mild to low-risk, moderate hypersensitivity reactions (HSRs) to platinums (carboplatin and cisplatin). This was a single institutional retrospective review. Gynecologic oncology patients with a documented history of mild or low-risk, moderate immediate HSRs to carboplatin/cisplatin and continued treatment with 4-step, one-solution desensitization protocols in the outpatient infusion center were included. Patients with delayed HSRs or immediate high-risk, moderate or severe HSRs were excluded. The primary end point was the rate of successful administrations of each course of platinums. From January 2011 to June 2013, eighteen eligible patients were evaluated for outpatient 4-step, one-solution desensitization. Thirteen patients had a history of HSRs to carboplatin and 5 with HSRs to cisplatin. All of 18 patients successfully completed 94 (98.9%) of 95 desensitization courses in the outpatient infusion center. Eight of 8 (100%) patients with initial mild HSRs completed 29/29 (100%) desensitization courses, and 9 of 10 (90%) of patients with initial moderate HSRs completed 65/66 (94%) desensitization courses. In total, 65/95 (68%) desensitizations resulted in no breakthrough reactions, and mild, moderate and severe breakthrough reactions were seen in 19%, 12% and 1% desensitizations, respectively. No patients were hospitalized during desensitization. The outpatient rapid, 4-step, one-solution desensitization protocol was effective and appeared safe among gynecologic oncology patients who experienced mild to low-risk, moderate HSRs to carboplatin/cisplatin. Copyright © 2014 Elsevier Inc. All rights reserved.

  11. 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-.

  12. Synthesis of the reported structure of piperazirum using a nitro-Mannich reaction as the key stereochemical determining step

    Directory of Open Access Journals (Sweden)

    James C. Anderson

    2013-08-01

    Full Text Available Piperazirum, isolated from Arum palaestinum Boiss, was originally assigned as r-3,c-5-diisobutyl-c-6-isopropylpiperazin-2-one. The reported structure was synthesised diastereoselectively using a key nitro-Mannich reaction to set up the C5/C6 relative stereochemistry. The structure was unambiguously assigned by single crystal X-ray diffraction but the spectroscopic data did not match those reported for the natural product. The structure of the natural product must therefore be revised.

  13. Influence of the reaction conditions on the enzyme catalyzed transesterification of castor oil: A possible step in biodiesel production.

    Science.gov (United States)

    Andrade, Thalles A; Errico, Massimiliano; Christensen, Knud V

    2017-11-01

    The identification of the influence of the reaction parameters is of paramount importance when defining a process design. In this work, non-edible castor oil was reacted with methanol to produce a possible component for biodiesel blends, using liquid enzymes as the catalyst. Temperature, alcohol-to-oil molar ratio, enzyme and added water contents were the reaction parameters evaluated in the transesterification reactions. The optimal conditions, giving the optimal final FAME yield and FFA content in the methyl ester-phase was identified. At 35°C, 6.0 methanol-to-oil molar ratio, 5wt% of enzyme and 5wt% of water contents, 94% of FAME yield and 6.1% of FFA in the final composition were obtained. The investigation was completed with the analysis of the component profiles, showing that at least 8h are necessary to reach a satisfactory FAME yield together with a minor FFA content. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Exploring nuclear reactions relevant to Stellar and Big-Bang Nucleosynthesis using High-Energy-Density plasmas at OMEGA and the NIF

    Science.gov (United States)

    Gatu Johnson, M.

    2017-10-01

    Thermonuclear reaction rates and nuclear processes have been explored traditionally by means of accelerator experiments, which are difficult to execute at conditions relevant to Stellar Nucleosynthesis (SN) and Big Bang Nucleosynthesis (BBN). High-Energy-Density (HED) plasmas closely mimic astrophysical environments and are an excellent complement to accelerator experiments in exploring SN and BBN-relevant nuclear reactions. To date, our work using HED plasmas at OMEGA and NIF has focused on the complementary 3He+3He, T+3He and T +T reactions. First studies of the T +T reaction indicated the significance of the 5He ground-state resonance in the T +T neutron spectrum. Subsequent T +T experiments showed that the strength of this resonance varies with center-of-mass (c-m) energy in the range of 16-50 keV, a variation that is not fundamentally understood. Studies of the 3He+3He and T+3He reactions have also been conducted at OMEGA at c-m energies of 165 keV and 80 keV, respectively, and the results revealed three things. First, a large cross section for the T+3He- γ branch can be ruled out as an explanation for the anomalously high abundance of 6Li in primordial material. Second, the results contrasted to theoretical modeling indicate that the mirror-symmetry assumption is not enough to capture the differences between T +T and 3He+3He reactions. Third, the elliptical spectrum assumed in the analysis of 3He+3He data obtained in accelerator experiments is incorrect. Preliminary data from recent experiments at the NIF exploring the 3He+3He reaction at c-m energies of 60 keV and 100 keV also indicate that the underlying physics changes with c-m energy. In this talk, we describe these findings and future directions for exploring light-ion reactions at OMEGA and the NIF. The work was supported in part by the US DOE, LLE, and LLNL.

  15. Simulation of reaction diffusion processes over biologically relevant size and time scales using multi-GPU workstations.

    Science.gov (United States)

    Hallock, Michael J; Stone, John E; Roberts, Elijah; Fry, Corey; Luthey-Schulten, Zaida

    2014-05-01

    Simulation of in vivo cellular processes with the reaction-diffusion master equation (RDME) is a computationally expensive task. Our previous software enabled simulation of inhomogeneous biochemical systems for small bacteria over long time scales using the MPD-RDME method on a single GPU. Simulations of larger eukaryotic systems exceed the on-board memory capacity of individual GPUs, and long time simulations of modest-sized cells such as yeast are impractical on a single GPU. We present a new multi-GPU parallel implementation of the MPD-RDME method based on a spatial decomposition approach that supports dynamic load balancing for workstations containing GPUs of varying performance and memory capacity. We take advantage of high-performance features of CUDA for peer-to-peer GPU memory transfers and evaluate the performance of our algorithms on state-of-the-art GPU devices. We present parallel e ciency and performance results for simulations using multiple GPUs as system size, particle counts, and number of reactions grow. We also demonstrate multi-GPU performance in simulations of the Min protein system in E. coli . Moreover, our multi-GPU decomposition and load balancing approach can be generalized to other lattice-based problems.

  16. The role of MgCl2 compounds in preparation of Tin oxide micro particles by one-step solid - state chemical reaction method and characterization of microstructure

    International Nuclear Information System (INIS)

    Hojabry, A.; Rezainik, Y.; Abdoljavad, N.; Moghimi, N.; Shakib, M.

    2007-01-01

    In this paper, Tin oxide (SnO 2 ) nano crystals have been synthesized by one-step solid-state chemical reactions method. In the first step, the powder of SnCl 4 . 5H 2 O was mixed with MgCl 2 and Mg(OH) 2 with a weight ratio of Sn to Mg (2:1) in the air atmosphere at room, and then annealed at 200 d egree C , 400 d egree C and 600 d egree C in air for 4 h to give different size of nanoparticles. This method is a simple, efficient and economic preparation for SnO 2 nanoparticles with adjustable grain sizes in the range of 7-32 nm in high yield. The microstructure and morphology of SnO 2 nanoparticles have been studied by X-ray diffraction (XRD), scanning electron microscopy and thermal analysis (thermogravimetric analysis -differential thermal analysis).

  17. Graphite Carbon-Supported Mo2C Nanocomposites by a Single-Step Solid State Reaction for Electrochemical Oxygen Reduction.

    Science.gov (United States)

    Huang, K; Bi, K; Liang, C; Lin, S; Wang, W J; Yang, T Z; Liu, J; Zhang, R; Fan, D Y; Wang, Y G; Lei, M

    2015-01-01

    Novel graphite-molybdenum carbide nanocomposites (G-Mo2C) are synthesized by a typical solid state reaction with melamine and MoO3 as precursors under inert atmosphere. The characterization results indicate that G-Mo2C composites are composed of high crystallization and purity of Mo2C and few layers of graphite carbon. Mo2C nanoparticles with sizes ranging from 5 to 50 nm are uniformly supported by surrounding graphite layers. It is believed that Mo atom resulting from the reduction of MoO3 is beneficial to the immobilization of graphite carbon. Moreover, the electrocatalytic performances of G-Mo2C for ORR in alkaline medium are investigated by cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry test with 3M methanol. The results show that G-Mo2C has a considerable catalytic activity and superior methanol tolerance performance for the oxygen reduction reaction (ORR) benefiting from the chemical interaction between the carbide nanoparticles and graphite carbon.

  18. Standardization of a two-step real-time polymerase chain reaction based method for species-specific detection of medically important Aspergillus species.

    Science.gov (United States)

    Das, P; Pandey, P; Harishankar, A; Chandy, M; Bhattacharya, S; Chakrabarti, A

    2017-01-01

    Standardization of Aspergillus polymerase chain reaction (PCR) poses two technical challenges (a) standardization of DNA extraction, (b) optimization of PCR against various medically important Aspergillus species. Many cases of aspergillosis go undiagnosed because of relative insensitivity of conventional diagnostic methods such as microscopy, culture or antigen detection. The present study is an attempt to standardize real-time PCR assay for rapid sensitive and specific detection of Aspergillus DNA in EDTA whole blood. Three nucleic acid extraction protocols were compared and a two-step real-time PCR assay was developed and validated following the recommendations of the European Aspergillus PCR Initiative in our setup. In the first PCR step (pan-Aspergillus PCR), the target was 28S rDNA gene, whereas in the second step, species specific PCR the targets were beta-tubulin (for Aspergillus fumigatus, Aspergillus flavus, Aspergillus terreus), gene and calmodulin gene (for Aspergillus niger). Species specific identification of four medically important Aspergillus species, namely, A. fumigatus, A. flavus, A. niger and A. terreus were achieved by this PCR. Specificity of the PCR was tested against 34 different DNA source including bacteria, virus, yeast, other Aspergillus sp., other fungal species and for human DNA and had no false-positive reactions. The analytical sensitivity of the PCR was found to be 102 CFU/ml. The present protocol of two-step real-time PCR assays for genus- and species-specific identification for commonly isolated species in whole blood for diagnosis of invasive Aspergillus infections offers a rapid, sensitive and specific assay option and requires clinical validation at multiple centers.

  19. Structural zinc(II thiolate complexes relevant to the modeling of Ada repair protein: Application toward alkylation reactions

    Directory of Open Access Journals (Sweden)

    Mohamed M. Ibrahim

    2014-11-01

    Full Text Available The TtZn(II-bound perchlorate complex [TtZn–OClO3] 1 (Ttxyly = hydrotris[N-xylyl-thioimidazolyl]borate was used for the synthesis of zinc(II-bound ethanthiothiol complex [TtZn–SCH2CH3] 2 and its hydrogen-bond containing analog Tt–ZnSCH2CH2–NH(COOC(CH33 3. These thiolate complexes were examined as structural models for the active sites of Ada repair protein toward methylation reactions. The Zn[S3O] coordination sphere in complex 1 includes three thione donors from the ligand Ttixyl and one oxygen donor from the perchlorate coligand in ideally tetrahedral arrangement around the zinc center. The average Zn(1–S(thione bond length is 2.344 Å, and the Zn(1–O(1 bond length is 1.917 Å.

  20. First cross-section measurements of the reactions Ag,109107(p ,γ )Cd,110108 at energies relevant to the p process

    Science.gov (United States)

    Khaliel, A.; Mertzimekis, T. J.; Asimakopoulou, E.-M.; Kanellakopoulos, A.; Lagaki, V.; Psaltis, A.; Psyrra, I.; Mavrommatis, E.

    2017-09-01

    Background: One of the primary objectives of the field of Nuclear Astrophysics is the study of the elemental and isotopic abundances in the universe. Although significant progress has been made in understanding the mechanisms behind the production of a large number of nuclides in the isotopic chart, there are still many open questions regarding a number of neutron-deficient nuclei, the p nuclei. To that end, experimentally deduced nuclear reaction cross sections can provide invaluable input to astrophysical models. Purpose: The reactions Ag,109107(p ,γ )Cd,110108 have been studied at energies inside the astrophysically relevant energy window in an attempt to provide experimental data required for the testing of reaction-rate predictions in terms of the statistical model of Hauser-Feshbach around the p nucleus 108Cd. Methods: The experiments were performed with in-beam γ -ray spectroscopy with proton beams accelerated by the Tandem Van de Graaff Accelerator at NCSR "Demokritos" impinging a target of natural silver. A set of high-purity germanium detectors was employed to record the emitted radiation. Results: A first set of total cross-section measurements in radiative proton-capture reactions involving Ag,109107, producing the p -nucleus 108Cd, inside the astrophysically relevant energy window is reported. The experimental results are compared to theoretical calculations, using talys. An overall good agreement between the data and the theoretical calculations has been found. Conclusions: The results reported in this work add new information to the relatively unexplored p process. The present measurements can serve as a reference point in understanding the nuclear parameters in the related astrophysical environments and for future theoretical modeling and experimental works.

  1. Chemical reactions in the nitrogen-acetone ice induced by cosmic ray analogues: relevance for the Solar system

    Science.gov (United States)

    de Barros, A. L. F.; Andrade, D. P. P.; da Silveira, E. F.; Alcantara, K. F.; Boduch, P.; Rothard, H.

    2018-02-01

    The radiolysis of 10:1 nitrogen:acetone mixture, condensed at 11 K, by 40 MeV 58Ni11 + ions is studied. These results are representative of studies concerning Solar system objects, such as transneptunian objects, exposed to cosmic rays. Bombardment by cosmic rays triggers chemical reactions leading to synthesis of larger molecules. In this work, destruction cross-sections of acetone and nitrogen molecules in solid phase are determined and compared with those for pure acetone. The N2 column density decreases very fast indicating that, under irradiation, nitrogen leaves quickly a porous sample. The most abundant molecular species formed in the radiolysis are C3H6, C2H6, N3, CO, CH4 and CO2. Some N-bearing species are also formed, but with low production yield. Dissolving acetone in nitrogen decreases the formation cross-sections of CH4, CO2 and H2CO, while increases those for CO and C2H6 species. This fact may explain the presence of C2H6 in Pluto's surface where CH4 is not pure, but diluted in an N2 matrix. The formation of more complex molecules, such as HNCO and, possibly, glycine is observed, suggesting the formation of small prebiotic species in objects beyond Neptune from acetone diluted in a N2 matrix irradiated by cosmic rays.

  2. Water permeability, hybrid layer long-term integrity and reaction mechanism of a two-step adhesive system.

    Science.gov (United States)

    Grégoire, Geneviève; Dabsie, Firas; Delannée, Mathieu; Akon, Bernadette; Sharrock, Patrick

    2010-07-01

    Our aim was to investigate the reaction mechanism of formation of the hybrid layer by a HEMA-containing self-etch adhesive and to study fluid filtration, contact angle and interfacial ultrastructure by SEM following a 1 year ageing period. Acidic behaviour and chemical interactions between Silorane System Adhesive and dentine were studied by potentiometric titrations, atomic absorption spectroscopy and infrared spectroscopy. The hydrophilicity of the adhesive was evaluated using the sessile drop method and dentine permeability by hydraulic conductance. The morphological study of the dentine/adhesive system interface was conducted using SEM. The Silorane System Adhesive behaved as a multi-acid with several different pK(a) values. When the adhesive was in contact with dentine, the acid was progressively consumed and calcium ions were released. The acrylate substituted phosphonate bound strongly to apatite crystals. The polyacrylic acid copolymer reacted with calcium ions and formed an interpenetrating polymer network (IPN). Water contact angle measurements showed rapid spreading on primer (angles reached 15 degrees at 30s) and larger contact angles when the Silorane bonding layer was added (from over 60 degrees to 44 degrees ). A thick, homogeneous hybrid layer was observed both initially and after 1 year of ageing, with a corresponding hydraulic conductance of -48.50% initially and -52.07% at 12 months. The Silorane System Adhesive is capable of both dissolving calcium ions and binding to apatite surfaces. The results showed the hydrophilicity of the adhesive, which formed an IPN-like hybrid layer that conserved adequate impermeability over a 1-year period. Copyright 2010 Elsevier Ltd. All rights reserved.

  3. A Two-Step Lyssavirus Real-Time Polymerase Chain Reaction Using Degenerate Primers with Superior Sensitivity to the Fluorescent Antigen Test

    Directory of Open Access Journals (Sweden)

    Vanessa Suin

    2014-01-01

    Full Text Available A generic two-step lyssavirus real-time reverse transcriptase polymerase chain reaction (qRT-PCR, based on a nested PCR strategy, was validated for the detection of different lyssavirus species. Primers with 17 to 30% of degenerate bases were used in both consecutive steps. The assay could accurately detect RABV, LBV, MOKV, DUVV, EBLV-1, EBLV-2, and ABLV. In silico sequence alignment showed a functional match with the remaining lyssavirus species. The diagnostic specificity was 100% and the sensitivity proved to be superior to that of the fluorescent antigen test. The limit of detection was ≤1 50% tissue culture infectious dose. The related vesicular stomatitis virus was not recognized, confirming the selectivity for lyssaviruses. The assay was applied to follow the evolution of rabies virus infection in the brain of mice from 0 to 10 days after intranasal inoculation. The obtained RNA curve corresponded well with the curves obtained by a one-step monospecific RABV-qRT-PCR, the fluorescent antigen test, and virus titration. Despite the presence of degenerate bases, the assay proved to be highly sensitive, specific, and reproducible.

  4. A two-step lyssavirus real-time polymerase chain reaction using degenerate primers with superior sensitivity to the fluorescent antigen test.

    Science.gov (United States)

    Suin, Vanessa; Nazé, Florence; Francart, Aurélie; Lamoral, Sophie; De Craeye, Stéphane; Kalai, Michael; Van Gucht, Steven

    2014-01-01

    A generic two-step lyssavirus real-time reverse transcriptase polymerase chain reaction (qRT-PCR), based on a nested PCR strategy, was validated for the detection of different lyssavirus species. Primers with 17 to 30% of degenerate bases were used in both consecutive steps. The assay could accurately detect RABV, LBV, MOKV, DUVV, EBLV-1, EBLV-2, and ABLV. In silico sequence alignment showed a functional match with the remaining lyssavirus species. The diagnostic specificity was 100% and the sensitivity proved to be superior to that of the fluorescent antigen test. The limit of detection was ≤ 1 50% tissue culture infectious dose. The related vesicular stomatitis virus was not recognized, confirming the selectivity for lyssaviruses. The assay was applied to follow the evolution of rabies virus infection in the brain of mice from 0 to 10 days after intranasal inoculation. The obtained RNA curve corresponded well with the curves obtained by a one-step monospecific RABV-qRT-PCR, the fluorescent antigen test, and virus titration. Despite the presence of degenerate bases, the assay proved to be highly sensitive, specific, and reproducible.

  5. Single-molecule Imaging Analysis of Elementary Reaction Steps of Trichoderma reesei Cellobiohydrolase I (Cel7A) Hydrolyzing Crystalline Cellulose Iα and IIII*

    Science.gov (United States)

    Shibafuji, Yusuke; Nakamura, Akihiko; Uchihashi, Takayuki; Sugimoto, Naohisa; Fukuda, Shingo; Watanabe, Hiroki; Samejima, Masahiro; Ando, Toshio; Noji, Hiroyuki; Koivula, Anu; Igarashi, Kiyohiko; Iino, Ryota

    2014-01-01

    Trichoderma reesei cellobiohydrolase I (TrCel7A) is a molecular motor that directly hydrolyzes crystalline celluloses into water-soluble cellobioses. It has recently drawn attention as a tool that could be used to convert cellulosic materials into biofuel. However, detailed mechanisms of action, including elementary reaction steps such as binding, processive hydrolysis, and dissociation, have not been thoroughly explored because of the inherent challenges associated with monitoring reactions occurring at the solid/liquid interface. The crystalline cellulose Iα and IIII were previously reported as substrates with different crystalline forms and different susceptibilities to hydrolysis by TrCel7A. In this study, we observed that different susceptibilities of cellulose Iα and IIII are highly dependent on enzyme concentration, and at nanomolar enzyme concentration, TrCel7A shows similar rates of hydrolysis against cellulose Iα and IIII. Using single-molecule fluorescence microscopy and high speed atomic force microscopy, we also determined kinetic constants of the elementary reaction steps for TrCel7A against cellulose Iα and IIII. These measurements were performed at picomolar enzyme concentration in which density of TrCel7A on crystalline cellulose was very low. Under this condition, TrCel7A displayed similar binding and dissociation rate constants for cellulose Iα and IIII and similar fractions of productive binding on cellulose Iα and IIII. Furthermore, once productively bound, TrCel7A processively hydrolyzes and moves along cellulose Iα and IIII with similar translational rates. With structural models of cellulose Iα and IIII, we propose that different susceptibilities at high TrCel7A concentration arise from surface properties of substrate, including ratio of hydrophobic surface and number of available lanes. PMID:24692563

  6. Two-step multiplex polymerase chain reaction improves the speed and accuracy of genotyping using DNA from noninvasive and museum samples.

    Science.gov (United States)

    Arandjelovic, M; Guschanski, K; Schubert, G; Harris, T R; Thalmann, O; Siedel, H; Vigilant, L

    2009-01-01

    Many studies in molecular ecology rely upon the genotyping of large numbers of low-quantity DNA extracts derived from noninvasive or museum specimens. To overcome low amplification success rates and avoid genotyping errors such as allelic dropout and false alleles, multiple polymerase chain reaction (PCR) replicates for each sample are typically used. Recently, two-step multiplex procedures have been introduced which drastically increase the success rate and efficiency of genotyping. However, controversy still exists concerning the amount of replication needed for suitable control of error. Here we describe the use of a two-step multiplex PCR procedure that allows rapid genotyping using at least 19 different microsatellite loci. We applied this approach to quantified amounts of noninvasive DNAs from western chimpanzee, western gorilla, mountain gorilla and black and white colobus faecal samples, as well as to DNA from ~100-year-old gorilla teeth from museums. Analysis of over 45 000 PCRs revealed average success rates of > 90% using faecal DNAs and 74% using museum specimen DNAs. Average allelic dropout rates were substantially reduced compared to those obtained using conventional singleplex PCR protocols, and reliable genotyping using low (< 25 pg) amounts of template DNA was possible. However, four to five replicates of apparently homozygous results are needed to avoid allelic dropout when using the lowest concentration DNAs (< 50 pg/reaction), suggesting that use of protocols allowing routine acceptance of homozygous genotypes after as few as three replicates may lead to unanticipated errors when applied to low-concentration DNAs. © 2008 The Authors. Journal compilation © 2008 Blackwell Publishing Ltd.

  7. The founding period of the Secretaría de Trabajo y Previsión (1943-1946: first organizational steps and relevant figures

    Directory of Open Access Journals (Sweden)

    María Paula Luciani

    2015-04-01

    Full Text Available Through the analysis of a range of state documents, biographies and specialized publications, among others, this article aims at reconstructing the first organizational steps of the Labour and Social Security sphere during the military government of 1943-1946, when after several decades of functioning of the Departamento Nacional del Trabajo, labour issues acquired a renewed importance in terms of state organization. In this period, several figures, beyond the names of Juan Perón and his most well- known contributors, helped to build the basis of the new Secretaría de Trabajo y Previsión. Often underestimated by the researchers, these pages also try to take them into consideration

  8. Major achievements of the European shield blanket R and D during the ITER EDA, and their relevance for future next step machines

    Energy Technology Data Exchange (ETDEWEB)

    Daenner, W. E-mail: daenner@ipp.mpg.de; Cardella, A.; Jones, L.; Lorenzetto, P.; Maisonnier, D.; Malavasi, G.; Peacock, A.; Rodgers, E.; Tavassoli, F

    2000-11-01

    In the frame of the international thermonuclear experimental reactors (ITER) collaboration, the European home team (EU HT) has committed significant efforts on the R and D for the Shield Blanket. This paper summarises the main achievements of this programme, which have been obtained over the last 7 years. The depth of R and D extends from generic activities up to the manufacture of prototypes, but has, in accordance with the design progress, reached different stages of maturity for the various components. New ITER options being considered since early 1998 have not made these activities irrelevant. With few exceptions, the results are still applicable for less ambitious next step machines, or transferable to components with similar functions or requirements.

  9. Two-step bacterial broad-range polymerase chain reaction analysis of heart valve tissue improves bacteriological diagnosis of infective endocarditis.

    Science.gov (United States)

    Boussier, Rémi; Rogez, Sylvie; François, Bruno; Denes, Eric; Ploy, Marie-Cécile; Garnier, Fabien

    2013-03-01

    Positive heart valve (HV) culture is a major Duke's criterion for the diagnosis of infective endocarditis but is poorly sensitive. Two broad-range 16S rDNA polymerase chain reaction (PCR) methods were applied to 31 HV samples: first, a real-time method, then conventional end-point PCR was applied to HV samples on which the first PCR was negative. Five specific real-time PCR procedures were also used in order to identify Bartonella spp., Tropheryma whipplei, Chlamydophila pneumoniae, Mycoplasma pneumonia, and Coxiella burnetii. A strategy combining the 2-step broad-range PCR methods improved the sensitivity of the molecular method from 38.7% to 58%. Specific PCR identified 1 T. whipplei, which was also identified by conventional end-point PCR. These results confirm that blood culture is the gold standard for the diagnosis of infective endocarditis, shows that molecular methods applied to HV can be useful when blood culture is negative, and that 2-step broad-range PCR approach seems to be more sensitive. Copyright © 2013 Elsevier Inc. All rights reserved.

  10. Two-step protein labeling by using lipoic acid ligase with norbornene substrates and subsequent inverse-electron demand Diels-Alder reaction.

    Science.gov (United States)

    Best, Marcel; Degen, Anna; Baalmann, Mathis; Schmidt, Tobias T; Wombacher, Richard

    2015-05-26

    Inverse-electron-demand Diels-Alder cycloaddition (DAinv ) between strained alkenes and tetrazines is a highly bio-orthogonal reaction that has been applied in the specific labeling of biomolecules. In this work we present a two-step labeling protocol for the site-specific labeling of proteins based on attachment of a highly stable norbornene derivative to a specific peptide sequence by using a mutant of the enzyme lipoic acid ligase A (LplA(W37V) ), followed by the covalent attachment of tetrazine-modified fluorophores to the norbornene moiety through the bio-orthogonal DAinv  . We investigated 15 different norbornene derivatives for their selective enzymatic attachment to a 13-residue lipoic acid acceptor peptide (LAP) by using a standardized HPLC protocol. Finally, we used this two-step labeling strategy to label proteins in cell lysates in a site-specific manner and performed cell-surface labeling on living cells. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Stepped MS(All) Relied Transition (SMART): An approach to rapidly determine optimal multiple reaction monitoring mass spectrometry parameters for small molecules.

    Science.gov (United States)

    Ye, Hui; Zhu, Lin; Wang, Lin; Liu, Huiying; Zhang, Jun; Wu, Mengqiu; Wang, Guangji; Hao, Haiping

    2016-02-11

    Multiple reaction monitoring (MRM) is a universal approach for quantitative analysis because of its high specificity and sensitivity. Nevertheless, optimization of MRM parameters remains as a time and labor-intensive task particularly in multiplexed quantitative analysis of small molecules in complex mixtures. In this study, we have developed an approach named Stepped MS(All) Relied Transition (SMART) to predict the optimal MRM parameters of small molecules. SMART requires firstly a rapid and high-throughput analysis of samples using a Stepped MS(All) technique (sMS(All)) on a Q-TOF, which consists of serial MS(All) events acquired from low CE to gradually stepped-up CE values in a cycle. The optimal CE values can then be determined by comparing the extracted ion chromatograms for the ion pairs of interest among serial scans. The SMART-predicted parameters were found to agree well with the parameters optimized on a triple quadrupole from the same vendor using a mixture of standards. The parameters optimized on a triple quadrupole from a different vendor was also employed for comparison, and found to be linearly correlated with the SMART-predicted parameters, suggesting the potential applications of the SMART approach among different instrumental platforms. This approach was further validated by applying to simultaneous quantification of 31 herbal components in the plasma of rats treated with a herbal prescription. Because the sMS(All) acquisition can be accomplished in a single run for multiple components independent of standards, the SMART approach are expected to find its wide application in the multiplexed quantitative analysis of complex mixtures. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Analyzing powers and interference between one- and multi-step processes in (polarized p, t) reactions on medium-mass vibrational nuclei

    International Nuclear Information System (INIS)

    Yagi, K.; Kunori, S.; Aoki, Y.; Nagano, K.; Tagishi, Y.

    1978-01-01

    A neutron-number (N) dependence of analyzing powers A (theta) has been observed for the first time in (polarized p, t) reactions leading to the quadrupole vibrational states (2 1 + ) in 98 Ru, sup(102,108)Pd, 114 Cd, 116 Sn, and sup(120,126)Te. Although analyzing powers for the ground-state transitions A(theta,0 sub(g)sup(+)) are very similar to each other, those for the 2 1 + transitions A(theta,2 1 + ) for the nuclei belonging to the beginning of the N = 50 - 82 shell are markedly different, having almost opposite signs, from A(theta,2 1 + ) for nuclei belonging to the latter half of the major shell. The difference is explained as a result of a sign change of the interference between one- and inelastic multi-step processes in two-neutron pickup reactions. Nuclear structure effects on such an interference are discussed on the basis of the microscopic description of collective quadrupole oscillation of nuclei. (author)

  13. Treatment for the recoil effects of the multi-step heavy-ion nucleon transfers with the orthogonalized coupled-reaction-channel theory

    International Nuclear Information System (INIS)

    Misono, S.; Imanishi, B.

    1997-02-01

    We have investigated recoil effects in heavy-ion reactions for the nucleon transfers, and the validity of the spatially local approximation for the non-local transfer interaction defined by the orthogonalized coupled-reaction-channel (OCRC) theory. This approximation makes it easier to treat multi-step transfer processes with the coupled channel method and makes it possible to define the nucleon molecular orbitals with the inclusion of the recoil effects. The transfer interaction is expanded in a power series of the momentum operator, and is approximated by the first order term, i.e., the spatially local term. The numerical calculation for the core-symmetric systems 12 C+ 13 C and 16 O+ 17 O with this approximation shows that the recoil effects are well included in the results at energies lower than a few MeV/nucleon. Furthermore, the OCRC formalism allows us even to employ the complete no-recoil approximation for the calculation of cross sections, even though it is not adequate to use this approximation in the distorted wave Born approximation (DWBA) method. As to polarization, however, the no-recoil approximation is not good even in the OCRC formalism. We discuss the recoil effects on nucleon molecular-orbital states. It is shown that states of the covalent molecular orbitals of the valence (transferred) nucleon are little affected by the recoil effects, as already suggested by Korotky et al. in the full finite-range DWBA analysis of the transfer reaction, 13 C( 13 C, 12 C) 14 C. (author). 59 refs

  14. S-factor measurement of the 2H(α,γ)6Li reaction at energies relevant for Big-Bang nucleosynthesis

    International Nuclear Information System (INIS)

    Anders, Michael

    2013-01-01

    For about 20 years now, observations of 6 Li in several old metal-poor stars inside the halo of our galaxy have been reported, which are largely independent of the stars' metallicity, and which point to a possible primordial origin. The observations exceed the predictions of the Standard Big-Bang Nucleosynthesis model by a factor of 500. In the relevant energy range, no directly measured S-factors were available yet for the main production reaction 2 H(α,γ) 6 Li, while different theoretical estimations have an uncertainty of up to two orders of magnitude. The very small cross section in the picobarn range has been measured with a deuterium gas target at the LUNA accelerator (Laboratory for Underground Nuclear Astrophysics), located deep underground inside Laboratori Nazionali del Gran Sasso in Italy. A beam-induced, neutron-caused background in the γ-detector occurred which had to be analyzed carefully and subtracted in an appropriate way, to finally infer the weak signal of the reaction. For this purpose, a method to parameterize the Compton background has been developed. The results are a contribution to the discussion about the accuracy of the recent 6 Li observations, and to the question if it is necessary to include new physics into the Standard Big-Bang Nucleosynthesis model.

  15. The adverse drug reaction reporting assignment for specialist oncology nurses: a preliminary evaluation of quality, relevance and educational value in a prospective cohort study.

    Science.gov (United States)

    Schutte, Tim; van Eekeren, Rike; Richir, Milan; van Staveren, Jojanneke; van Puijenbroek, Eugène; Tichelaar, Jelle; van Agtmael, Michiel

    2018-01-01

    In a new prescribing qualification course for specialist oncology nurses, we thought that it is important to emphasize pharmacovigilance and adverse drug reaction (ADR) reporting. We aimed to develop and evaluate an ADR reporting assignment for specialist oncology nurses. The quality of report documentation was assessed with the "Clinical Documentation tool to assess Individual Case Safety Reports" (ClinDoc). The relevance of the reports was evaluated in terms of ADR seriousness, the listing for additional monitoring of the drug by European Medicines Agency (EMA), and lack of labelling information about the ADR. Nurses' opinions of the assignment were evaluated using an E-survey. Thirty-three ADRs were reported, 32 (97%) of which were well documented according to ClinDoc. Thirteen ADRs (39%) were "serious" according to CIOMS criteria. In five cases (15%), the suspect drugs were listed for additional monitoring by EMA and in seven cases (21%), the ADR was not mentioned in the Summary of Product Characteristics. Twenty-five (78.1%) of the 32 enrolled nurses completed the E-survey. Most were > 45 years of age (68%), female (92%) and had extensive clinical experience (6-33 years). All agreed or completely agreed that the reporting assignment was useful, that it fitted in daily practice and that it increased their attention for medication/patient safety. A large majority (84.0%) agreed the assignment changed how they dealt with ADRs. Specialist oncology nurses are capable of reporting ADRs, and they considered the assignment useful. The assignment yielded valuable, relevant, and well-documented ADR reports for pharmacovigilance practice.

  16. Micellar induced regioselectivity in the two-step consecutive reaction of SO3(2-) with Br-(CH2CH2)n-Br (n=2-5).

    Science.gov (United States)

    Currie, Fredrik; Jarvoll, Patrik; Holmberg, Krister; Romsted, Laurence S; Gunaseelan, Krishnan

    2007-08-15

    High field (800 MHz) (1)H NMR was used to monitor the two-step consecutive reaction of excess SO(3)(2-) with symmetrical bifunctional alpha,omega-dibromoalkanes with butane (DBB), hexane (DBH), octane (DBO), and decane (DBD) chains in CTAB micelles at 25 degrees C. The first-order rate constant for the first substitution step for DBB and DBH is about 5 times faster than for the second, but the kinetics for DBO and DBD were not cleanly first-order. After 40 min, the solution contained about 80% of the intermediate bromoalkanesulfonate from DBB and DBH and the remainder is alkanedisulfonate and unreacted starting material. The same reactions were carried out in homogeneous MeOH/D(2)O solutions at 50 degrees C. The rate constants for all four alpha,omega-dibromoalkanes were first-order throughout the time course of the reaction and the same within +/-10%. However, because micellar solutions are organized on the nanoscale and bring together lipophilic and hydrophilic reactants into a small reaction volume at the micellar interface, they speed this substitution reaction considerably compared to reaction in MeOH/D(2)O. The CTAB micelles also induce a significant regioselectivity in product formation by speeding the first step of the consecutive reaction more than the second. The results are consistent with the bromoalkanesulfonate intermediates having a radial orientation within the micelles with the -CH(2)SO(3)(-) group in the interfacial region and the -CH(2)Br group directed into the micellar core such that the concentration of -CH(2)Br groups in the reactive zone, i.e., the micellar interface, is significantly reduced. These results provide the first example of self-assembled surfactant system altering the relative rates of the reaction steps of a consecutive reaction and, in doing so, enhancing monosubstitution of a symmetrically disubstituted species.

  17. One-step hydroprocessing of fatty acids into renewable aromatic hydrocarbons over Ni/HZSM-5: insights into the major reaction pathways.

    Science.gov (United States)

    Xing, Shiyou; Lv, Pengmei; Wang, Jiayan; Fu, Junying; Fan, Pei; Yang, Lingmei; Yang, Gaixiu; Yuan, Zhenhong; Chen, Yong

    2017-01-25

    For high caloricity and stability in bio-aviation fuels, a certain content of aromatic hydrocarbons (AHCs, 8-25 wt%) is crucial. Fatty acids, obtained from waste or inedible oils, are a renewable and economic feedstock for AHC production. Considerable amounts of AHCs, up to 64.61 wt%, were produced through the one-step hydroprocessing of fatty acids over Ni/HZSM-5 catalysts. Hydrogenation, hydrocracking, and aromatization constituted the principal AHC formation processes. At a lower temperature, fatty acids were first hydrosaturated and then hydrodeoxygenated at metal sites to form long-chain hydrocarbons. Alternatively, the unsaturated fatty acids could be directly deoxygenated at acid sites without first being saturated. The long-chain hydrocarbons were cracked into gases such as ethane, propane, and C 6 -C 8 olefins over the catalysts' Brønsted acid sites; these underwent Diels-Alder reactions on the catalysts' Lewis acid sites to form AHCs. C 6 -C 8 olefins were determined as critical intermediates for AHC formation. As the Ni content in the catalyst increased, the Brønsted-acid site density was reduced due to coverage by the metal nanoparticles. Good performance was achieved with a loading of 10 wt% Ni, where the Ni nanoparticles exhibited a polyhedral morphology which exposed more active sites for aromatization.

  18. Rudimentary simple, single step fabrication of nano-flakes like AgCd alloy electro-catalyst for oxygen reduction reaction in alkaline fuel cell

    International Nuclear Information System (INIS)

    Bhandary, Nimai; Basu, Suddhasatwa; Ingole, Pravin P.

    2016-01-01

    In this work, for the first time, we report rudimentary simple, single step fabrication of an electro-catalyst based on AgCd alloy nanoparticles with flakes like geometry which shows highly efficient activity towards oxygen reduction reaction (ORR). A simple potentiostatic deposition method has been employed for co-depositing AgCd alloy nanostructures with flakes like shapes along with dendrites on the surface of carbon fibre paper. The chemico-physical properties of the catalyst are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDXS). Electro-catalytic activity of AgCd alloy based electro-catalyst towards ORR is studied in alkaline medium by cyclic voltammetry and rotating ring disk electrode (RRDE) technique. Electrochemical in-situ FTIR measurements are also performed to identify the species generated during ORR process. Based on the results from electro-catalysis experiment, it is concluded that nano-alloyed AgCd electrodeposited on carbon paper shows excellent activity for ORR, following four electron pathways with H_2O_2 yield less than 15%. The combination of low cost of Ag and Cd, fast and facile method of its fabrication and higher activity towards ORR makes the AgCd electro-catalyst an attractive catalyst of choice for alkaline fuel cell.

  19. One-step and low-temperature synthesis of iodine-doped graphene and its multifunctional applications for hydrogen evolution reaction and electrochemical sensing

    International Nuclear Information System (INIS)

    Chu, Ke; Wang, Fan; Zhao, Xiao-lin; Wei, Xiao-ping; Wang, Xin-wei; Tian, Ye

    2017-01-01

    Iodine (I) has emerged as a powerful heteroatom dopant for efficiently tailoring the electrocatalytic properties of graphene. However, the preparation methods of I-doped graphene (I-G) and its electrocatalysis applications remain largely unexplored. Herein, a one-step and low-temperature hydrothermal approach was developed for the successful synthesis of I-G with a high I-doping level (0.52 at.%). The resulting I-G was then applied as a metal-free catalyst for hydrogen evolution reaction (HER) and electrochemical sensing. It was shown that the I-G exhibited a dramatically enhanced HER activity compared to undoped graphene, attributed to the critical role of I-doping in offering large exposed active sites and high electron transfer capability. Furthermore, I-G also displayed attractive sensing performances for highly sensitive and selective detection of dopamine. These findings demonstrate that the hydrothermally synthesized I-G can be a promising electrocatalyst for multifunctional applications in water-splitting and electrochemical sensing.

  20. Hidden Hydride Transfer as a Decisive Mechanistic Step in the Reactions of the Unligated Gold Carbide [AuC]+ with Methane under Ambient Conditions.

    Science.gov (United States)

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

    2016-10-10

    The reactivity of the cationic gold carbide [AuC] + (bearing an electrophilic carbon atom) towards methane has been studied using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The product pairs generated, that is, Au + /C 2 H 4 , [Au(C 2 H 2 )] + /H 2 , and [C 2 H 3 ] + /AuH, point to the breaking and making of C-H, C-C, and H-H bonds under single-collision conditions. The mechanisms of these rather efficient reactions have been elucidated by high-level quantum-chemical calculations. As a major result, based on molecular orbital and NBO-based charge analysis, an unprecedented hydride transfer from methane to the carbon atom of [AuC] + has been identified as a key step. Also, the origin of this novel mechanistic scenario has been addressed. The mechanistic insights derived from this study may provide guidance for the rational design of carbon-based catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Importance of sequential two-step transfer process in a ΔS = 1 and ΔT = 1 inelastic transition of 14N(p, p')14N reaction

    International Nuclear Information System (INIS)

    Aoki, Y.; Kunori, S.; Nagano, K.; Toba, Y.; Yagi, K.

    1981-01-01

    Differential cross sections and vector analyzing powers for 14 N(p, p') and 14 N(p, d) reactions have been measured at E sub(p) = 21.0 MeV to elucidate the reaction mechanism and the effective interaction for the ΔS = ΔT = 1 transition in 14 N(p, p') 14 N(2.31 MeV) reaction. The data are analyzed in terms of finite-range distorted wave Borm approximation (DWBA) which include direct, knock-on exchange and (p, d)(d, p') two-step processes. Shell model wave functions of Cohen and Kurath are used. The data for the first excited state is reasonably well explained by introducing two-step process. The two-step process explains half of the experimental intensity. Moreover vector analyzing power can hardly be explained without introducing this two-step process. Vector analyzing power of protons leading to the second excited state in 14 N is better explained by introducing macroscopic calculation. The data for 14 N(p, d) 13 N(gs) reaction are well explained by a suitable choice of deuteron optical potential. Knock-on exchange contribution is relatively small. Importance of this two-step process for ΔS = ΔT = 1 transition is discussed up to 40 MeV. (author)

  2. Adsorption and diffusion of H and NH{sub x} as key steps of the NH{sub x} dehydrogenation reaction at the V{sub 2}O{sub 5} (010) surface

    Energy Technology Data Exchange (ETDEWEB)

    Gruber, Mathis; Hermann, Klaus [Fritz-Haber-Institut der MPG, und Sfb 546, Berlin (Germany)

    2009-07-01

    Various selective oxidation reactions as the selective catalytic reduction (SCR) of NO{sub x} or the ammoxidation of propane/propene to acrylonitrile are processed on vanadium based metal-oxide catalysts in the presence of ammonia. In the reactions the intermediates NH{sub 2}, NH{sub 3}, and NH{sub 4} are involved indicating that the adsorption and dehydrogenation of NH{sub x}, x < 4, are important steps. We have performed theoretical studies of corresponding reaction steps where the catalyst is simulated by a finite section of the V{sub 2}O{sub 5} (010) surface. The calculations apply density-functional theory combined with clusters modeling the adsorbate system. The substrate lowers corresponding dehydrogenation energies considerably compared with values for the gas phase reaction. However, the lowering is too small to make dehydrogenation of NH{sub 3} likely to happen. Our results on the role of oxygen vacancies for the dehydrogenation indicate that such surface defects become important for the reaction. Besides the energetics also the diffusion at the surface influences the reaction. A nudged elastic band (NEB) routine has been implemented to evaluate diffusion paths and barriers. Hydrogen diffusion on the surface will be discussed and additional examples for NH{sub x} diffusion will be shown. Based on these results possible reaction scenarios for the dehydrogenation reaction will be presented.

  3. Protonation mechanism and location of rate-determining steps for the Ascaris suum nicotinamide adenine dinucleotide-malic enzyme reaction from isotope effects and pH studies

    International Nuclear Information System (INIS)

    Kiick, D.M.; Harris, B.G.; Cook, P.F.

    1986-01-01

    The pH dependence of the kinetic parameters and the primary deuterium isotope effects with nicotinamide adenine dinucleotide (NAD) and also thionicotinamide adenine dinucleotide (thio-NAD) as the nucleotide substrates were determined in order to obtain information about the chemical mechanism and location of rate-determining steps for the Ascaris suum NAD-malic enzyme reaction. The maximum velocity with thio-NAD as the nucleotide is pH-independent from pH 4.2 to 9.6, while with NAD, V decreases below a pK of 4.8. V/K for both nucleotides decreases below a pK of 5.6 and above a pK of 8.9. Both the tartronate pKi and V/Kmalate decrease below a pK of 4.8 and above a pK of 8.9. Oxalate is competitive vs. malate above pH 7 and noncompetitive below pH 7 with NAD as the nucleotide. The oxalate Kis increases from a constant value above a pK of 4.9 to another constant value above a pK of 6.7. The oxalate Kii also increases above a pK of 4.9, and this inhibition is enhanced by NADH. In the presence of thio-NAD the inhibition by oxalate is competitive vs. malate below pH 7. For thio-NAD, both DV and D(V/K) are pH-independent and equal to 1.7. With NAD as the nucleotide, DV decreases to 1.0 below a pK of 4.9, while D(V/KNAD) and D(V/Kmalate) are pH-independent. Above pH 7 the isotope effects on V and the V/K values for NAD and malate are equal to 1.45, the pH-independent value of DV above pH 7. Results indicate that substrates bind to only the correctly protonated form of the enzyme. Two enzyme groups are necessary for binding of substrates and catalysis. Both NAD and malate are released from the Michaelis complex at equal rates which are equal to the rate of NADH release from E-NADH above pH 7. Below pH 7 NADH release becomes more rate-determining as the pH decreases until at pH 4.0 it completely limits the overall rate of the reaction

  4. Speciation, Dissolution, and Redox Reactions of Chromium Relevant to Pretreatment and Separation of High-Level Tank Wastes (First Year of Funding: FY 1998)

    International Nuclear Information System (INIS)

    Rai, Dhanpat; Rao, Linfeng; Clark, Sue B.; Hess, Nancy J.

    2000-01-01

    Chromium, one of the problematic elements in tank sludges, is presently considered to be the most important constituent in defining the total volume of HLW glass to be produced from the Hanford tank wastes. This is because (1) it greatly complicates the vitrification process by forming separate phases in the molten glass and, (2) more importantly, current sludge washing processes are not effective in removing Cr. Inadequate removal of chromium from sludges could result in production of an unacceptably large volume of HLW glass. The removal of Cr from tank sludges is complicated by factors including the complex chemistry of Cr, lack of fundamental data applicable to the HLW chemical systems (high heterogeneity, high ionic strength, high alkalinity and the presence of inorganic and organic ligands, etc.), and the need to avoid processes that may adversely enhance the solubility of Pu and other actinides. Significant gaps exist in the fundamental understanding of Cr chemistry in tank-like environments. Without such data/understanding, these strategies cannot be appropriately evaluated or optimized. The primary objective of the research being carried out under this project is to develop such data/understanding for HLW tank processing. Pacific Northwest and Lawrence Berkeley National Laboratories in collaboration with Washington State University are developing fundamental data on the precipitation/dissolution reactions of Cr(III) compounds and the kinetics of oxidation of Cr(III) to Cr(VI) at room and elevated temperatures and under conditions relevant to high-level waste processing. This integrated approach involving measurement of solubility and oxidation rate constants and spectroscopic characterization of aqueous and solid species as a function of ionic strength, alkalinity, redox conditions and temperature will provide thermodynamic and kinetic data. These data are necessary to predict changes in Cr solubility and speciation in response to changes in pretreatment

  5. Multi-step processes in the (d, t) and (d, {sup 3}He) reactions on {sup 116}Sn and {sup 208}Pb targets at E{sub d} = 200 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Langevin-Joliot, H.; Van de Wiele, J.; Guillot, J. [Institut de Physique Nucleaire, IN2P3/CNRS, 91 - Orsay (France); Koning, A.J. [Nuclear Research and Consultancy Group NRG, NL (Netherlands)

    2000-07-01

    The role of multi-step processes in the reactions {sup 116}Sn(d,t), {sup 208}Pb(d,t) and {sup 116}Sn(d,{sup 3}He), previously studied at E{sub d} = 200 MeV at forward angles and for relatively low energy transfers, has been investigated. We have performed for the first time multi-step calculations taking into account systematically collective excitations in the second and higher order step inelastic transitions. A calculation code based on the Feshbach, Kerman and Koonin model has been modified to handle explicitly these collective excitations, most important in the forward angle domain. One step double differential pick-up cross sections were built from finite range distorted wave results spread in energy using known or estimated hole state characteristics. It is shown that two-step cross sections calculated using the above method compare rather well with those deduced via coupled channel calculations for the same collective excitations. The multi-step calculations performed up to 6 steps reproduce reasonably well the {sup 115}Sn, {sup 207}Pb and {sup 115}In experimental spectra measured up to E{sub x}{approx}- 40 MeV and 15 deg. The relative contributions of steps of increasing order to pick-up cross sections at E{sub d} = 200 MeV and 150 MeV are discussed. (authors)

  6. Measurement of the cross section of the 8Li(d,α)6He reaction of possible relevance to big bang nucleosynthesis

    International Nuclear Information System (INIS)

    Sahin, L.; Boyd, R.N.; Cole, A.L.; Famiano, M.; Gueray, R.T.; Murphy, A. St.J.; Oezkan, N.; Kolata, J.J.; Guimaraes, V.; Hencheck, M.

    2002-01-01

    We report measurements of the cross section of the 8 Li(d,α) 6 He reaction in the energy range E c.m. =2.3-3.5 MeV using a 8 Li-radioactive beam on a CD 2 foil. The astrophysical S factor and reaction rate were calculated from the measured cross section. The 6 He nuclei produced in the reaction were detected in solid-state detector telescopes. This reaction might have affected the primordial abundance of 6 Li in big bang nucleosynthesis, since 6 He beta decays to 6 Li. However, several big bang nucleosynthesis network calculations were found to be insensitive to this reaction, suggesting that the 8 Li(d,α) 6 He reaction does not affect 6 Li primordial production

  7. Some calculated (p,α) cross-sections using the alpha particle knock-on and triton pick-up reaction mechanisms: An optimisation of the single-step Feshbach-Kerman-Koonin (FKK) theory

    Energy Technology Data Exchange (ETDEWEB)

    Olise, Felix S.; Ajala, Afis; Olamiyl, Hezekiah B. [Dept. of Physics and Engineering Physics, Obafemi Awolowo University, Ile-Ife (Nigeria)

    2016-04-15

    The Feshbach-Kerman-Koonin (FKK) multi-step direct (MSD) theory of pre-equilibrium reactions has been used to compute the single-step cross-sections for some (p,α) reactions using the knock-on and pick-up reaction mechanisms at two incident proton energies. For the knock-on mechanism, the reaction was assumed to have taken place by the direct ejection of a preformed alpha cluster in a shell-model state of the target. But the reaction was assumed to have taken place by the pick-up of a preformed triton cluster (also bound in a shell-model state of the target core) by the incident proton for the pick-up mechanism. The Yukawa forms of potential were used for the proton-alpha (for the knock-on process) and proton-triton (for the pick-up process) interaction and several parameter sets for the proton and alpha-particle optical potentials. The calculated cross-sections for both mechanisms gave satisfactory fits to the experimental data. Furthermore, it has been shown that some combinations of the calculated distorted wave Born approximation cross-sections for the two reaction mechanisms in the FKK MSD theory are able to give better fits to the experimental data, especially in terms of range of agreement. In addition, the theory has been observed to be valid over a wider range of energy.

  8. Some Calculated (p,α Cross-Sections Using the Alpha Particle Knock-On and Triton Pick-Up Reaction Mechanisms: An Optimisation of the Single-Step Feshbach–Kerman–Koonin (FKK Theory

    Directory of Open Access Journals (Sweden)

    Felix S. Olise

    2016-04-01

    Full Text Available The Feshbach–Kerman–Koonin (FKK multi-step direct (MSD theory of pre-equilibrium reactions has been used to compute the single-step cross-sections for some (p,α reactions using the knock-on and pick-up reaction mechanisms at two incident proton energies. For the knock-on mechanism, the reaction was assumed to have taken place by the direct ejection of a preformed alpha cluster in a shell-model state of the target. But the reaction was assumed to have taken place by the pick-up of a preformed triton cluster (also bound in a shell-model state of the target core by the incident proton for the pick-up mechanism. The Yukawa forms of potential were used for the proton-alpha (for the knock-on process and proton-triton (for the pick-up process interaction and several parameter sets for the proton and alpha-particle optical potentials. The calculated cross-sections for both mechanisms gave satisfactory fits to the experimental data. Furthermore, it has been shown that some combinations of the calculated distorted wave Born approximation cross-sections for the two reaction mechanisms in the FKK MSD theory are able to give better fits to the experimental data, especially in terms of range of agreement. In addition, the theory has been observed to be valid over a wider range of energy.

  9. In-beam γ-ray spectroscopy of two-step fragmentation reactions at relativistic energies. The case of 36Ca

    International Nuclear Information System (INIS)

    Doornenbal, P.

    2007-01-01

    A two-step fragmentation experiment has been performed at GSI with the RISING setup. It combines the fragment separator FRS, which allows for the production of radioactive heavy ions at relativistic energies, with a high resolution γ-spectrometer. This combination offers unique possibilities for nuclear structure investigations like the test of shell model predictions far from stability. Within the present work the question if the N=14(16) shell stabilisation in Z=8 oxygen isotopes and the N=20 shell quenching in 32 Mg are symmetric with respect to the isospin projection quantum number Tz has been addressed. New γ-ray decays were found in the neutron deficient 36 Ca and 36 K by impinging a radioactive ion beam of 37 Ca on a secondary 9 Be target. The fragmentation products were selected with the calorimeter telescope CATE and the emitted γ-rays were measured with Ge Cluster, MINIBALL, and BaF 2 HECTOR detectors. For 36 Ca the 2 1 + →0 g.s. + transition energy was determined to be 3015(16) keV, which is the heaviest T=2 nucleus from which γ-spectroscopic information has been obtained so far. A comparison between the experimental 2 1 + energies of 36 Ca and its mirror nucleus 36 S yielded a mirror energy difference of ΔE M =-276(16) keV. In order to understand the large ΔE M value, the experimental single-particle energies from the A=17, T=1/2 mirror nuclei were taken and applied onto modified isospin symmetric USD interactions in shell model calculations. These calculations were in agreement with the experimental result and showed that the experimental single-particle energies may account empirically for the one body part of Thomas-Ehrman and/or Coulomb effects. A method to extract the lifetime of excited states in fragmentation reactions was investigated. Therefore, the dependence between the lifetime of an excited state and the average de-excitation velocity and trajectory of the nuclei in relativistic fragmentation experiments has been studied. Known

  10. In-beam {gamma}-ray spectroscopy of two-step fragmentation reactions at relativistic energies. The case of {sup 36}Ca

    Energy Technology Data Exchange (ETDEWEB)

    Doornenbal, P.

    2007-10-23

    A two-step fragmentation experiment has been performed at GSI with the RISING setup. It combines the fragment separator FRS, which allows for the production of radioactive heavy ions at relativistic energies, with a high resolution {gamma}-spectrometer. This combination offers unique possibilities for nuclear structure investigations like the test of shell model predictions far from stability. Within the present work the question if the N=14(16) shell stabilisation in Z=8 oxygen isotopes and the N=20 shell quenching in {sup 32}Mg are symmetric with respect to the isospin projection quantum number Tz has been addressed. New {gamma}-ray decays were found in the neutron deficient {sup 36}Ca and {sup 36}K by impinging a radioactive ion beam of {sup 37}Ca on a secondary {sup 9}Be target. The fragmentation products were selected with the calorimeter telescope CATE and the emitted {gamma}-rays were measured with Ge Cluster, MINIBALL, and BaF{sub 2} HECTOR detectors. For {sup 36}Ca the 2{sub 1}{sup +}{yields}0{sub g.s.}{sup +} transition energy was determined to be 3015(16) keV, which is the heaviest T=2 nucleus from which {gamma}-spectroscopic information has been obtained so far. A comparison between the experimental 2{sub 1}{sup +} energies of {sup 36}Ca and its mirror nucleus {sup 36}S yielded a mirror energy difference of {delta}E{sub M}=-276(16) keV. In order to understand the large {delta}E{sub M} value, the experimental single-particle energies from the A=17, T=1/2 mirror nuclei were taken and applied onto modified isospin symmetric USD interactions in shell model calculations. These calculations were in agreement with the experimental result and showed that the experimental single-particle energies may account empirically for the one body part of Thomas-Ehrman and/or Coulomb effects. A method to extract the lifetime of excited states in fragmentation reactions was investigated. Therefore, the dependence between the lifetime of an excited state and the average de

  11. One-step simultaneous differential scanning calorimetry-FTIR microspectroscopy to quickly detect continuous pathways in the solid-state glucose/asparagine Maillard reaction.

    Science.gov (United States)

    Hwang, Deng-Fwu; Hsieh, Tzu-Feng; Lin, Shan-Yang

    2013-01-01

    The stepwise reaction pathway of the solid-state Maillard reaction between glucose (Glc) and asparagine (Asn) was investigated using simultaneous differential scanning calorimetry (DSC)-FTIR microspectroscopy. The color change and FTIR spectra of Glc-Asn physical mixtures (molar ratio = 1:1) preheated to different temperatures followed by cooling were also examined. The successive reaction products such as Schiff base intermediate, Amadori product, and decarboxylated Amadori product in the solid-state Glc-Asn Maillard reaction were first simultaneously evidenced by this unique DSC-FTIR microspectroscopy. The color changed from white to yellow-brown to dark brown, and appearance of new IR peaks confirmed the formation of Maillard reaction products. The present study clearly indicates that this unique DSC-FTIR technique not only accelerates but also detects precursors and products of the Maillard reaction in real time.

  12. 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)

  13. Highly Regio- and Stereoselective Diels-Alder Cycloadditions via Two-Step and Multicomponent Reactions Promoted by Infrared Irradiation under Solvent-Free Conditions

    Science.gov (United States)

    Flores-Conde, Maria Ines; Reyes, Leonor; Herrera, Rafael; Rios, Hulme; Vazquez, Miguel A.; Miranda, Rene; Tamariz, Joaquin; Delgado, Francisco

    2012-01-01

    Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1–3 with the Knoevenagel adducts 4–6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13–17), under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13–16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO) calculations. PMID:22489113

  14. Highly Regio- and Stereoselective Diels-Alder Cycloadditions via Two-Step and Multicomponent Reactions Promoted by Infrared Irradiation under Solvent-Free Conditions

    Directory of Open Access Journals (Sweden)

    Francisco Delgado

    2012-02-01

    Full Text Available Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1–3 with the Knoevenagel adducts 4–6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13–17, under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13–16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO calculations.

  15. Intramolecular Diels–Alder reaction as a key step in tandem or sequential processes: a versatile tool for the synthesis of fused and bridged bicyclic or polycyclic compounds.

    Digital Repository Service at National Institute of Oceanography (India)

    Parvatkar, P.T.; Kadam, H.K.; Tilve, S.G.

    This review summarizes the recent examples of tandem or sequential reactions used for the last 10 years for the synthesis of fused and bridged bicyclic or polycyclic compounds with IMDA cycloaddition as the key means to access these compounds...

  16. Step sites in syngas catalysis

    DEFF Research Database (Denmark)

    Rostrup-Nielsen, J.; Nørskov, Jens Kehlet

    2006-01-01

    Step sites play an important role in many catalytic reactions. This paper reviews recent results on metal catalysts for syngas reactions with emphasis on steam reforming. Modern characterization techniques (STEM, HREM...) and theoretical calculations (DFT) has allowed a more quantitative explanat......Step sites play an important role in many catalytic reactions. This paper reviews recent results on metal catalysts for syngas reactions with emphasis on steam reforming. Modern characterization techniques (STEM, HREM...) and theoretical calculations (DFT) has allowed a more quantitative...... explanation of the impact of step sites on catalyst activity and side reactions such as carbon formation. This leads to a discussion of principles for catalyst promotion....

  17. The single-process biochemical reaction of Rubisco: a unified theory and model with the effects of irradiance, CO₂ and rate-limiting step on the kinetics of C₃ and C₄ photosynthesis from gas exchange.

    Science.gov (United States)

    Farazdaghi, Hadi

    2011-02-01

    Photosynthesis is the origin of oxygenic life on the planet, and its models are the core of all models of plant biology, agriculture, environmental quality and global climate change. A theory is presented here, based on single process biochemical reactions of Rubisco, recognizing that: In the light, Rubisco activase helps separate Rubisco from the stored ribulose-1,5-bisphosphate (RuBP), activates Rubisco with carbamylation and addition of Mg²(+), and then produces two products, in two steps: (Step 1) Reaction of Rubisco with RuBP produces a Rubisco-enediol complex, which is the carboxylase-oxygenase enzyme (Enco) and (Step 2) Enco captures CO₂ and/or O₂ and produces intermediate products leading to production and release of 3-phosphoglycerate (PGA) and Rubisco. PGA interactively controls (1) the carboxylation-oxygenation, (2) electron transport, and (3) triosephosphate pathway of the Calvin-Benson cycle that leads to the release of glucose and regeneration of RuBP. Initially, the total enzyme participates in the two steps of the reaction transitionally and its rate follows Michaelis-Menten kinetics. But, for a continuous steady state, Rubisco must be divided into two concurrently active segments for the two steps. This causes a deviation of the steady state from the transitional rate. Kinetic models are developed that integrate the transitional and the steady state reactions. They are tested and successfully validated with verifiable experimental data. The single-process theory is compared to the widely used two-process theory of Farquhar et al. (1980. Planta 149, 78-90), which assumes that the carboxylation rate is either Rubisco-limited at low CO₂ levels such as CO₂ compensation point, or RuBP regeneration-limited at high CO₂. Since the photosynthesis rate cannot increase beyond the two-process theory's Rubisco limit at the CO₂ compensation point, net photosynthesis cannot increase above zero in daylight, and since there is always respiration at

  18. Microscale Synthesis, Reactions, and (Super 1)H NMR Spectroscopic Investigations of Square Planar Macrocyclic, Tetramido-N Co(III) Complexes Relevant to Green Chemistry

    Science.gov (United States)

    Watson, Tanya T.; Uffelman, Erich S.; Lee, Daniel W., III; Doherty, Jonathan R.; Schulze, Carl; Burke, Amy L.; Bonnema, Kristen, R.

    2004-01-01

    The microscale preparation, characterization, and reactivity of a square planar Co(III) complex that has grown out of a program to introduce experiments of relevance to green chemistry into the undergraduate curriculum is presented. The given experiments illustrate the remarkable redox and aqueous acid-base stability that make the macrocycles very…

  19. The 76Ge(n,p)76Ga reaction and its relevance to searches for the neutrino-less double-beta decay of 76Ge

    Science.gov (United States)

    Tornow, W.; Bhike, Megha; Fallin, B.; Krishichayan, Fnu

    2015-10-01

    The 76Ge(n,p)76Ga reaction and the subsequent β decay of 76Ga to 76Ge has been used to excite the 3951.9 keV state of 76Ge, which decays by emission of a 2040.7 keV γ ray. Using HPGe detectors, the associated pulse-height signal may be undistinguishable from the potential signal produced in neutrino-less double-beta decay of 76Ge with its Q-value of 2039.0 keV. In the neutron energy range between 10 and 20 MeV the production cross section of the 2040.7 keV γ ray is approximately 0.1 mb. In the same experiment γ rays of energy 2037.9 keV resulting from the 76Ge(n, γ)77Ge reaction were clearly observed. Adding the 76Ge(n,n' γ)76Ge reaction, which also produces the 2040.7 keV γ ray with a cross section value of the order of 0.1 mb clearly shows that great care has to be taken to eliminate neutron-induced backgrounds in searches for neutrino-less double-beta decay of 76Ge. This work was supported by the U.S. DOE under Grant NO. DE-FG02-97ER41033.

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

    Science.gov (United States)

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

    2016-03-01

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

  1. Low-Temperature Thermal Reactions Between SO2 and H2O2 and Their Relevance to the Jovian Icy Satellites

    Science.gov (United States)

    Loeffler, Mark J.; Hudson, Reggie L.

    2013-01-01

    Here we present first results on a non-radiolytic, thermally-driven reaction sequence in solid H2O +SO2 + H2O2 mixtures at 50-130 K, which produces sulfate (SO(-2)/(4)), and has an activation energy of 53 kJ/mole. We suspect that these results may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto.

  2. Li depletion effects on Li2TiO3 reaction with H2 in thermo-chemical environment relevant to breeding blanket for fusion power plants

    International Nuclear Information System (INIS)

    Alvani, Carlo; Casadio, Sergio; Contini, Vittoria; Giorgi, Rossella; Mancini, Maria Rita; Tsuchiya, Kunihiko; Kawamura, Hiroshi

    2005-07-01

    This is a report of the Working Group in the Subtask on Solid Breeder Blankets under the Implementing Agreement on a Co-operative Programme on Nuclear Technology of Fusion Reactors (International Energy Agency (IEA)). This Working Group (Task F and WG-F) was performed from 2000 to 2004 by a collaboration of European Union (EU) and Japan (JA). In this report, lithium depletion effects on the reaction of lithium titanate (Li 2 TiO 3 ) with hydrogen (H 2 ) in thermo-chemical environment were discussed. The reaction of Li 2 TiO 3 ceramics with H 2 was studied in a thermo-chemical environment simulating (excepting irradiation) that of the hottest pebble-bed zone of breeding-blanket actually designed for fusion power plants. This 'reduction' as performed at 900degC in Ar+0.1%H, purge gas (He+0.1%H 2 being the designed reference') was found to be enhanced by TiO 2 doping of the specimens of simulate 6 Li-burn-up expected to reach 20% at their end-of-life. The reaction rates, however, were so slow to be not significantly extrapolated to the breeder material service time (years). In Ar+3%H 2 , faster reaction rates allowed a better identification of the process evolution (kinetics) by Temperature-Programmed Reduction' (TPR) and 'Oxidation' (TPO), and combined TG-DTA thermal analysis. The reduction of pure Li 4/5 TiO 12/5 spinel phase to Li 4/5 TiO 12/5-y was found to reach in one day the steady state at the O-vacancy concentration y=0.2. Complimentary microscopy (SEM) and spectroscopy (XRD, XPS) techniques were used to characterize the reaction products among which the presence of the orthorhombic Li v TiO 2 (0 ≤ v ≤ 1/2) and Li 2 TiO 3 could be diagnosed. So that the complete spinel reduction to Li 1/2 TiO 2 was obtained according to a scheme involving the Li 1/2 TiO 2 -Li 4/5 TiO 12/5 spinel phase solid solution for which y=3v/(10-5v). The reduction rate of pure meta-titanate to Li 2 TiO 3-x was found much lower (x approx. = 0.01) and even possibly due to the presence

  3. Study of two-step mechanisms in the 12C(p,d)11C reaction at 45 MeV

    International Nuclear Information System (INIS)

    Couvert, Pierre.

    1974-01-01

    An attempt was made to find the nuclear reaction mechanisms explaining the intensity and behavior of the cross sections in the 12 C(p,d) 11 C reaction at 45 MeV. First, the conventional interpretation of the experimental data leads to two closely related conclusions. The behavior of the cross-sections measured cannot be explained without including the intermediate stage of collective 2 + 12 C excitation or accounting for its possible interference with the direct capture of a neutron. The relative intensity of the different mechanisms is directly bound up with the value of the nuclear structure parameters of the wave function adopted. As a result this study is found to be an excellent wave function test and the results obtained seem to prove that the wave function calculated by Clegg for 11 B is also suitable for 11 C. Next a two-stage process was introduced, using inelastic deuteron scattering on 11 C as the intermediate stage. The problem which then arises is to determine the deformation parameters of the final nucleus in its different excitation states. The model adopted is in fact very crude and only gives quantitative information on the physical reality of such a process. Some improvement is shown to be obtained by finite range and non-local potential corrections. It is observed that track-transitions, which correspond in fact to new processes interfering with those already introduced play an important part. The most realistic way to treat the problem is thus to make an exact calculation within the coupled equation system, keeping strictly to physically justified hypotheses [fr

  4. Synthesis and Characterization of WO3/Graphene Nanocomposites for Enhanced Photocatalytic Activities by One-Step In-Situ Hydrothermal Reaction

    Directory of Open Access Journals (Sweden)

    Xiaoxiao Hu

    2018-01-01

    Full Text Available Tungsten trioxide (WO3 nanorods are synthesized on the surface of graphene (GR sheets by using a one-step in-situ hydrothermal method employing sodium tungstate (Na2WO4·2H2O and graphene oxide (GO as precursors. The resulting WO3/GR nanocomposites are characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy. The results confirm that the interface between WO3 nanorod and graphene contains chemical bonds. The enhanced optical absorption properties are measured by UV-vis diffuse reflectance spectra. The photocatalytic activity of the WO3/GR nanocomposites under visible light is evaluated by the photodegradation of methylene blue, where the degradation rate of WO3/GR nanocomposites is shown to be double that of pure WO3. This is attributed to the synergistic effect of graphene and the WO3 nanorod, which greatly enhances the photocatalytic performance of the prepared sample, reduces the recombination of the photogenerated electron-hole pairs and increases the visible light absorption efficiency. Finally, the photocatalytic mechanism of the WO3/GR nanocomposites is presented. The synthesis of the prepared sample is convenient, direct and environmentally friendly. The study reports a highly efficient composite photocatalyst for the degradation of contaminants that can be applied to cleaning up the environment.

  5. One-step liquid phase chemical method to prepare carbon-based amorphous molybdenum sulfides: As the effective hydrogen evolution reaction catalysts

    International Nuclear Information System (INIS)

    Guo, Mengmeng; Wu, Qikang; Yu, Miaomiao; Wang, Yinling; Li, Maoguo

    2017-01-01

    Two different kinds of carbon-based amorphous molybdenum sulfide composite catalysts (activated carbon supported amorphous molybdenum sulfide and acetylene black supported amorphous molybdenum sulfide) had been prepared in a facile and scalable one-step liquid phase chemical method. The morphological and structural information of catalysts was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and it’s electro-catalytic HER activity were evaluated by linear sweep voltammetry(LSV), amperometric i-t technology and AC impedance technology. The as-prepared carbon-based amorphous molybdenum sulfides showed greatly enhanced electro-catalytic activity for HER compared with pure amorphous molybdenum sulfides. Especially, the nano-sized acetylene black supported molybdenum sulfide exhibited excellent electro-catalytic HER performances with a low onset potential of −116 mV versus reverse hydrogen electrode (RHE) and a small Tafel slope of 51 mV per decade.

  6. Specific activities and the relevant gamma ray dose rates at 1 meter from radioisotopes and isomers following thermal neutron capture reaction

    International Nuclear Information System (INIS)

    Eissa, E.A.; Aly, R.A.; Gomaa, M.A.; Hassan, A.M.

    1995-01-01

    Calculations were performed for the specific activity of 245 gamma-ray emitting radioisotopes and isomers produced in 48, 72 and 96 hour irradiation periods of the natural isotopic mixture of their 77 elements with thermal neutron flux 1.0 E + 13 n/cm 2 .5, at the core of the (ET-R R-1) reactor. The relevant gamma-ray dose rate at a point 1 meter apart from each radioisotope or isomer was evaluated whenever the specific gamma-ray dose rate constant is available. The irradiation time factor (ITF) for the irradiation periods 24, 48, 72 and 96 hours are reported for each of the 248 gamma-ray emitters. The average of (ITF) over these 248 radionuclides for each irradiation period is taken as a measure of the feasibility of the irradiation time. The results favour the increase of the irradiation period from the conventional 48 to 72 hours but not to 96 hours. A programme was established in the VAX computer to carry out the above mentioned calculations. Tables of the present work are very useful for isotope production and reactor safety. 1 fig., 2 tabs

  7. SYBR green-based one step quantitative real-time polymerase chain reaction assay for the detection of Zika virus in field-caught mosquitoes.

    Science.gov (United States)

    Tien, Wei-Ping; Lim, Gareth; Yeo, Gladys; Chiang, Suzanna Nicole; Chong, Chee-Seng; Ng, Lee-Ching; Hapuarachchi, Hapuarachchige Chanditha

    2017-09-19

    The monitoring of vectors is one of the key surveillance measures to assess the risk of arbovirus transmission and the success of control strategies in endemic regions. The recent re-emergence of Zika virus (ZIKV) in the tropics, including Singapore, emphasizes the need to develop cost-effective, rapid and accurate assays to monitor the virus spread by mosquitoes. As ZIKV infections largely remain asymptomatic, early detection of ZIKV in the field-caught mosquitoes enables timely implementation of appropriate mosquito control measures. We developed a rapid, sensitive and specific real-time reverse transcription polymerase chain reaction (rRT-PCR) assay for the detection of ZIKV in field-caught mosquitoes. The primers and PCR cycling conditions were optimized to minimize non-specific amplification due to cross-reactivity with the genomic material of Aedes aegypti, Aedes albopictus, Culex quinquefasciatus, Culex tritaeniorhynchus, Culex sitiens and Anopheles sinensis, as well as accompanying microbiota. The performance of the assay was further evaluated with a panel of flaviviruses and alphaviruses as well as in field-caught Ae. aegypti mosquitoes confirmed to be positive for ZIKV. As compared to a probe-based assay, the newly developed assay demonstrated 100% specificity and comparable detection sensitivity for ZIKV in mosquitoes. Being a SYBR Green-based method, the newly-developed assay is cost-effective and easy to adapt, thus is applicable to large-scale vector surveillance activities in endemic countries, including those with limited resources and expertise. The amplicon size (119 bp) also allows sequencing to confirm the virus type. The primers flank relatively conserved regions of ZIKV genome, so that, the assay is able to detect genetically diverse ZIKV strains. Our findings, therefore, testify the potential use of the newly-developed assay in vector surveillance programmes for ZIKV in endemic regions.

  8. Microchip capillary electrophoresis with laser-induced fluorescence combined with one-step duplex reverse-transcription polymerase chain reaction for the rapid detection of Enterovirus 71 and Coxsackievirus A16 in throat swab specimens.

    Science.gov (United States)

    Jia, Ruan; Chengjun, Sun; Heng, Chen; Chen, Zhou; Yuanqian, Li; Yongxin, Li

    2015-07-01

    Enterovirus 71 and Coxsackievirus A16 are the main pathogens causing hand-foot-mouth disease. In this paper, microchip capillary electrophoresis with laser-induced fluorescence combined with one-step duplex reverse transcript-polymerase chain reaction has been developed for the detection of Enterovirus 71 and Coxsackievirus A16 in throat swab specimens. The specific reverse transcription-polymerase chain reaction amplicons labeled with SYBR Orange were separated by microchip capillary electrophoresis and detected by laser induced fluorescence detector within 7 min. The intraday and interday relative standard deviation of migration time for DNA Marker was in the range of 1.36-2.94 and 2.78-3.96%, respectively. The detection limits were as low as 2.06 × 10(3) copies/mL for Enterovirus 71 and 5 × 10(3) copies/mL for Coxsackievirus A16. No cross-reactivity was observed with rotavirus, astrovirus, norovirus, and adenovirus, which showed good specificity of the method. This assay was validated using 100 throat swab specimens that were detected by real-time reverse-transcript polymerase chain reaction in parallel and the two methods produced the same results. This study provided a rapid, sensitive and specific method for the detection of Enterovirus 71 and Coxsackievirus A16, which make a contribution to significant time and cost saving for the identification and treatment of patients. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Why does the Y326I mutant of monoamine oxidase B decompose an endogenous amphetamine at a slower rate than the wild type enzyme? Reaction step elucidated by multiscale molecular simulations.

    Science.gov (United States)

    Pregeljc, Domen; Jug, Urška; Mavri, Janez; Stare, Jernej

    2018-02-07

    This work investigates the Y326I point mutation effect on the kinetics of oxidative deamination of phenylethylamine (PEA) catalyzed by the monoamine oxidase B (MAO B) enzyme. PEA is a neuromodulator capable of affecting the plasticity of the brain and is responsible for the mood enhancing effect caused by physical exercise. Due to a similar functionality, PEA is often regarded as an endogenous amphetamine. The rate limiting step of the deamination was simulated at the multiscale level, employing the Empirical Valence Bond approach for the quantum treatment of the involved valence states, whereas the environment (solvated protein) was represented with a classical force field. A comparison of the reaction free energy profiles delivered by simulation of the reaction in the wild type MAO B and its Y326I mutant yields an increase in the barrier by 1.06 kcal mol -1 upon mutation, corresponding to a roughly 6-fold decrease in the reaction rate. This is in excellent agreement with the experimental kinetic studies. Inspection of simulation trajectories reveals possible sources of the point mutation effect, namely vanishing favorable electrostatic interactions between PEA and a Tyr326 side chain and an increased amount of water molecules at the active site due to the replacement of tyrosine by a less spacious isoleucine residue, thereby increasing the dielectric shielding of the catalytic environment provided by the enzyme.

  10. A Reaction Database for Small Molecule Pharmaceutical Processes Integrated with Process Information

    DEFF Research Database (Denmark)

    Papadakis, Emmanouil; Anantpinijwatna, Amata; Woodley, John

    2017-01-01

    This article describes the development of a reaction database with the objective to collect data for multiphase reactions involved in small molecule pharmaceutical processes with a search engine to retrieve necessary data in investigations of reaction-separation schemes, such as the role of organic......; compounds participating in the reaction; use of organic solvents and their function; information for single step and multistep reactions; target products; reaction conditions and reaction data. Information for reactor scale-up together with information for the separation and other relevant information...

  11. Reações cutâneas graves adversas a drogas: aspectos relevantes ao diagnóstico e ao tratamento - Parte II Severe cutaneous adverse drug reactions: relevant aspects to diagnosis and treatment - Part II

    Directory of Open Access Journals (Sweden)

    Paulo Ricardo Criado

    2004-10-01

    Full Text Available As reações cutâneas graves adversas à droga são as que geralmente necessitam de internação hospitalar, por vezes em unidade de terapia intensiva ou de queimados, com observação minuciosa dos sinais vitais e da função de órgãos internos. O objetivo é descrever estas reações facilitando o seu reconhecimento e tratamento. Fazem parte deste grupo a Síndrome de Hipersensibilidade à Droga (SHD, a Pustulose Exantemática Generalizada Aguda (PEGA, a Necrose Cutânea induzida por Anticoagulante, as Vasculites de Pequenos Vasos (VPV, a Vasculite de Hipersensibilidade ao Propiltiouracil (VHP e as Reações tipo Doença do Soro (RDS. A SHD tem-se tornado de elevada relevância clínica devido ao uso amplo dos anticonvulsivantes aromáticos e da dapsona, utilizada no tratamento de doenças como a acne e a hanseníase. A PEGA é determinada principalmente pelos derivados beta-lactâmicos e tem como principal diagnóstico diferencial a psoríase pustulosa generalizada. As VPV tegumentares podem refletir uma doença multissistêmica subjacente, com danos graves em órgãos nobres, como os rins, pulmões e sistema hematológico, com morbidade elevada e possível letalidade. Abordamos as características clínicas e o tratamento destas reações adversas à droga.Severe cutaneous adverse drug reactions generally require hospitalization, sometimes in intensive care or burns units, for observation of the vital signs and the visceral function. The objective was to describe these reactions in order to facilitate recognition and treatment. This group of drug reactions includes drug hypersensitivity syndrome (DHS, acute generalized exanthematous pustulosis (AGEP, anticoagulant-induced skin necrosis, small-vessel vasculitis (SVV, propylthiouracil hypersensitivity vasculitis and serum sickness disease. DHS has been most relevant due to universal prescription of aromatic anticonvulsant drugs and dapsone use in the treatment of some diseases such as acne

  12. Synthesis of Stable and Soluble One-Handed Helical Homopoly(substituted acetylenes without the Coexistence of Any Other Chiral Moieties via Two-Step Polymer Reactions in Membrane State: Molecular Design of the Starting Monomer

    Directory of Open Access Journals (Sweden)

    Takashi Kaneko

    2012-01-01

    Full Text Available A soluble and stable one-handed helical poly(substituted phenylacetylene without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer followed by two-step polymer reactions in membrane state: (1 removing the chiral groups (desubstitution; and (2 introduction of achiral long alkyl groups at the same position as the desubstitution to enhance the solubility of the resulting one-handed helical polymer (resubstitution. The starting chiral monomer should have four characteristic substituents: (i a chiral group bonded to an easily hydrolyzed spacer group; (ii two hydroxyl groups; (iii a long rigid hydrophobic spacer between the chiral group and the polymerizing group; (iv a long achiral group near the chiral group. As spacer group a carbonate ester was selected. The two hydroxyl groups formed intramolecular hydrogen bonds stabilizing a one-handed helical structure in solution before and after the two-step polymer reactions in membrane state. The rigid long hydrophobic spacer, a phenylethynylphenyl group, enhanced the solubility of the starting polymer, and realized effective chiral induction from the chiral side groups to the main chain in the asymmetric-induced polymerization. The long alkyl group near the chiral group avoided shrinkage of the membrane and kept the reactivity of resubstitution in membrane state after removing the chiral groups. The g value (g = ([θ]/3,300/ε for the CD signal assigned to the main chain in the obtained final polymer was almost the same as that of the starting polymer in spite of the absence of any other chiral moieties. Moreover, since the one-handed helical structure was maintained by the intramolecular hydrogen bonds in a solution, direct observation of the one-handed helicity of the final homopolymer has been realized in CD for the solution for the first time.

  13. Pressure-driven one-step solid phase-based on-chip sample preparation on a microfabricated plastic device and integration with flow-through polymerase chain reaction (PCR).

    Science.gov (United States)

    Tran, Hong Hanh; Trinh, Kieu The Loan; Lee, Nae Yoon

    2013-10-01

    In this study, we fabricate a monolithic poly(methylmethacrylate) (PMMA) microdevice on which solid phase-based DNA preparation and flow-through polymerase chain reaction (PCR) units were functionally integrated for one-step sample preparation and amplification operated by pressure. Chelex resin, which is used as a solid support for DNA preparation, can capture denatured proteins but releases DNA, and the purified DNA can then be used as a template in a subsequent amplification process. Using the PMMA microdevices, DNA was successfully purified from both Escherichia coli and human hair sample, and the plasmid vector inserted in E. coli and the D1S80 locus in human genomic DNA were successfully amplified from on-chip purified E. coli and human hair samples. Furthermore, the integration potential of the proposed sample preparation and flow-through PCR units was successfully demonstrate on a monolithic PMMA microdevice with a seamless flow, which could pave the way for a pressure-driven, simple one-step sample preparation and amplification with greatly decreased manufacture cost and enhanced device disposability. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. Investigation of activation cross section data of alpha particle induced nuclear reaction on molybdenum up to 40 MeV: Review of production routes of medically relevant {sup 97,103}Ru

    Energy Technology Data Exchange (ETDEWEB)

    Tárkányi, F. [Institute of Nuclear Research of the Hungarian Academy of Sciences, Debrecen (Hungary); Hermanne, A., E-mail: aherman@vub.ac.be [Cyclotron Laboratory, Vrije Universiteit Brussel, Brussels (Belgium); Ditrói, F.; Takács, S. [Institute of Nuclear Research of the Hungarian Academy of Sciences, Debrecen (Hungary); Ignatyuk, A. [Institute of Physics and Power Engineering (IPPE), Obninsk (Russian Federation)

    2017-05-15

    The main goals of this investigations were to expand and consolidate reliable activation cross-section data for the {sup nat}Mo(α,x) reactions in connection with production of medically relevant {sup 97,103}Ru and the use of the {sup nat}Mo(α,x){sup 97}Ru reaction for monitoring beam parameters. The excitation functions for formation of the gamma-emitting radionuclides {sup 94}Ru, {sup 95}Ru, {sup 97}Ru, {sup 103}Ru, {sup 93m}Tc, {sup 93g}Tc(m+), {sup 94m}Tc, {sup 94g}Tc, {sup 95m}Tc, {sup 95g}Tc, {sup 96g}Tc(m+), {sup 99m}Tc, {sup 93m}Mo, {sup 99}Mo(cum), {sup 90}Nb(m+) and {sup 88}Zr were measured up to 40 MeV alpha-particle energy by using the stacked foil technique and activation method. Data of our earlier similar experiments were re-evaluated and resulted in corrections on the reported results. Our experimental data were compared with critically analyzed literature data and with the results of model calculations, obtained by using the ALICE-IPPE, EMPIRE 3.1 (Rivoli) and TALYS codes (TENDL-2011 and TENDL-2015 on-line libraries). Nuclear data for different production routes of {sup 97}Ru and {sup 103}Ru are compiled and reviewed.

  15. Some Environmentally Relevant Reactions of Cerium Oxide

    Directory of Open Access Journals (Sweden)

    Janoš Pavel

    2014-12-01

    Full Text Available Reactive forms of cerium oxide were prepared by a thermal decomposition of various precursors, namely carbonates, oxalates and citrates, commercially available nanocrystalline cerium oxide (nanoceria was involved in the study for comparison. Scanning electron microscopy (SEM and x-ray diffraction analysis (XRD were used to examine the morphology and crystallinity of the samples, respectively, whereas the Brunauer-Emmett-Teller (BET method of nitrogen adsorption was used to determine surface areas. Interactions of cerium oxide with some phosphorus-containing compounds were investigated. Some of the examined samples, especially those prepared by annealing from carbonate precursors, exhibited an outstanding ability to destroy highly toxic organophosphates, such as pesticides (parathion methyl, or nerve agents (soman, VX. There were identified some relations between the degradation efficiency of cerium oxides and their crystallinity. It was also shown that cerium oxide is able to destroy one of widely used flame retardants - triphenyl phosphate. A phosphatase-mimetic activity of various cerium oxides was examined with the aid of a standardized phosphatase test.

  16. Effects of carbon source and carbon content on electrochemical performances of Li{sub 4}Ti{sub 5}O{sub 12}/C prepared by one-step solid-state reaction

    Energy Technology Data Exchange (ETDEWEB)

    Hu Xuebu [College of Chemistry and Materials Science, Sichuan Normal University, Chengdu, Sichuan 610066 (China); Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, Sichuan 610041 (China); Lin Ziji [China National Quality Supervision and Inspection Center for Alcoholic Beverage Products and Processed Food, Luzhou, Sichuan 646100 (China); Yang Kerun [Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, Sichuan 610041 (China); Hua, Yongjian [China Aviation Lithium Battery Co. Ltd., Luoyang, Henan 471009 (China); Deng Zhenghua, E-mail: zhdeng@cioc.ac.cn [Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, Sichuan 610041 (China)

    2011-05-30

    Highlights: > A simple route to prepare the Li{sub 4}Ti{sub 5}O{sub 12}/C by one-step solid-state reaction. > Carbon source and carbon content are two important factors on the electrochemical performances of Li{sub 4}Ti{sub 5}O{sub 12}/C. > As-prepared Li{sub 4}Ti{sub 5}O{sub 12}/C under optimized conditions shows excellent electrochemical performances. - Abstract: Li{sub 4}Ti{sub 5}O{sub 12}/C composites were synthesized by one-step solid-state reaction method using four commonly used organic compounds or organic polymers as carbon source, i.e., polyacrylate acid (PAA), citric acid (CA), maleic acid (MA) and polyvinyl alcohol (PVA). The physical characteristics of Li{sub 4}Ti{sub 5}O{sub 12}/C composites were investigated by X-ray diffraction, electron microscopy, Raman spectroscopy, particle size distribution and thermogravimetry-derivative thermogravimetry techniques. Their electrochemical properties were characterized by cyclic voltammograms, electrochemical impedance spectra, constant current charge-discharge and rate charge-discharge. These analyses indicated that the carbon source and carbon content have a great effect on the physical and electrochemical performances of Li{sub 4}Ti{sub 5}O{sub 12}/C composites. An ideal carbon source and appropriate carbon content effectively improved the electrical contact between the Li{sub 4}Ti{sub 5}O{sub 12} particles, which enhanced the discharge capacity and rate capability of Li{sub 4}Ti{sub 5}O{sub 12}/C composites. PAA was the best carbon source for the synthesis of Li{sub 4}Ti{sub 5}O{sub 12}/C composites. When the carbon content was 3.49 wt.% (LiOH.H{sub 2}O/PAA molar ratio of 1), as-prepared Li{sub 4}Ti{sub 5}O{sub 12}/C showed the maximum discharge capacity. At 0.2 C, initial capacity of the optimized sample was 168.6 mAh g{sup -1} with capacity loss of 2.8% after 50 cycles. At 8 and 10 C, it showed discharge capacities of 143.5 and 132.7 mAh g{sup -1}, with capacity loss of 8.7 and 9.9% after 50 cycles

  17. One-step synthesis of shell/core structural boron and nitrogen co-doped graphitic carbon/nanodiamond as efficient electrocatalyst for the oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Liu, Xiaoxu; Wang, Yanhui; Dong, Liang; Chen, Xi; Xin, Guoxiang; Zhang, Yan; Zang, Jianbing

    2016-01-01

    Shell/core structural boron and nitrogen co-doped graphitic carbon/nanodiamond (BN-C/ND) non-noble metal catalyst has been synthesized by a simple one-step heat-treatment of the mixture with nanodiamond, melamine, boric acid and FeCl 3 . In the process of the surface graphitization of nanodiamond with catalysis by FeCl 3 , B and N atoms from the decomposition of boric acid and melamine were directly introduced into the graphite lattice to form B, N co-doped graphitic carbon shell, while the core still retained the diamond structure. Electrochemical measurements of the BN-C/ND catalyst show much higher electrocatalytic activities towards oxygen reduction reaction (ORR) in alkaline medium than its analogues doped with B or N alone (B-C/ND or N-C/ND). The high catalytic activity of BN-C/ND is attributed to the synergetic effect caused by co-doping of C/ND with B and N. Meanwhile, the BN-C/ND exhibits an excellent electrochemical stability due to the special shell/core structure. There is almost no alteration occurred in the cyclic voltammetry measurements for BN-C/ND before and after 5000 cycles. All experimental results prove that the BN-C/ND may be exploited as a potentially efficient and inexpensive non-noble metal cathode catalyst for ORR to substitute Pt-based catalysts in fuel cells.

  18. Aligning Metabolic Pathways Exploiting Binary Relation of Reactions.

    Directory of Open Access Journals (Sweden)

    Yiran Huang

    Full Text Available Metabolic pathway alignment has been widely used to find one-to-one and/or one-to-many reaction mappings to identify the alternative pathways that have similar functions through different sets of reactions, which has important applications in reconstructing phylogeny and understanding metabolic functions. The existing alignment methods exhaustively search reaction sets, which may become infeasible for large pathways. To address this problem, we present an effective alignment method for accurately extracting reaction mappings between two metabolic pathways. We show that connected relation between reactions can be formalized as binary relation of reactions in metabolic pathways, and the multiplications of zero-one matrices for binary relations of reactions can be accomplished in finite steps. By utilizing the multiplications of zero-one matrices for binary relation of reactions, we efficiently obtain reaction sets in a small number of steps without exhaustive search, and accurately uncover biologically relevant reaction mappings. Furthermore, we introduce a measure of topological similarity of nodes (reactions by comparing the structural similarity of the k-neighborhood subgraphs of the nodes in aligning metabolic pathways. We employ this similarity metric to improve the accuracy of the alignments. The experimental results on the KEGG database show that when compared with other state-of-the-art methods, in most cases, our method obtains better performance in the node correctness and edge correctness, and the number of the edges of the largest common connected subgraph for one-to-one reaction mappings, and the number of correct one-to-many reaction mappings. Our method is scalable in finding more reaction mappings with better biological relevance in large metabolic pathways.

  19. Application of stepping motor

    International Nuclear Information System (INIS)

    1980-10-01

    This book is divided into three parts, which is about practical using of stepping motor. The first part has six chapters. The contents of the first part are about stepping motor, classification of stepping motor, basic theory og stepping motor, characteristic and basic words, types and characteristic of stepping motor in hybrid type and basic control of stepping motor. The second part deals with application of stepping motor with hardware of stepping motor control, stepping motor control by microcomputer and software of stepping motor control. The last part mentions choice of stepping motor system, examples of stepping motor, measurement of stepping motor and practical cases of application of stepping motor.

  20. Step out - Step in Sequencing Games

    NARCIS (Netherlands)

    Musegaas, M.; Borm, P.E.M.; Quant, M.

    2014-01-01

    In this paper a new class of relaxed sequencing games is introduced: the class of Step out - Step in sequencing games. In this relaxation any player within a coalition is allowed to step out from his position in the processing order and to step in at any position later in the processing order.

  1. Step out-step in sequencing games

    NARCIS (Netherlands)

    Musegaas, Marieke; Borm, Peter; Quant, Marieke

    2015-01-01

    In this paper a new class of relaxed sequencing games is introduced: the class of Step out–Step in sequencing games. In this relaxation any player within a coalition is allowed to step out from his position in the processing order and to step in at any position later in the processing order. First,

  2. Step-by-step cyclic processes scheduling

    DEFF Research Database (Denmark)

    Bocewicz, G.; Nielsen, Izabela Ewa; Banaszak, Z.

    2013-01-01

    Automated Guided Vehicles (AGVs) fleet scheduling is one of the big problems in Flexible Manufacturing System (FMS) control. The problem is more complicated when concurrent multi-product manufacturing and resource deadlock avoidance policies are considered. The objective of the research is to pro......Automated Guided Vehicles (AGVs) fleet scheduling is one of the big problems in Flexible Manufacturing System (FMS) control. The problem is more complicated when concurrent multi-product manufacturing and resource deadlock avoidance policies are considered. The objective of the research...... is to provide a declarative model enabling to state a constraint satisfaction problem aimed at AGVs fleet scheduling subject to assumed itineraries of concurrently manufactured product types. In other words, assuming a given layout of FMS’s material handling and production routes of simultaneously manufactured...... orders, the main objective is to provide the declarative framework aimed at conditions allowing one to calculate the AGVs fleet schedule in online mode. An illustrative example of the relevant algebra-like driven step-by-stem cyclic scheduling is provided....

  3. Relevance of equilibrium in multifragmentation

    International Nuclear Information System (INIS)

    Furuta, Takuya; Ono, Akira

    2009-01-01

    The relevance of equilibrium in a multifragmentation reaction of very central 40 Ca + 40 Ca collisions at 35 MeV/nucleon is investigated by using simulations of antisymmetrized molecular dynamics (AMD). Two types of ensembles are compared. One is the reaction ensemble of the states at each reaction time t in collision events simulated by AMD, and the other is the equilibrium ensemble prepared by solving the AMD equation of motion for a many-nucleon system confined in a container for a long time. The comparison of the ensembles is performed for the fragment charge distribution and the excitation energies. Our calculations show that there exists an equilibrium ensemble that well reproduces the reaction ensemble at each reaction time t for the investigated period 80≤t≤300 fm/c. However, there are some other observables that show discrepancies between the reaction and equilibrium ensembles. These may be interpreted as dynamical effects in the reaction. The usual static equilibrium at each instant is not realized since any equilibrium ensemble with the same volume as that of the reaction system cannot reproduce the fragment observables

  4. Nucleon induced reactions

    International Nuclear Information System (INIS)

    Gmuca, S.; Antalik, R.; Kristiak, J.

    1988-01-01

    The collection contains full texts of 37 contributions; all fall within the INIS Subject Scope. The topics treated include some unsolved problems of nuclear reactions and relevant problems of nuclear structure at low and intermediate energies. (Z.S.)

  5. Space Drive Physics: Introduction and Next Steps

    Science.gov (United States)

    Millis, M. G.

    Research toward the visionary goal of propellantless ``space drives'' is introduced, covering key physics issues and a listing of roughly 2-dozen approaches. The targeted advantage of a space drive is to circumvent the propellant constraints of rockets and the maneuvering limits of light sails by using the interactions between the spacecraft and its surrounding space for propulsion. At present, the scientific foundations from which to engineer a space drive have not been discovered and, objectively, might be impossible. Although no propulsion breakthroughs appear imminent, the subject has matured to where the relevant questions have been broached and are beginning to be answered. The critical make-break issues include; conservation of momentum, uncertain sources of reaction mass, and the net-external thrusting requirement. Note: space drives are not necessarily faster- than-light devices. Speed limits are a separate, unanswered issue. Relevant unsolved physics includes; the sources and mechanisms of inertial frames, coupling of gravitation and electromagnetism, and the nature of the quantum vacuum. The propulsion approaches span mostly stages 1 through 3 of the scientific method (defining the problem, collecting data, and articulating hypotheses), while some have matured to stage 4 (testing hypotheses). Nonviable approaches include `stiction drives,' `gyroscopic antigravity,' and `lifters.' No attempt is made to gauge the prospects of the remaining approaches. Instead, a list of next-step research questions is derived from the examination of these goals, unknowns, and concepts.

  6. 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

  7. Communication: Equilibrium rate coefficients from atomistic simulations: The O(3P) + NO(2Π) → O2(X3Σg−) + N(4S) reaction at temperatures relevant to the hypersonic flight regime

    International Nuclear Information System (INIS)

    Castro-Palacio, Juan Carlos; Bemish, Raymond J.; Meuwly, Markus

    2015-01-01

    The O( 3 P) + NO( 2 Π) → O 2 (X 3 Σ g − ) + N( 4 S) reaction is among the N- and O- involving reactions that dominate the energetics of the reactive air flow around spacecraft during hypersonic atmospheric re-entry. In this regime, the temperature in the bow shock typically ranges from 1000 to 20 000 K. The forward and reverse rate coefficients for this reaction derived directly from trajectory calculations over this range of temperature are reported in this letter. Results compare well with the established equilibrium constants for the same reaction from thermodynamic quantities derived from spectroscopy in the gas phase which paves the way for large-scale in silico investigations of equilibrium rates under extreme conditions

  8. Communication: Equilibrium rate coefficients from atomistic simulations: The O((3)P) + NO((2)Π) → O2(X(3)Σg(-)) + N((4)S) reaction at temperatures relevant to the hypersonic flight regime.

    Science.gov (United States)

    Castro-Palacio, Juan Carlos; Bemish, Raymond J; Meuwly, Markus

    2015-03-07

    The O((3)P) + NO((2)Π) → O2(X(3)Σg(-)) + N((4)S) reaction is among the N- and O- involving reactions that dominate the energetics of the reactive air flow around spacecraft during hypersonic atmospheric re-entry. In this regime, the temperature in the bow shock typically ranges from 1000 to 20,000 K. The forward and reverse rate coefficients for this reaction derived directly from trajectory calculations over this range of temperature are reported in this letter. Results compare well with the established equilibrium constants for the same reaction from thermodynamic quantities derived from spectroscopy in the gas phase which paves the way for large-scale in silico investigations of equilibrium rates under extreme conditions.

  9. Investigation of the complex reaction coordinate of acid catalyzed amide hydrolysis from molecular dynamics simulations

    International Nuclear Information System (INIS)

    Zahn, Dirk

    2004-01-01

    The rate-determining step of acid catalyzed peptide hydrolysis is the nucleophilic attack of a water molecule to the carbon atom of the amide group. Therein the addition of the hydroxyl group to the amide carbon atom involves the association of a water molecule transferring one of its protons to an adjacent water molecule. The protonation of the amide nitrogen atom follows as a separate reaction step. Since the nucleophilic attack involves the breaking and formation of several bonds, the underlying reaction coordinate is rather complex. We investigate this reaction step from path sampling Car-Parrinello molecular dynamics simulations. This approach does not require the predefinition of reaction coordinates and is thus particularly suited for investigating reaction mechanisms. From our simulations the most relevant components of the reaction coordinate are elaborated. Though the C···O distance of the oxygen atom of the water molecule performing the nucleophilic attack and the corresponding amide carbon atom is a descriptor of the reaction progress, a complete picture of the reaction coordinate must include all three molecules taking part in the reaction. Moreover, the proton transfer is found to depend on favorable solvent configurations. Thus, also the arrangement of non-reacting, i.e. solvent water molecules needs to be considered in the reaction coordinate

  10. Why relevance theory is relevant for lexicography

    DEFF Research Database (Denmark)

    Bothma, Theo; Tarp, Sven

    2014-01-01

    This article starts by providing a brief summary of relevance theory in information science in relation to the function theory of lexicography, explaining the different types of relevance, viz. objective system relevance and the subjective types of relevance, i.e. topical, cognitive, situational...... that is very important for lexicography as well as for information science, viz. functional relevance. Since all lexicographic work is ultimately aimed at satisfying users’ information needs, the article then discusses why the lexicographer should take note of all these types of relevance when planning a new...... dictionary project, identifying new tasks and responsibilities of the modern lexicographer. The article furthermore discusses how relevance theory impacts on teaching dictionary culture and reference skills. By integrating insights from lexicography and information science, the article contributes to new...

  11. Excitation functions of proton-induced reactions on natural Nd in the 10-30 MeV energy range, and production of radionuclides relevant for double-beta decay

    Czech Academy of Sciences Publication Activity Database

    Lebeda, Ondřej; Lozza, V.; Schrock, P.; Štursa, Jan; Zuber, K.

    2012-01-01

    Roč. 89, č. 4 (2012), 049905/1-049905/12 ISSN 0556-2813 R&D Projects: GA MŠk LA09013 Institutional research plan: CEZ:AV0Z10480505 Keywords : proton-induced reactions * radionuclides Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 3.715, year: 2012

  12. Application of an automated protocol for the analysis of the temporal parameters of the response of reaction tennis players during the execution of split-step and volley Aplicación de un protocolo automatizado para el análisis de los parámetros temporales de la respuesta de reacción en jugadores de tenis durante la ejecución de split-step y volea

    Directory of Open Access Journals (Sweden)

    V. Luis

    2010-09-01

    Full Text Available

    This study is aimed to show the design and application process of an automated system to recording in real time the temporary parameters of tennis players reaction response during the execution of the technical-tactical movement called “split-step and second volley”. The knowledge about temporary characteristics of the action will be make used of identify the variables to cause in that and also to design an investigation to permit an improvement of the tennis players efficiency in this sequence of the play. In this way, the use of the technological system will allow a precise analysis of player’s motor response and the eminent information about the defined action
    KEY WORDS: Tennis, split-step and volley, automated system of measure, reaction response

    El propósito de este trabajo consiste en mostrar el proceso de diseño y la aplicación de un sistema automatizado de medida para el registro en tiempo real de los parámetros temporales de la respuesta de reacción en jugadores de tenis durante la ejecución de una acción técnico-táctica denominada “split-step y segunda volea”. El conocimiento generado en cuanto a las características temporales de la acción se empleará para identificar las variables que determinan la eficacia en la misma y diseñar una investigación que permita optimizar el rendimiento de los tenistas en esta secuencia del juego. Así, el empleo de este sistema tecnológico permitirá un análisis preciso de la respuesta motriz de los jugadores y la extracción de información relevante acerca de la acción definida.
    PALABRAS CLAVE: Tenis, split-step y volea, sistema automatizado de medida, respuesta de reacción.

  13. Deep learning relevance

    DEFF Research Database (Denmark)

    Lioma, Christina; Larsen, Birger; Petersen, Casper

    2016-01-01

    train a Recurrent Neural Network (RNN) on existing relevant information to that query. We then use the RNN to "deep learn" a single, synthetic, and we assume, relevant document for that query. We design a crowdsourcing experiment to assess how relevant the "deep learned" document is, compared...... to existing relevant documents. Users are shown a query and four wordclouds (of three existing relevant documents and our deep learned synthetic document). The synthetic document is ranked on average most relevant of all....

  14. Internship guide : Work placements step by step

    NARCIS (Netherlands)

    Haag, Esther

    2013-01-01

    Internship Guide: Work Placements Step by Step has been written from the practical perspective of a placement coordinator. This book addresses the following questions : what problems do students encounter when they start thinking about the jobs their degree programme prepares them for? How do you

  15. The way to collisions, step by step

    CERN Multimedia

    2009-01-01

    While the LHC sectors cool down and reach the cryogenic operating temperature, spirits are warming up as we all eagerly await the first collisions. No reason to hurry, though. Making particles collide involves the complex manoeuvring of thousands of delicate components. The experts will make it happen using a step-by-step approach.

  16. The redox-Mannich reaction.

    Science.gov (United States)

    Chen, Weijie; Seidel, Daniel

    2014-06-06

    A complement to the classic three-component Mannich reaction, the redox-Mannich reaction, utilizes the same starting materials but incorporates an isomerization step that enables the facile preparation of ring-substituted β-amino ketones. Reactions occur under relatively mild conditions and are facilitated by benzoic acid.

  17. Stepping out: dare to step forward, step back, or just stand still and breathe.

    Science.gov (United States)

    Waisman, Mary Sue

    2012-01-01

    It is important to step out and make a difference. We have one of the most unique and diverse professions that allows for diversity in thought and practice, permitting each of us to grow in our unique niches and make significant contributions. I was frightened to 'step out' to go to culinary school at the age of 46, but it changed forever the way I look at my profession and I have since experienced the most enjoyable and innovative career. There are also times when it is important to 'step back' to relish the roots of our profession; to help bring food back into nutrition; to translate all of our wonderful science into a language of food that Canadians understand. We all need to take time to 'just stand still and breathe': to celebrate our accomplishments, reflect on our actions, ensure we are heading toward our vision, keep the profession vibrant and relevant, and cherish one another.

  18. Synthesis of 9H-indeno [1, 2-b] pyrazine and 11H-indeno [1, 2-b] quinoxaline derivatives in one-step reaction from 2-bromo-4-chloro-1-indanone

    OpenAIRE

    Jasouri, S.; Khalafy, J.; Badali, M.; Prager, R.H.

    2011-01-01

    The reaction of 2-bromo-4-chloro-1-indanone with 2,3-diaminomaleonitrile, benzene-1,2-diamine and 4-methylbenzene-1,2-diamine in glacial acetic acid gave 8-chloro-9H-indeno[1,2-b]pyrazine-2,3-dicarbonitrile, 1-chloro-11H-indeno[1,2-b]quinoxa-line and 1-chloro-7-methyl-11H-indeno[1,2-b]quinoxaline, respectively, in good yield.

  19. Two steps simultaneous analysis of reactivity of L-norvaline in the T-for-H exchange reaction. Application of Taft equation to influence of Polar effect and steric effect

    International Nuclear Information System (INIS)

    Kataoka, Noriaki; Imaizumi, Hiroshi; Saito, Hiroshi; Sato, Takayuki; Kano, Naoki

    2010-01-01

    In order to quantitatively evaluate the influence of tritium ( 3 H or T) on ecosystem and the reactivity of materials having H atoms, the hydrogen isotope exchange reaction (T-for-H exchange reaction) between L-norvaline and HTO vapor was observed at 50-70degC in the gas-solid system. Applying the A''-McKay plot method to data obtained in the reaction, the rate constants of the functional groups in the material were obtained. Comparing these rate constants, following seven matters have been found in the T-for-H exchange reaction. (1) The reactivity of the functional groups in L-norvaline increases with increasing temperature. (2) As to L-norvaline, 1) the temperature dependence of each functional group increases with the following order: COOH group > NH 2 one. 2) the reactivity of COOH group is 2.2 times greater than that of NH 2 one. (3) As to the influence of the substituent, the reactivity of COOH group is larger than that of the NH 2 one. (4) It seems that the reactivity of the amino acid follows Taft equation. (5) Applying Taft equation, the ratio of influence of polar effect to steric one is 10:0 in NH 2 group, and is 3:7 in COOH one. (6) Using the A - McKay plot method, the reactivity of each functional group in an amino acid is able to be nondestructively, quantitatively and simultaneously analyzed without using masking reagent. (7) The method used in this work may be useful to quickly determine the reactivity of the functional groups in the materials. (author)

  20. Microsoft Office professional 2010 step by step

    CERN Document Server

    Cox, Joyce; Frye, Curtis

    2011-01-01

    Teach yourself exactly what you need to know about using Office Professional 2010-one step at a time! With STEP BY STEP, you build and practice new skills hands-on, at your own pace. Covering Microsoft Word, PowerPoint, Outlook, Excel, Access, Publisher, and OneNote, this book will help you learn the core features and capabilities needed to: Create attractive documents, publications, and spreadsheetsManage your e-mail, calendar, meetings, and communicationsPut your business data to workDevelop and deliver great presentationsOrganize your ideas and notes in one placeConnect, share, and accom

  1. The elementary steps of the photodissociation and recombination reactions of iodine molecules enclosed in cages and channels of zeolite crystals: A femtosecond time-resolved study of the geometry effect

    International Nuclear Information System (INIS)

    Flachenecker, G.; Materny, A.

    2004-01-01

    We present femtosecond time-resolved pump-probe experiments on iodine molecules enclosed into well-defined cages and channels of different crystalline SiO 2 modifications of zeolites. The new experimental results obtained from iodine in TON (Silica-ZSM-22), FER (Silica-Ferrierit), and MFI (Silicalit-1) porosils are compared with data published earlier on the iodine/DDR (Decadodecasil 3R) porosil system [Flachenecker et al., Phys. Chem. Chem. Phys. 5, 865 (2003)]. A summary of all findings is given. The processes analyzed by means of the ultrafast spectroscopy are the vibrational relaxation as well as the dissociation and recombination reactions, which are caused by the interaction of the photo-excited iodine molecules with the cavity walls of the porosils. A clear dependence of the observed dynamics on the geometry of the surrounding lattice structure can be seen. These measurements are supported by temperature-dependent experiments. Making use of a theoretical model which is based on the classical Langevin equation, an analysis of the geometry-reaction relation is performed. The Brownian dynamics simulations show that in contrast to the vibrational relaxation the predissociation dynamics are independent of the frequency of collisions with the surroundings. From the results obtained in the different surroundings, we conclude that mainly local fields are responsible for the crossing from the bound B state to the repulsive a/a ' states of the iodine molecules

  2. A Reaction Database for Small Molecule Pharmaceutical Processes Integrated with Process Information

    Directory of Open Access Journals (Sweden)

    Emmanouil Papadakis

    2017-10-01

    Full Text Available This article describes the development of a reaction database with the objective to collect data for multiphase reactions involved in small molecule pharmaceutical processes with a search engine to retrieve necessary data in investigations of reaction-separation schemes, such as the role of organic solvents in reaction performance improvement. The focus of this reaction database is to provide a data rich environment with process information available to assist during the early stage synthesis of pharmaceutical products. The database is structured in terms of reaction classification of reaction types; compounds participating in the reaction; use of organic solvents and their function; information for single step and multistep reactions; target products; reaction conditions and reaction data. Information for reactor scale-up together with information for the separation and other relevant information for each reaction and reference are also available in the database. Additionally, the retrieved information obtained from the database can be evaluated in terms of sustainability using well-known “green” metrics published in the scientific literature. The application of the database is illustrated through the synthesis of ibuprofen, for which data on different reaction pathways have been retrieved from the database and compared using “green” chemistry metrics.

  3. Fostering Autonomy through Syllabus Design: A Step-by-Step Guide for Success

    Science.gov (United States)

    Ramírez Espinosa, Alexánder

    2016-01-01

    Promoting learner autonomy is relevant in the field of applied linguistics due to the multiple benefits it brings to the process of learning a new language. However, despite the vast array of research on how to foster autonomy in the language classroom, it is difficult to find step-by-step processes to design syllabi and curricula focused on the…

  4. Step by Step Microsoft Office Visio 2003

    CERN Document Server

    Lemke, Judy

    2004-01-01

    Experience learning made easy-and quickly teach yourself how to use Visio 2003, the Microsoft Office business and technical diagramming program. With STEP BY STEP, you can take just the lessons you need, or work from cover to cover. Either way, you drive the instruction-building and practicing the skills you need, just when you need them! Produce computer network diagrams, organization charts, floor plans, and moreUse templates to create new diagrams and drawings quicklyAdd text, color, and 1-D and 2-D shapesInsert graphics and pictures, such as company logosConnect shapes to create a basic f

  5. Two Step Wittig/Dihydroxylation Synthetic Route to Higher Sugars

    DEFF Research Database (Denmark)

    Jørgensen, Morten; Madsen, Robert

    1999-01-01

    Higher carbon sugars are obtained by a two carbon, two step chain elongation of aldoses involving first a Wittig reaction and then an osmium tetroxide catalyzed dihydroxylation......Higher carbon sugars are obtained by a two carbon, two step chain elongation of aldoses involving first a Wittig reaction and then an osmium tetroxide catalyzed dihydroxylation...

  6. Free Modal Algebras Revisited: The Step-by-Step Method

    NARCIS (Netherlands)

    Bezhanishvili, N.; Ghilardi, Silvio; Jibladze, Mamuka

    2012-01-01

    We review the step-by-step method of constructing finitely generated free modal algebras. First we discuss the global step-by-step method, which works well for rank one modal logics. Next we refine the global step-by-step method to obtain the local step-by-step method, which is applicable beyond

  7. Diabetes PSA (:30) Step By Step

    Centers for Disease Control (CDC) Podcasts

    2009-10-24

    First steps to preventing diabetes. For Hispanic and Latino American audiences.  Created: 10/24/2009 by National Diabetes Education Program (NDEP), a joint program of the Centers for Disease Control and Prevention and the National Institutes of Health.   Date Released: 10/24/2009.

  8. Diabetes PSA (:60) Step By Step

    Centers for Disease Control (CDC) Podcasts

    2009-10-24

    First steps to preventing diabetes. For Hispanic and Latino American audiences.  Created: 10/24/2009 by National Diabetes Education Program (NDEP), a joint program of the Centers for Disease Control and Prevention and the National Institutes of Health.   Date Released: 10/24/2009.

  9. Fast-Rate Capable Electrode Material with Higher Energy Density than LiFePO4: 4.2V LiVPO4F Synthesized by Scalable Single-Step Solid-State Reaction.

    Science.gov (United States)

    Kim, Minkyung; Lee, Seongsu; Kang, Byoungwoo

    2016-03-01

    Use of compounds that contain fluorine (F) as electrode materials in lithium ion batteries has been considered, but synthesizing single-phase samples of these compounds is a difficult task. Here, it is demonstrated that a simple scalable single-step solid-state process with additional fluorine source can obtain highly pure LiVPO 4 F. The resulting material with submicron particles achieves very high rate capability ≈100 mAh g -1 at 60 C-rate (1-min discharge) and even at 200 C-rate (18 s discharge). It retains superior capacity, ≈120 mAh g -1 at 10 C charge/10 C discharge rate (6-min) for 500 cycles with >95% retention efficiency. Furthermore, LiVPO 4 F shows low polarization even at high rates leading to higher operating potential >3.45 V (≈3.6 V at 60 C-rate), so it achieves high energy density. It is demonstrated for the first time that highly pure LiVPO 4 F can achieve high power capability comparable to LiFePO 4 and much higher energy density (≈521 Wh g -1 at 20 C-rate) than LiFePO 4 even without nanostructured particles. LiVPO 4 F can be a real substitute of LiFePO 4.

  10. Alpha particle induced reactions on {sup nat}Cr up to 39 MeV: Experimental cross-sections, comparison with theoretical calculations and thick target yields for medically relevant {sup 52g}Fe production

    Energy Technology Data Exchange (ETDEWEB)

    Hermanne, A.; Adam Rebeles, R. [Cyclotron Laboratory, Vrije Universiteit Brussel, Brussel 1090 (Belgium); Tárkányi, F.; Takács, S. [Institute of Nuclear Research, Hungarian Academy of Science, 4026 Debrecen (Hungary)

    2015-08-01

    Thin {sup nat}Cr targets were obtained by electroplating, using 23.75 μm Cu foils as backings. In five stacked foil irradiations, followed by high resolution gamma spectroscopy, the cross sections for production of {sup 52g}Fe, {sup 49,51cum}Cr, {sup 52cum,54,56cum}Mn and {sup 48cum}V in Cr and {sup 61}Cu,{sup 68}Ga in Cu were measured up to 39 MeV incident α-particle energy. Reduced uncertainty is obtained by simultaneous remeasurement of the {sup nat}Cu(α,x){sup 67,66}Ga monitor reactions over the whole energy range. Comparisons with the scarce literature values and results from the TENDL-2013 on-line library, based on the theoretical code family TALYS-1.6, were made. A discussion of the production routes for {sup 52g}Fe with achievable yields and contamination rates was made.

  11. Microsoft Office Word 2007 step by step

    CERN Document Server

    Cox, Joyce

    2007-01-01

    Experience learning made easy-and quickly teach yourself how to create impressive documents with Word 2007. With Step By Step, you set the pace-building and practicing the skills you need, just when you need them!Apply styles and themes to your document for a polished lookAdd graphics and text effects-and see a live previewOrganize information with new SmartArt diagrams and chartsInsert references, footnotes, indexes, a table of contentsSend documents for review and manage revisionsTurn your ideas into blogs, Web pages, and moreYour all-in-one learning experience includes:Files for building sk

  12. Making Rainforests Relevant.

    Science.gov (United States)

    Lustbader, Sara

    1995-01-01

    Describes a program for teaching about tropical rainforests in a concrete way using what's outside the door. This activity uses an eastern deciduous hardwood forest as an example. Step-by-step instructions include introductory activities, plus descriptions of stations in the forest to be visited. Resources include books, audio-visual materials,…

  13. Mechanochemical Association Reaction of Interfacial Molecules Driven by Shear.

    Science.gov (United States)

    Khajeh, Arash; He, Xin; Yeon, Jejoon; Kim, Seong H; Martini, Ashlie

    2018-05-29

    Shear-driven chemical reaction mechanisms are poorly understood because the relevant reactions are often hidden between two solid surfaces moving in relative motion. Here, this phenomenon is explored by characterizing shear-induced polymerization reactions that occur during vapor phase lubrication of α-pinene between sliding hydroxylated and dehydroxylated silica surfaces, complemented by reactive molecular dynamics simulations. The results suggest that oxidative chemisorption of the α-pinene molecules at reactive surface sites, which transfers oxygen atoms from the surface to the adsorbate molecule, is the critical activation step. Such activation takes place more readily on the dehydroxylated surface. During this activation, the most strained part of the α-pinene molecules undergoes a partial distortion from its equilibrium geometry, which appears to be related to the critical activation volume for mechanical activation. Once α-pinene molecules are activated, association reactions occur between the newly attached oxygen and one of the carbon atoms in another molecule, forming ether bonds. These findings have general implications for mechanochemistry because they reveal that shear-driven reactions may occur through reaction pathways very different from their thermally induced counterparts and specifically the critical role of molecular distortion in such reactions.

  14. Making Deferred Taxes Relevant

    NARCIS (Netherlands)

    Brouwer, Arjan; Naarding, Ewout

    2018-01-01

    We analyse the conceptual problems in current accounting for deferred taxes and provide solutions derived from the literature in order to make International Financial Reporting Standards (IFRS) deferred tax numbers value-relevant. In our view, the empirical results concerning the value relevance of

  15. Parsimonious relevance models

    NARCIS (Netherlands)

    Meij, E.; Weerkamp, W.; Balog, K.; de Rijke, M.; Myang, S.-H.; Oard, D.W.; Sebastiani, F.; Chua, T.-S.; Leong, M.-K.

    2008-01-01

    We describe a method for applying parsimonious language models to re-estimate the term probabilities assigned by relevance models. We apply our method to six topic sets from test collections in five different genres. Our parsimonious relevance models (i) improve retrieval effectiveness in terms of

  16. Astrophysical relevance of γ transition energies

    International Nuclear Information System (INIS)

    Rauscher, Thomas

    2008-01-01

    The relevant γ energy range is explicitly identified where additional γ strength must be located to have an impact on astrophysically relevant reactions. It is shown that folding the energy dependences of the transmission coefficients and the level density leads to maximal contributions for γ energies of 2≤E γ ≤4 unless quantum selection rules allow isolated states to contribute. Under this condition, electric dipole transitions dominate. These findings allow us to more accurately judge the relevance of modifications of the γ strength for astrophysics

  17. Focal cryotherapy: step by step technique description

    Directory of Open Access Journals (Sweden)

    Cristina Redondo

    Full Text Available ABSTRACT Introduction and objective: Focal cryotherapy emerged as an efficient option to treat favorable and localized prostate cancer (PCa. The purpose of this video is to describe the procedure step by step. Materials and methods: We present the case of a 68 year-old man with localized PCa in the anterior aspect of the prostate. Results: The procedure is performed under general anesthesia, with the patient in lithotomy position. Briefly, the equipment utilized includes the cryotherapy console coupled with an ultrasound system, argon and helium gas bottles, cryoprobes, temperature probes and an urethral warming catheter. The procedure starts with a real-time trans-rectal prostate ultrasound, which is used to outline the prostate, the urethra and the rectal wall. The cryoprobes are pretested and placed in to the prostate through the perineum, following a grid template, along with the temperature sensors under ultrasound guidance. A cystoscopy confirms the right positioning of the needles and the urethral warming catheter is installed. Thereafter, the freeze sequence with argon gas is started, achieving extremely low temperatures (-40°C to induce tumor cell lysis. Sequentially, the thawing cycle is performed using helium gas. This process is repeated one time. Results among several series showed a biochemical disease-free survival between 71-93% at 9-70 month- follow-up, incontinence rates between 0-3.6% and erectile dysfunction between 0-42% (1–5. Conclusions: Focal cryotherapy is a feasible procedure to treat anterior PCa that may offer minimal morbidity, allowing good cancer control and better functional outcomes when compared to whole-gland treatment.

  18. Culturally Relevant Cyberbullying Prevention

    OpenAIRE

    Phillips, Gregory John

    2017-01-01

    In this action research study, I, along with a student intervention committee of 14 members, developed a cyberbullying intervention for a large urban high school on the west coast. This high school contained a predominantly African American student population. I aimed to discover culturally relevant cyberbullying prevention strategies for African American students. The intervention committee selected video safety messages featuring African American actors as the most culturally relevant cyber...

  19. 2-Step IMAT and 2-Step IMRT in three dimensions

    International Nuclear Information System (INIS)

    Bratengeier, Klaus

    2005-01-01

    the additional segment as well as the integral across the segment profile was demonstrated to be an important value. This product was up to a factor of 3 larger than in the 2-D case. Even in three dimensions, the optimized 2-Step IMAT increased the homogeneity of the dose distribution in the PTV profoundly. Rules for adaptation to varying target-OAR combinations were deduced. It can be concluded that 2-Step IMAT and 2-Step IMRT are also applicable in three dimensions. In the majority of cases, weights between 0.5 and 2 will occur for the additional segment. The width-weight product of the second segment is always smaller than the normalized radius of the OAR. The width-weight product of the additional segment is strictly connected to the relevant diameter of the organ at risk and the target volume. The derived formulas can be helpful to adapt an IMRT plan to altering target shapes

  20. Steps towards an evolutionary physics

    CERN Document Server

    Tiezzi, E

    2006-01-01

    If thermodynamics is to physics as logic is to philosophy, recent theoretical advancements lend new coherence to the marvel and dynamism of life on Earth. Enzo Tiezzi's "Steps Towards an Evolutionary Physics" is a primer and guide, to those who would to stand on the shoulders of giants to attain this view: Heisenberg, Planck, Bateson, Varela, and Prigogine as well as notable contemporary scientists. The adventure of such a free and enquiring spirit thrives not so much on answers as on new questions. The book offers a new gestalt on the uncertainty principle and concept of probability. A wide range of examples, enigmas, and paradoxes lead one's imagination on an exquisite dance. Among the applications are: songs and shapes of nature, oscillatory reactions, orientors, goal functions and configurations of processes, and "dissipative structures and the city". Ecodynamics is a new science, which proposes a cross-fertilization between Charles Darwin and Ilya Prigogine. As an enigma in thermodynamics, Entropy forms ...

  1. Exploring chemical reaction mechanisms through harmonic Fourier beads path optimization.

    Science.gov (United States)

    Khavrutskii, Ilja V; Smith, Jason B; Wallqvist, Anders

    2013-10-28

    Here, we apply the harmonic Fourier beads (HFB) path optimization method to study chemical reactions involving covalent bond breaking and forming on quantum mechanical (QM) and hybrid QM∕molecular mechanical (QM∕MM) potential energy surfaces. To improve efficiency of the path optimization on such computationally demanding potentials, we combined HFB with conjugate gradient (CG) optimization. The combined CG-HFB method was used to study two biologically relevant reactions, namely, L- to D-alanine amino acid inversion and alcohol acylation by amides. The optimized paths revealed several unexpected reaction steps in the gas phase. For example, on the B3LYP∕6-31G(d,p) potential, we found that alanine inversion proceeded via previously unknown intermediates, 2-iminopropane-1,1-diol and 3-amino-3-methyloxiran-2-ol. The CG-HFB method accurately located transition states, aiding in the interpretation of complex reaction mechanisms. Thus, on the B3LYP∕6-31G(d,p) potential, the gas phase activation barriers for the inversion and acylation reactions were 50.5 and 39.9 kcal∕mol, respectively. These barriers determine the spontaneous loss of amino acid chirality and cleavage of peptide bonds in proteins. We conclude that the combined CG-HFB method further advances QM and QM∕MM studies of reaction mechanisms.

  2. Nuclear reactions in Monte Carlo codes

    CERN Document Server

    Ferrari, Alfredo

    2002-01-01

    The physics foundations of hadronic interactions as implemented in most Monte Carlo codes are presented together with a few practical examples. The description of the relevant physics is presented schematically split into the major steps in order to stress the different approaches required for the full understanding of nuclear reactions at intermediate and high energies. Due to the complexity of the problem, only a few semi-qualitative arguments are developed in this paper. The description will be necessarily schematic and somewhat incomplete, but hopefully it will be useful for a first introduction into this topic. Examples are shown mostly for the high energy regime, where all mechanisms mentioned in the paper are at work and to which perhaps most of the readers are less accustomed. Examples for lower energies can be found in the references. (43 refs) .

  3. Ion-Molecule Reaction Dynamics.

    Science.gov (United States)

    Meyer, Jennifer; Wester, Roland

    2017-05-05

    We review the recent advances in the investigation of the dynamics of ion-molecule reactions. During the past decade, the combination of single-collision experiments in crossed ion and neutral beams with the velocity map ion imaging detection technique has enabled a wealth of studies on ion-molecule reactions. These methods, in combination with chemical dynamics simulations, have uncovered new and unexpected reaction mechanisms, such as the roundabout mechanism and the subtle influence of the leaving group in anion-molecule nucleophilic substitution reactions. For this important class of reactions, as well as for many fundamental cation-molecule reactions, the information obtained with crossed-beam imaging is discussed. The first steps toward understanding micro-solvation of ion-molecule reaction dynamics are presented. We conclude with the presentation of several interesting directions for future research.

  4. The Limits to Relevance

    Science.gov (United States)

    Averill, M.; Briggle, A.

    2006-12-01

    Science policy and knowledge production lately have taken a pragmatic turn. Funding agencies increasingly are requiring scientists to explain the relevance of their work to society. This stems in part from mounting critiques of the "linear model" of knowledge production in which scientists operating according to their own interests or disciplinary standards are presumed to automatically produce knowledge that is of relevance outside of their narrow communities. Many contend that funded scientific research should be linked more directly to societal goals, which implies a shift in the kind of research that will be funded. While both authors support the concept of useful science, we question the exact meaning of "relevance" and the wisdom of allowing it to control research agendas. We hope to contribute to the conversation by thinking more critically about the meaning and limits of the term "relevance" and the trade-offs implicit in a narrow utilitarian approach. The paper will consider which interests tend to be privileged by an emphasis on relevance and address issues such as whose goals ought to be pursued and why, and who gets to decide. We will consider how relevance, narrowly construed, may actually limit the ultimate utility of scientific research. The paper also will reflect on the worthiness of research goals themselves and their relationship to a broader view of what it means to be human and to live in society. Just as there is more to being human than the pragmatic demands of daily life, there is more at issue with knowledge production than finding the most efficient ways to satisfy consumer preferences or fix near-term policy problems. We will conclude by calling for a balanced approach to funding research that addresses society's most pressing needs but also supports innovative research with less immediately apparent application.

  5. Relevant Subspace Clustering

    DEFF Research Database (Denmark)

    Müller, Emmanuel; Assent, Ira; Günnemann, Stephan

    2009-01-01

    Subspace clustering aims at detecting clusters in any subspace projection of a high dimensional space. As the number of possible subspace projections is exponential in the number of dimensions, the result is often tremendously large. Recent approaches fail to reduce results to relevant subspace...... clusters. Their results are typically highly redundant, i.e. many clusters are detected multiple times in several projections. In this work, we propose a novel model for relevant subspace clustering (RESCU). We present a global optimization which detects the most interesting non-redundant subspace clusters...... achieves top clustering quality while competing approaches show greatly varying performance....

  6. The Seven Step Strategy

    Science.gov (United States)

    Schaffer, Connie

    2017-01-01

    Many well-intended instructors use Socratic or leveled questioning to facilitate the discussion of an assigned reading. While this engages a few students, most can opt to remain silent. The seven step strategy described in this article provides an alternative to classroom silence and engages all students. Students discuss a single reading as they…

  7. Reaction mechanisms of metal complexes

    CERN Document Server

    Hay, R W

    2000-01-01

    This text provides a general background as a course module in the area of inorganic reaction mechanisms, suitable for advanced undergraduate and postgraduate study and/or research. The topic has important research applications in the metallurgical industry and is of interest in the science of biochemistry, biology, organic, inorganic and bioinorganic chemistry. In addition to coverage of substitution reactions in four-, five- and six-coordinate complexes, the book contains further chapters devoted to isomerization and racemization reactions, to the general field of redox reactions, and to the reactions of coordinated ligands. It is relevant in other fields such as organic, bioinorganic and biological chemistry, providing a bridge to organic reaction mechanisms. The book also contains a chapter on the kinetic background to the subject with many illustrative examples which should prove useful to those beginning research. Provides a general background as a course module in the area of inorganic reaction mechanis...

  8. Identifying Relevant Studies in Software Engineering

    DEFF Research Database (Denmark)

    Zhang, He; Ali Babar, Muhammad; Tell, Paolo

    2011-01-01

    Context: Systematic literature review (SLR) has become an important research methodology in software engineering since the introduction of evidence-based software engineering (EBSE) in 2004. One critical step in applying this methodology is to design and execute appropriate and effective search....... Objective: The main objective of the research reported in this paper is to improve the search step of undertaking SLRs in software engineering (SE) by devising and evaluating systematic and practical approaches to identifying relevant studies in SE. Method: We have systematically selected and analytically...

  9. Is Information Still Relevant?

    Science.gov (United States)

    Ma, Lia

    2013-01-01

    Introduction: The term "information" in information science does not share the characteristics of those of a nomenclature: it does not bear a generally accepted definition and it does not serve as the bases and assumptions for research studies. As the data deluge has arrived, is the concept of information still relevant for information…

  10. HETC-3STEP included fragmentation process

    Energy Technology Data Exchange (ETDEWEB)

    Shigyo, Nobuhiro; Iga, Kiminori; Ishibashi, Kenji [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering

    1997-03-01

    High Energy Transport Code (HETC) based on the cascade-evaporation model is modified to calculate the fragmentation cross section. For the cascade process, nucleon-nucleon cross sections are used for collision computation; effective in-medium-corrected cross sections are adopted instead of the original free-nucleon collision. The exciton model is adopted for improvement of backward nucleon-emission cross section for low-energy nucleon-incident events. The fragmentation reaction is incorporated into the original HETC as a subroutine set by the use of the systematics of the reaction. The modified HETC (HETC-3STEP/FRG) reproduces experimental fragment yields to a reasonable degree. (author)

  11. Lateral step initiation behavior in older adults.

    Science.gov (United States)

    Sparto, Patrick J; Jennings, J Richard; Furman, Joseph M; Redfern, Mark S

    2014-02-01

    Older adults have varied postural responses during induced and voluntary lateral stepping. The purpose of the research was to quantify the occurrence of different stepping strategies during lateral step initiation in older adults and to relate the stepping responses to retrospective history of falls. Seventy community-ambulating older adults (mean age 76 y, range 70-94 y) performed voluntary lateral steps as quickly as possible to the right or left in response to a visual cue, in a blocked design. Vertical ground reaction forces were measured using a forceplate, and the number and latency of postural adjustments were quantified. Subjects were assigned to groups based on their stepping strategy. The frequency of trials with one or two postural adjustments was compared with data from 20 younger adults (mean age 38 y, range 21-58 y). Logistic regression was used to relate presence of a fall in the previous year with the number and latency of postural adjustments. In comparison with younger adults, who almost always demonstrated one postural adjustment when stepping laterally, older adults constituted a continuous distribution in the percentage of step trials made with one postural adjustment (from 0% to 100% of trials). Latencies of the initial postural adjustment and foot liftoff varied depending on the number of postural adjustments made. A history of falls was associated a larger percentage of two postural adjustments, and a longer latency of foot liftoff. In conclusion, the number and latency of postural adjustments made during voluntary lateral stepping provides additional evidence that lateral control of posture may be a critical indicator of aging. Copyright © 2013 Elsevier B.V. All rights reserved.

  12. Direct NO decomposition over stepped transition-metal surfaces

    DEFF Research Database (Denmark)

    Falsig, Hanne; Bligaard, Thomas; Christensen, Claus H.

    2007-01-01

    We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition-metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Bronsted-Evans-Polanyi (BEP) relations for the activation barriers of dissociation...

  13. Self Blocking of CO Dissociation on a Stepped Ruthenium Surface

    DEFF Research Database (Denmark)

    Vendelbo, Søren Bastholm; Johansson, Martin; Mowbray, Duncan

    2010-01-01

    The influence of steps on CO reactions has been studied on a Ru(0 1 (1) over bar 5 4) single crystal with a step density of 4%. Based on temperature programmed desorption (TPD) and oxygen titration experiments as well as density functional theory (DFT) calculations, we show that the CO dissociation...

  14. Linear step drive

    International Nuclear Information System (INIS)

    Haniger, L.; Elger, R.; Kocandrle, L.; Zdebor, J.

    1986-01-01

    A linear step drive is described developed in Czechoslovak-Soviet cooperation and intended for driving WWER-1000 control rods. The functional principle is explained of the motor and the mechanical and electrical parts of the drive, power control, and the indicator of position are described. The motor has latches situated in the reactor at a distance of 3 m from magnetic armatures, it has a low structural height above the reactor cover, which suggests its suitability for seismic localities. Its magnetic circuits use counterpoles; the mechanical shocks at the completion of each step are damped using special design features. The position indicator is of a special design and evaluates motor position within ±1% of total travel. A drive diagram and the flow chart of both the control electronics and the position indicator are presented. (author) 4 figs

  15. Computational Abstraction Steps

    DEFF Research Database (Denmark)

    Thomsen, Lone Leth; Thomsen, Bent; Nørmark, Kurt

    2010-01-01

    and class instantiations. Our teaching experience shows that many novice programmers find it difficult to write programs with abstractions that materialise to concrete objects later in the development process. The contribution of this paper is the idea of initiating a programming process by creating...... or capturing concrete values, objects, or actions. As the next step, some of these are lifted to a higher level by computational means. In the object-oriented paradigm the target of such steps is classes. We hypothesise that the proposed approach primarily will be beneficial to novice programmers or during...... the exploratory phase of a program development process. In some specific niches it is also expected that our approach will benefit professional programmers....

  16. Step 3: Manage Your Diabetes

    Science.gov (United States)

    ... please turn JavaScript on. Feature: Type 2 Diabetes Step 3: Manage Your Diabetes Past Issues / Fall 2014 ... 2 Diabetes" Articles Diabetes Is Serious But Manageable / Step 1: Learn About Diabetes / Step 2: Know Your ...

  17. Quasielastic reactions

    International Nuclear Information System (INIS)

    Henning, W.

    1979-01-01

    Quasielastic reaction studies, because of their capability to microscopically probe nuclear structure, are still of considerable interest in heavy-ion reactions. The recent progress in understanding various aspects of the reaction mechanism make this aim appear closer. The relation between microscopic and macroscopic behavior, as suggested, for example, by the single proton transfer data to individual final states or averaged excitation energy intervals, needs to be explored. It seems particularly useful to extend measurements to higher incident energies, to explore and understand nuclear structure aspects up to the limit of the energy range where they are important

  18. Clinical Relevance of Adipokines

    Directory of Open Access Journals (Sweden)

    Matthias Blüher

    2012-10-01

    Full Text Available The incidence of obesity has increased dramatically during recent decades. Obesity increases the risk for metabolic and cardiovascular diseases and may therefore contribute to premature death. With increasing fat mass, secretion of adipose tissue derived bioactive molecules (adipokines changes towards a pro-inflammatory, diabetogenic and atherogenic pattern. Adipokines are involved in the regulation of appetite and satiety, energy expenditure, activity, endothelial function, hemostasis, blood pressure, insulin sensitivity, energy metabolism in insulin sensitive tissues, adipogenesis, fat distribution and insulin secretion in pancreatic β-cells. Therefore, adipokines are clinically relevant as biomarkers for fat distribution, adipose tissue function, liver fat content, insulin sensitivity, chronic inflammation and have the potential for future pharmacological treatment strategies for obesity and its related diseases. This review focuses on the clinical relevance of selected adipokines as markers or predictors of obesity related diseases and as potential therapeutic tools or targets in metabolic and cardiovascular diseases.

  19. Information Needs/Relevance

    OpenAIRE

    Wildemuth, Barbara M.

    2009-01-01

    A user's interaction with a DL is often initiated as the result of the user experiencing an information need of some kind. Aspects of that experience and how it might affect the user's interactions with the DL are discussed in this module. In addition, users continuously make decisions about and evaluations of the materials retrieved from a DL, relative to their information needs. Relevance judgments, and their relationship to the user's information needs, are discussed in this module. Draft

  20. Distinguishing Biologically Relevant Hexoses by Water Adduction to the Lithium-Cationized Molecule.

    Science.gov (United States)

    Campbell, Matthew T; Chen, Dazhe; Wallbillich, Nicholas J; Glish, Gary L

    2017-10-03

    A method to distinguish the four most common biologically relevant underivatized hexoses, d-glucose, d-galactose, d-mannose, and d-fructose, using only mass spectrometry with no prior separation/derivatization step has been developed. Electrospray of a solution containing hexose and a lithium salt generates [Hexose+Li] + . The lithium-cationized hexoses adduct water in a quadrupole ion trap. The rate of this water adduction reaction can be used to distinguish the four hexoses. Additionally, for each hexose, multiple lithiation sites are possible, allowing for multiple structures of [Hexose+Li] + . Electrospray produces at least one structure that reacts with water and at least one that does not. The ratio of unreactive lithium-cationized hexose to total lithium-cationized hexose is unique for the four hexoses studied, providing a second method for distinguishing the isomers. Use of the water adduction reaction rate or the unreactive ratio provides two separate methods for confidently (p ≤ 0.02) distinguishing the most common biologically relevant hexoses using only femtomoles of hexose. Additionally, binary mixtures of glucose and fructose were studied. A calibration curve was created by measuring the reaction rate of various samples with different ratios of fructose and glucose. The calibration curve was used to accurately measure the percentage of fructose in three samples of high fructose corn syrup (<4% error).

  1. Compensatory stepping responses in individuals with stroke: a pilot study.

    Science.gov (United States)

    Lakhani, Bimal; Mansfield, Avril; Inness, Elizabeth L; McIlroy, William E

    2011-05-01

    Impaired postural control and a high incidence of falls are commonly observed following stroke. Compensatory stepping responses are critical to reactive balance control. We hypothesize that, following a stroke, individuals with unilateral limb dyscontrol will be faced with the unique challenge of controlling such rapid stepping reactions that may eventually be linked to the high rate of falling. The objectives of this exploratory pilot study were to investigate compensatory stepping in individuals poststroke with regard to: (1) choice of initial stepping limb (paretic or non-paretic); (2) step characteristics; and (3) differences in step characteristics when the initial step is taken with the paretic vs. the non-paretic limb. Four subjects following stroke (38-165 days post) and 11 healthy young adults were recruited. Anterior and posterior perturbations were delivered by using a weight drop system. Force plates recorded centre-of-pressure excursion prior to the onset of stepping and step timing. Of the four subjects, three only attempted to step with their non-paretic limb and one stepped with either limb. Time to foot-off was generally slow, whereas step onset time and swing time were comparable to healthy controls. Two of the four subjects executed multistep responses in every trial, and attempts to force stepping with the paretic limb were unsuccessful in three of the four subjects. Despite high clinical balance scores, these individuals with stroke demonstrated impaired compensatory stepping responses, suggesting that current clinical evaluations might not accurately reflect reactive balance control in this population.

  2. cycloaddition reactions

    Indian Academy of Sciences (India)

    Unknown

    Molecular Modeling Group, Organic Chemical Sciences, Indian Institute of Chemical Technology,. Hyderabad ... thus obtained are helpful to model the regioselectivity ... compromise to model Diels–Alder reactions involving ...... acceptance.

  3. Concise Access to 2-Aroylbenzothiazoles by Redox Condensation Reaction between o-Halonitrobenzenes, Acetophenones, and Elemental Sulfur.

    Science.gov (United States)

    Nguyen, Thanh Binh; Pasturaud, Karine; Ermolenko, Ludmila; Al-Mourabit, Ali

    2015-05-15

    A wide range of 2-aroylbenzothiazoles 3 including some pharmacologically relevant derivatives can be obtained in high yields by simply heating o-halonitrobenzenes 1, acetophenones 2, elemental sulfur, and N-methylmorpholine. This three-component nitro methyl coupling was found to occur in an excellent atom-, step-, and redox-efficient manner in which elemental sulfur played the role of nucleophile building block and redox moderating agent to fulfill electronic requirements of the global reaction.

  4. Comparative analysis of single-step and two-step biodiesel production using supercritical methanol on laboratory-scale

    International Nuclear Information System (INIS)

    Micic, Radoslav D.; Tomić, Milan D.; Kiss, Ferenc E.; Martinovic, Ferenc L.; Simikić, Mirko Ð.; Molnar, Tibor T.

    2016-01-01

    Highlights: • Single-step supercritical transesterification compared to the two-step process. • Two-step process: oil hydrolysis and subsequent supercritical methyl esterification. • Experiments were conducted in a laboratory-scale batch reactor. • Higher biodiesel yields in two-step process at milder reaction conditions. • Two-step process has potential to be cost-competitive with the single-step process. - Abstract: Single-step supercritical transesterification and two-step biodiesel production process consisting of oil hydrolysis and subsequent supercritical methyl esterification were studied and compared. For this purpose, comparative experiments were conducted in a laboratory-scale batch reactor and optimal reaction conditions (temperature, pressure, molar ratio and time) were determined. Results indicate that in comparison to a single-step transesterification, methyl esterification (second step of the two-step process) produces higher biodiesel yields (95 wt% vs. 91 wt%) at lower temperatures (270 °C vs. 350 °C), pressures (8 MPa vs. 12 MPa) and methanol to oil molar ratios (1:20 vs. 1:42). This can be explained by the fact that the reaction system consisting of free fatty acid (FFA) and methanol achieves supercritical condition at milder reaction conditions. Furthermore, the dissolved FFA increases the acidity of supercritical methanol and acts as an acid catalyst that increases the reaction rate. There is a direct correlation between FFA content of the product obtained in hydrolysis and biodiesel yields in methyl esterification. Therefore, the reaction parameters of hydrolysis were optimized to yield the highest FFA content at 12 MPa, 250 °C and 1:20 oil to water molar ratio. Results of direct material and energy costs comparison suggest that the process based on the two-step reaction has the potential to be cost-competitive with the process based on single-step supercritical transesterification. Higher biodiesel yields, similar or lower energy

  5. Stepping Stones through Time

    Directory of Open Access Journals (Sweden)

    Emily Lyle

    2012-03-01

    Full Text Available Indo-European mythology is known only through written records but it needs to be understood in terms of the preliterate oral-cultural context in which it was rooted. It is proposed that this world was conceptually organized through a memory-capsule consisting of the current generation and the three before it, and that there was a system of alternate generations with each generation taking a step into the future under the leadership of a white or red king.

  6. SYSTEMATIZATION OF THE BASIC STEPS OF THE STEP-AEROBICS

    Directory of Open Access Journals (Sweden)

    Darinka Korovljev

    2011-03-01

    Full Text Available Following the development of the powerful sport industry, in front of us appeared a lot of new opportunities for creating of the new programmes of exercising with certain requisites. One of such programmes is certainly step-aerobics. Step-aerobics can be defined as a type of aerobics consisting of the basic aerobic steps (basic steps applied in exercising on stepper (step bench, with a possibility to regulate its height. Step-aerobics itself can be divided into several groups, depending on the following: type of music, working methods and adopted knowledge of the attendants. In this work, the systematization of the basic steps in step-aerobics was made on the basis of the following criteria: steps origin, number of leg motions in stepping and relating the body support at the end of the step. Systematization of the basic steps of the step-aerobics is quite significant for making a concrete review of the existing basic steps, thus making creation of the step-aerobics lesson easier

  7. The nuclear reaction matrix

    International Nuclear Information System (INIS)

    Krenciglowa, E.M.; Kung, C.L.; Kuo, T.T.S.; Osnes, E.; and Department of Physics, State University of New York at Stony Brook, Stony Brook, New York 11794)

    1976-01-01

    Different definitions of the reaction matrix G appropriate to the calculation of nuclear structure are reviewed and discussed. Qualitative physical arguments are presented in support of a two-step calculation of the G-matrix for finite nuclei. In the first step the high-energy excitations are included using orthogonalized plane-wave intermediate states, and in the second step the low-energy excitations are added in, using harmonic oscillator intermediate states. Accurate calculations of G-matrix elements for nuclear structure calculations in the Aapprox. =18 region are performed following this procedure and treating the Pauli exclusion operator Q 2 /sub p/ by the method of Tsai and Kuo. The treatment of Q 2 /sub p/, the effect of the intermediate-state spectrum and the energy dependence of the reaction matrix are investigated in detail. The present matrix elements are compared with various matrix elements given in the literature. In particular, close agreement is obtained with the matrix elements calculated by Kuo and Brown using approximate methods

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

    KAUST Repository

    Dehury, Niranjan

    2016-07-18

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

  9. [Relevant public health enteropathogens].

    Science.gov (United States)

    Riveros, Maribel; Ochoa, Theresa J

    2015-01-01

    Diarrhea remains the third leading cause of death in children under five years, despite recent advances in the management and prevention of this disease. It is caused by multiple pathogens, however, the prevalence of each varies by age group, geographical area and the scenario where cases (community vs hospital) are recorded. The most relevant pathogens in public health are those associated with the highest burden of disease, severity, complications and mortality. In our country, norovirus, Campylobacter and diarrheagenic E. coli are the most prevalent pathogens at the community level in children. In this paper we review the local epidemiology and potential areas of development in five selected pathogens: rotavirus, norovirus, Shiga toxin-producing E. coli (STEC), Shigella and Salmonella. Of these, rotavirus is the most important in the pediatric population and the main agent responsible for child mortality from diarrhea. The introduction of rotavirus vaccination in Peru will have a significant impact on disease burden and mortality from diarrhea. However, surveillance studies are needed to determine the impact of vaccination and changes in the epidemiology of diarrhea in Peru following the introduction of new vaccines, as well as antibiotic resistance surveillance of clinical relevant bacteria.

  10. 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)

  11. Optimizing Chemical Reactions with Deep Reinforcement Learning.

    Science.gov (United States)

    Zhou, Zhenpeng; Li, Xiaocheng; Zare, Richard N

    2017-12-27

    Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability.

  12. Strategies for innovation in multicomponent reaction design.

    Science.gov (United States)

    Ganem, Bruce

    2009-03-17

    By generating structural complexity in a single step from three or more reactants, multicomponent reactions (MCRs) make it possible to synthesize target compounds with greater efficiency and atom economy. The history of such reactions can be traced to the mid-19th century when Strecker first produced alpha-aminonitriles from the condensation of aldehydes with ammonia and hydrogen cyanide. Recently, academic chemists have renewed their interest in MCRs. In part, the pharmaceutical industry has fueled this resurgence because of the growing need to assemble libraries of structurally complex substances for evaluation as lead compounds in drug discovery and development programs. The application of MCRs to that increasingly important objective remains limited by the relatively small number of such reactions that can be broadly applied to prepare biologically relevant or natural-product-like molecular frameworks. We were interested in applying logic-based approaches, such as our single reactant replacement (SRR) approach, as a way both to improve known MCRs and to design new multiple-component routes to bioactive structures. This Account provides several examples that illustrate the use of SRR with known MCRs as starting points for synthetic innovation in this area. As part of our working hypothesis, we initially explored strategies for engineering improvements into known MCRs, either by increasing the dimensionality--that is, changing an n-component to an (n + 1)-component reaction--or broadening the scope of useful input structures, or both. By exhaustively applying retrosynthetic analysis to the cognate MCR to identify and exploit alternative entry points into the overall reaction manifold, we have devised several such re-engineered MCRs. Serendipitous findings have also augmented the yield of useful developments from our logic-inspired approach. In some cases, we have identified surprising links between different compound families that provide useful new entry points

  13. SPAR-H Step-by-Step Guidance

    International Nuclear Information System (INIS)

    Galyean, W.J.; Whaley, A.M.; Kelly, D.L.; Boring, R.L.

    2011-01-01

    This guide provides step-by-step guidance on the use of the SPAR-H method for quantifying Human Failure Events (HFEs). This guide is intended to be used with the worksheets provided in: 'The SPAR-H Human Reliability Analysis Method,' NUREG/CR-6883, dated August 2005. Each step in the process of producing a Human Error Probability (HEP) is discussed. These steps are: Step-1, Categorizing the HFE as Diagnosis and/or Action; Step-2, Rate the Performance Shaping Factors; Step-3, Calculate PSF-Modified HEP; Step-4, Accounting for Dependence, and; Step-5, Minimum Value Cutoff. The discussions on dependence are extensive and include an appendix that describes insights obtained from the psychology literature.

  14. SPAR-H Step-by-Step Guidance

    Energy Technology Data Exchange (ETDEWEB)

    W. J. Galyean; A. M. Whaley; D. L. Kelly; R. L. Boring

    2011-05-01

    This guide provides step-by-step guidance on the use of the SPAR-H method for quantifying Human Failure Events (HFEs). This guide is intended to be used with the worksheets provided in: 'The SPAR-H Human Reliability Analysis Method,' NUREG/CR-6883, dated August 2005. Each step in the process of producing a Human Error Probability (HEP) is discussed. These steps are: Step-1, Categorizing the HFE as Diagnosis and/or Action; Step-2, Rate the Performance Shaping Factors; Step-3, Calculate PSF-Modified HEP; Step-4, Accounting for Dependence, and; Step-5, Minimum Value Cutoff. The discussions on dependence are extensive and include an appendix that describes insights obtained from the psychology literature.

  15. Charge-exchange reactions on 36 S

    International Nuclear Information System (INIS)

    Fifield, L.K.; Catford, W.N.; Orr, N.A.; Ophel, T.R.; Etchegoyen, A.; Etchegoyen, M.C.

    1992-11-01

    A series of charge-exchange reactions on 36 S targets have been investigated at beam energies ∼7 MeV/A. Pronounced selectivities to different final states in 36 P are observed which depend on the projectile employed. An interpretation of the data in terms of one- and two-step pictures of the reaction mechanism is presented. At least two, and probably all, of the reactions have a significant 1-step contribution to the reaction mechanism at these energies. 22 refs., 5 tabs., 5 figs

  16. Consistent post-reaction vibrational energy redistribution in DSMC simulations using TCE model

    Science.gov (United States)

    Borges Sebastião, Israel; Alexeenko, Alina

    2016-10-01

    The direct simulation Monte Carlo (DSMC) method has been widely applied to study shockwaves, hypersonic reentry flows, and other nonequilibrium flow phenomena. Although there is currently active research on high-fidelity models based on ab initio data, the total collision energy (TCE) and Larsen-Borgnakke (LB) models remain the most often used chemistry and relaxation models in DSMC simulations, respectively. The conventional implementation of the discrete LB model, however, may not satisfy detailed balance when recombination and exchange reactions play an important role in the flow energy balance. This issue can become even more critical in reacting mixtures involving polyatomic molecules, such as in combustion. In this work, this important shortcoming is addressed and an empirical approach to consistently specify the post-reaction vibrational states close to thermochemical equilibrium conditions is proposed within the TCE framework. Following Bird's quantum-kinetic (QK) methodology for populating post-reaction states, the new TCE-based approach involves two main steps. The state-specific TCE reaction probabilities for a forward reaction are first pre-computed from equilibrium 0-D simulations. These probabilities are then employed to populate the post-reaction vibrational states of the corresponding reverse reaction. The new approach is illustrated by application to exchange and recombination reactions relevant to H2-O2 combustion processes.

  17. Electromyographic and biomechanical analysis of step negotiation in Charcot Marie Tooth subjects whose level walk is not impaired.

    Science.gov (United States)

    Lencioni, Tiziana; Piscosquito, Giuseppe; Rabuffetti, Marco; Sipio, Enrica Di; Diverio, Manuela; Moroni, Isabella; Padua, Luca; Pagliano, Emanuela; Schenone, Angelo; Pareyson, Davide; Ferrarin, Maurizio

    2018-05-01

    Charcot-Marie-Tooth (CMT) is a slowly progressive disease characterized by muscular weakness and wasting with a length-dependent pattern. Mildly affected CMT subjects showed slight alteration of walking compared to healthy subjects (HS). To investigate the biomechanics of step negotiation, a task that requires greater muscle strength and balance control compared to level walking, in CMT subjects without primary locomotor deficits (foot drop and push off deficit) during walking. We collected data (kinematic, kinetic, and surface electromyographic) during walking on level ground and step negotiation, from 98 CMT subjects with mild-to-moderate impairment. Twenty-one CMT subjects (CMT-NLW, normal-like-walkers) were selected for analysis, as they showed values of normalized ROM during swing and produced work at push-off at ankle joint comparable to those of 31 HS. Step negotiation tasks consisted in climbing and descending a two-step stair. Only the first step provided the ground reaction force data. To assess muscle activity, each EMG profile was integrated over 100% of task duration and the activation percentage was computed in four phases that constitute the step negotiation tasks. In both tasks, CMT-NLW showed distal muscle hypoactivation. In addition, during step-ascending CMT-NLW subjects had relevant lower activities of vastus medialis and rectus femoris than HS in weight-acceptance, and, on the opposite, a greater activation as compared to HS in forward-continuance. During step-descending, CMT-NLW showed a reduced activity of tibialis anterior during controlled-lowering phase. Step negotiation revealed adaptive motor strategies related to muscle weakness due to disease in CMT subjects without any clinically apparent locomotor deficit during level walking. In addition, this study provided results useful for tailored rehabilitation of CMT patients. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. The effects of age and step length on joint kinematics and kinetics of large out-and-back steps.

    Science.gov (United States)

    Schulz, Brian W; Ashton-Miller, James A; Alexander, Neil B

    2008-06-01

    Maximum step length (MSL) is a clinical test that has been shown to correlate with age, various measures of fall risk, and knee and hip joint extension speed, strength, and power capacities, but little is known about the kinematics and kinetics of the large out-and-back step utilized. Body motions and ground reaction forces were recorded for 11 unimpaired younger and 10 older women while attaining maximum step length. Joint kinematics and kinetics were calculated using inverse dynamics. The effects of age group and step length on the biomechanics of these large out-and-back steps were determined. Maximum step length was 40% greater in the younger than in the older women (P<0.0001). Peak knee and hip, but not ankle, angle, velocity, moment, and power were generally greater for younger women and longer steps. After controlling for age group, step length generally explained significant additional variance in hip and torso kinematics and kinetics (incremental R2=0.09-0.37). The young reached their peak knee extension moment immediately after landing of the step out, while the old reached their peak knee extension moment just before the return step liftoff (P=0.03). Maximum step length is strongly associated with hip kinematics and kinetics. Delays in peak knee extension moment that appear to be unrelated to step length, may indicate a reduced ability of older women to rapidly apply force to the ground with the stepping leg and thus arrest the momentum of a fall.

  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. Hippocampus discovery First steps

    Directory of Open Access Journals (Sweden)

    Eliasz Engelhardt

    Full Text Available The first steps of the discovery, and the main discoverers, of the hippocampus are outlined. Arantius was the first to describe a structure he named "hippocampus" or "white silkworm". Despite numerous controversies and alternate designations, the term hippocampus has prevailed until this day as the most widely used term. Duvernoy provided an illustration of the hippocampus and surrounding structures, considered the first by most authors, which appeared more than one and a half century after Arantius' description. Some authors have identified other drawings and texts which they claim predate Duvernoy's depiction, in studies by Vesalius, Varolio, Willis, and Eustachio, albeit unconvincingly. Considering the definition of the hippocampal formation as comprising the hippocampus proper, dentate gyrus and subiculum, Arantius and Duvernoy apparently described the gross anatomy of this complex. The pioneering studies of Arantius and Duvernoy revealed a relatively small hidden formation that would become one of the most valued brain structures.

  1. Other relevant biological papers

    International Nuclear Information System (INIS)

    Shimizu, M.

    1989-01-01

    A considerable number of CRESP-relevant papers concerning deep-sea biology and radioecology have been published. It is the purpose of this study to call attention to them. They fall into three general categories. The first is papers of general interest. They are mentioned only briefly, and include text references to the global bibliography at the end of the volume. The second are papers that are not only mentioned and referenced, but for various reasons are described in abstract form. The last is a list of papers compiled by H.S.J. Roe specifically for this volume. They are listed in bibliographic form, and are also included in the global bibliography at the end of the volume

  2. Theoretical insights into the effect of terrace width and step edge coverage on CO adsorption and dissociation over stepped Ni surfaces.

    Science.gov (United States)

    Yang, Kuiwei; Zhang, Minhua; Yu, Yingzhe

    2017-07-21

    Vicinal surfaces of Ni are model catalysts of general interest and great importance in computational catalysis. Here we report a comprehensive study conducted with density functional theory on Ni[n(111) × (100)] (n = 2, 3 and 4) surfaces to explore the effect of terrace width and step edge coverage on CO adsorption and dissociation, a probe reaction relevant to many industrial processes. The coordination numbers (CN), the generalized coordination numbers and the d band partial density of states (d-PDOS) of Ni are identified as descriptors to faithfully reflect the difference of the step edge region for Ni[n(111) × (100)]. Based on analysis of the energy diagrams for CO activation and dissociation as well as the structural features of the Ni(311), Ni(211) and Ni(533) surfaces, Ni(211) (n = 3) is proposed as a model of adequate representativeness for Ni[n(111) × (100)] (n≥ 3) surface groups in investigating small molecule activation over such stepped structures. Further, a series of Ni(211) surfaces with the step edge coverage ranging from 1/4 to 1 monolayer (ML) were utilized to assess their effect on CO activation. The results show that CO adsorption is not sensitive to the step edge coverage, which could readily approach 1 ML under a CO-rich atmosphere. In contrast, CO dissociation manifests strong coverage dependence when the coverage exceeds 1/2 ML, indicating that significant adsorbate-adsorbate interactions emerge. These results are conducive to theoretical studies of metal-catalyzed surface processes where the defects play a vital role.

  3. Robotics: The next step?

    Science.gov (United States)

    Broeders, Ivo A M J

    2014-02-01

    Robotic systems were introduced 15 years ago to support complex endoscopic procedures. The technology is increasingly used in gastro-intestinal surgery. In this article, literature on experimental- and clinical research is reviewed and ergonomic issues are discussed. literature review was based on Medline search using a large variety of search terms, including e.g. robot(ic), randomized, rectal, oesophageal, ergonomics. Review articles on relevant topics are discussed with preference. There is abundant evidence of supremacy in performing complex endoscopic surgery tasks when using the robot in an experimental setting. There is little high-level evidence so far on translation of these merits to clinical practice. Robotic systems may appear helpful in complex gastro-intestinal surgery. Moreover, dedicated computer based technology integrated in telepresence systems opens the way to integration of planning, diagnostics and therapy. The first high tech add-ons such as near infrared technology are under clinical evaluation. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Allergic reactions

    Science.gov (United States)

    ... that don't bother most people (such as venom from bee stings and certain foods, medicines, and pollens) can ... person. If the allergic reaction is from a bee sting, scrape the ... more venom. If the person has emergency allergy medicine on ...

  5. Astronomical sketching a step-by-step introduction

    CERN Document Server

    Handy, Richard; Perez, Jeremy; Rix, Erika; Robbins, Sol

    2007-01-01

    This book presents the amateur with fine examples of astronomical sketches and step-by-step tutorials in each medium, from pencil to computer graphics programs. This unique book can teach almost anyone to create beautiful sketches of celestial objects.

  6. Enantioselective solvent-free Robinson annulation reactions

    Indian Academy of Sciences (India)

    Unknown

    solvents to effect an asymmetric synthesis is an important step forward towards ... In continuation of our preliminary communication 2, we wish to ..... formation of chiral enamine 74 from the reaction of S-proline with pro-R carbonyl group.

  7. 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

  8. Learning to Predict Chemical Reactions

    Science.gov (United States)

    Kayala, Matthew A.; Azencott, Chloé-Agathe; Chen, Jonathan H.

    2011-01-01

    Being able to predict the course of arbitrary chemical reactions is essential to the theory and applications of organic chemistry. Approaches to the reaction prediction problems can be organized around three poles corresponding to: (1) physical laws; (2) rule-based expert systems; and (3) inductive machine learning. Previous approaches at these poles respectively are not high-throughput, are not generalizable or scalable, or lack sufficient data and structure to be implemented. We propose a new approach to reaction prediction utilizing elements from each pole. Using a physically inspired conceptualization, we describe single mechanistic reactions as interactions between coarse approximations of molecular orbitals (MOs) and use topological and physicochemical attributes as descriptors. Using an existing rule-based system (Reaction Explorer), we derive a restricted chemistry dataset consisting of 1630 full multi-step reactions with 2358 distinct starting materials and intermediates, associated with 2989 productive mechanistic steps and 6.14 million unproductive mechanistic steps. And from machine learning, we pose identifying productive mechanistic steps as a statistical ranking, information retrieval, problem: given a set of reactants and a description of conditions, learn a ranking model over potential filled-to-unfilled MO interactions such that the top ranked mechanistic steps yield the major products. The machine learning implementation follows a two-stage approach, in which we first train atom level reactivity filters to prune 94.00% of non-productive reactions with a 0.01% error rate. Then, we train an ensemble of ranking models on pairs of interacting MOs to learn a relative productivity function over mechanistic steps in a given system. Without the use of explicit transformation patterns, the ensemble perfectly ranks the productive mechanism at the top 89.05% of the time, rising to 99.86% of the time when the top four are considered. Furthermore, the system

  9. User perspectives on relevance criteria

    DEFF Research Database (Denmark)

    Maglaughlin, Kelly L.; Sonnenwald, Diane H.

    2002-01-01

    , partially relevant, or not relevant to their information need; and explained their decisions in an interview. Analysis revealed 29 criteria, discussed positively and negatively, that were used by the participants when selecting passages that contributed or detracted from a document's relevance......This study investigates the use of criteria to assess relevant, partially relevant, and not-relevant documents. Study participants identified passages within 20 document representations that they used to make relevance judgments; judged each document representation as a whole to be relevant...... matter, thought catalyst), full text (e.g., audience, novelty, type, possible content, utility), journal/publisher (e.g., novelty, main focus, perceived quality), and personal (e.g., competition, time requirements). Results further indicate that multiple criteria are used when making relevant, partially...

  10. STEP and fundamental physics

    Science.gov (United States)

    Overduin, James; Everitt, Francis; Worden, Paul; Mester, John

    2012-09-01

    The Satellite Test of the Equivalence Principle (STEP) will advance experimental limits on violations of Einstein's equivalence principle from their present sensitivity of two parts in 1013 to one part in 1018 through multiple comparison of the motions of four pairs of test masses of different compositions in a drag-free earth-orbiting satellite. We describe the experiment, its current status and its potential implications for fundamental physics. Equivalence is at the heart of general relativity, our governing theory of gravity and violations are expected in most attempts to unify this theory with the other fundamental interactions of physics, as well as in many theoretical explanations for the phenomenon of dark energy in cosmology. Detection of such a violation would be equivalent to the discovery of a new force of nature. A null result would be almost as profound, pushing upper limits on any coupling between standard-model fields and the new light degrees of freedom generically predicted by these theories down to unnaturally small levels.

  11. STEP and fundamental physics

    International Nuclear Information System (INIS)

    Overduin, James; Everitt, Francis; Worden, Paul; Mester, John

    2012-01-01

    The Satellite Test of the Equivalence Principle (STEP) will advance experimental limits on violations of Einstein's equivalence principle from their present sensitivity of two parts in 10 13 to one part in 10 18 through multiple comparison of the motions of four pairs of test masses of different compositions in a drag-free earth-orbiting satellite. We describe the experiment, its current status and its potential implications for fundamental physics. Equivalence is at the heart of general relativity, our governing theory of gravity and violations are expected in most attempts to unify this theory with the other fundamental interactions of physics, as well as in many theoretical explanations for the phenomenon of dark energy in cosmology. Detection of such a violation would be equivalent to the discovery of a new force of nature. A null result would be almost as profound, pushing upper limits on any coupling between standard-model fields and the new light degrees of freedom generically predicted by these theories down to unnaturally small levels. (paper)

  12. One-step microlithography

    Science.gov (United States)

    Kahlen, Franz-Josef; Sankaranarayanan, Srikanth; Kar, Aravinda

    1997-09-01

    Subject of this investigation is a one-step rapid machining process to create miniaturized 3D parts, using the original sample material. An experimental setup where metal powder is fed to the laser beam-material interaction region has been built. The powder is melted and forms planar, 2D geometries as the substrate is moved under the laser beam in XY- direction. After completing the geometry in the plane, the substrate is displaced in Z-direction, and a new layer of material is placed on top of the just completed deposit. By continuous repetition of this process, 3D parts wee created. In particular, the impact of the focal spot size of the high power laser beam on the smallest achievable structures was investigated. At a translation speed of 51 mm/s a minimum material thickness of 590 micrometers was achieved. Also, it was shown that a small Z-displacement has a negligible influence on the continuity of the material deposition over this power range. A high power CO2 laser was used as energy source, the material powder under investigation was stainless steel SS304L. Helium was used as shield gas at a flow rate of 15 1/min. The incident CO2 laser beam power was varied between 300 W and 400 W, with the laser beam intensity distribute in a donut mode. The laser beam was focused to a focal diameter of 600 (Mu) m.

  13. Step 1: Learn about Diabetes

    Science.gov (United States)

    ... please turn JavaScript on. Feature: Type 2 Diabetes Step 1: Learn About Diabetes Past Issues / Fall 2014 ... the whole family healthy! Here are four key steps to help you control your diabetes and live ...

  14. SPAR-H Step-by-Step Guidance

    Energy Technology Data Exchange (ETDEWEB)

    April M. Whaley; Dana L. Kelly; Ronald L. Boring; William J. Galyean

    2012-06-01

    Step-by-step guidance was developed recently at Idaho National Laboratory for the US Nuclear Regulatory Commission on the use of the Standardized Plant Analysis Risk-Human Reliability Analysis (SPAR-H) method for quantifying Human Failure Events (HFEs). This work was done to address SPAR-H user needs, specifically requests for additional guidance on the proper application of various aspects of the methodology. This paper overviews the steps of the SPAR-H analysis process and highlights some of the most important insights gained during the development of the step-by-step directions. This supplemental guidance for analysts is applicable when plant-specific information is available, and goes beyond the general guidance provided in existing SPAR-H documentation. The steps highlighted in this paper are: Step-1, Categorizing the HFE as Diagnosis and/or Action; Step-2, Rate the Performance Shaping Factors; Step-3, Calculate PSF-Modified HEP; Step-4, Accounting for Dependence, and; Step-5, Minimum Value Cutoff.

  15. Multiple stage miniature stepping motor

    International Nuclear Information System (INIS)

    Niven, W.A.; Shikany, S.D.; Shira, M.L.

    1981-01-01

    A stepping motor comprising a plurality of stages which may be selectively activated to effect stepping movement of the motor, and which are mounted along a common rotor shaft to achieve considerable reduction in motor size and minimum diameter, whereby sequential activation of the stages results in successive rotor steps with direction being determined by the particular activating sequence followed

  16. Strategies for Innovation in Multicomponent Reaction Design

    OpenAIRE

    Ganem, Bruce

    2009-01-01

    By generating structural complexity in a single step from three or more reactants, multicomponent reactions (MCRs) make it possible to synthesize target compounds with greater efficiency and atom economy. The history of such reactions can be traced to the mid-nineteenth century when Strecker first produced α-aminonitriles from the condensation of aldehydes with ammonia and hydrogen cyanide.

  17. Concise Synthesis of Macrocycles by Multicomponent Reactions

    NARCIS (Netherlands)

    Abdelraheem, Eman M. M.; Khaksar, Samad; Dömling, Alexander

    2018-01-01

    A short reaction pathway was devised to synthesize a library of artificial 18-27-membered macrocycles. The five-step reaction sequence involves ring opening of a cyclic anhydride with a diamine, esterification, coupling with an amino acid isocyanide, saponification, and, finally, macro-ring closure

  18. Hydrazine in the Ugi Tetrazole Reaction

    NARCIS (Netherlands)

    Patil, Pravin; Zhang, Ji; Kurpiewska, Katarzyna; Kalinowska-Tłuścik, Justyna; Dömling, Alexander

    2016-01-01

    We describe the hitherto unknown use of N-Boc-protected hydrazine in the Ugi tetrazole reaction to access a library of highly substituted 5-(hydrazinomethyl)-1-methyl-1H-tetrazoles. The reaction is very versatile and good to high yielding. A one-pot, two-step procedure is given.

  19. Learning to predict chemical reactions.

    Science.gov (United States)

    Kayala, Matthew A; Azencott, Chloé-Agathe; Chen, Jonathan H; Baldi, Pierre

    2011-09-26

    Being able to predict the course of arbitrary chemical reactions is essential to the theory and applications of organic chemistry. Approaches to the reaction prediction problems can be organized around three poles corresponding to: (1) physical laws; (2) rule-based expert systems; and (3) inductive machine learning. Previous approaches at these poles, respectively, are not high throughput, are not generalizable or scalable, and lack sufficient data and structure to be implemented. We propose a new approach to reaction prediction utilizing elements from each pole. Using a physically inspired conceptualization, we describe single mechanistic reactions as interactions between coarse approximations of molecular orbitals (MOs) and use topological and physicochemical attributes as descriptors. Using an existing rule-based system (Reaction Explorer), we derive a restricted chemistry data set consisting of 1630 full multistep reactions with 2358 distinct starting materials and intermediates, associated with 2989 productive mechanistic steps and 6.14 million unproductive mechanistic steps. And from machine learning, we pose identifying productive mechanistic steps as a statistical ranking, information retrieval problem: given a set of reactants and a description of conditions, learn a ranking model over potential filled-to-unfilled MO interactions such that the top-ranked mechanistic steps yield the major products. The machine learning implementation follows a two-stage approach, in which we first train atom level reactivity filters to prune 94.00% of nonproductive reactions with a 0.01% error rate. Then, we train an ensemble of ranking models on pairs of interacting MOs to learn a relative productivity function over mechanistic steps in a given system. Without the use of explicit transformation patterns, the ensemble perfectly ranks the productive mechanism at the top 89.05% of the time, rising to 99.86% of the time when the top four are considered. Furthermore, the system

  20. Effects of walking speed on the step-by-step control of step width.

    Science.gov (United States)

    Stimpson, Katy H; Heitkamp, Lauren N; Horne, Joscelyn S; Dean, Jesse C

    2018-02-08

    Young, healthy adults walking at typical preferred speeds use step-by-step adjustments of step width to appropriately redirect their center of mass motion and ensure mediolateral stability. However, it is presently unclear whether this control strategy is retained when walking at the slower speeds preferred by many clinical populations. We investigated whether the typical stabilization strategy is influenced by walking speed. Twelve young, neurologically intact participants walked on a treadmill at a range of prescribed speeds (0.2-1.2 m/s). The mediolateral stabilization strategy was quantified as the proportion of step width variance predicted by the mechanical state of the pelvis throughout a step (calculated as R 2 magnitude from a multiple linear regression). Our ability to accurately predict the upcoming step width increased over the course of a step. The strength of the relationship between step width and pelvis mechanics at the start of a step was reduced at slower speeds. However, these speed-dependent differences largely disappeared by the end of a step, other than at the slowest walking speed (0.2 m/s). These results suggest that mechanics-dependent adjustments in step width are a consistent component of healthy gait across speeds and contexts. However, slower walking speeds may ease this control by allowing mediolateral repositioning of the swing leg to occur later in a step, thus encouraging slower walking among clinical populations with limited sensorimotor control. Published by Elsevier Ltd.

  1. Quasielastic reactions

    International Nuclear Information System (INIS)

    Hansen, O.

    1983-01-01

    A brief review is presented of the experimental and theoretical situation regarding transfer reactions and inelastic scattering. In the first category there is little (very little) precision data for heavy projectiles and consequently almost no experience with quantitative theoretical analysis. For the inelastic scattering the rather extensive data strongly supports the coupled channels models with collective formfactors. At the most back angles, at intensities about 10 -5 of Rutherford scattering, a second, compound-like mechanism becomes dominant. The description of the interplay of these two opposite mechanisms provides a new challenge for our understanding

  2. Ligand Exchange Kinetics of Environmentally Relevant Metals

    Energy Technology Data Exchange (ETDEWEB)

    Panasci, Adele Frances [Univ. of California, Davis, CA (United States)

    2014-07-15

    The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb to mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as 237Np is a radioactive transuranic element with a half-life of 2 million years.

  3. Nuclear reactions

    International Nuclear Information System (INIS)

    Corner, J.; Richardson, K.; Fenton, N.

    1990-01-01

    Nuclear reactions' marks a new development in the study of television as an agency of public policy debate. During the Eighties, nuclear energy became a major international issue. The disasters at Three-mile Island and Chernobyl created a global anxiety about its risks and a new sensitivity to it among politicians and journalists. This book is a case-study into documentary depictions of nuclear energy in television and video programmes and into the interpretations and responses of viewers drawn from many different occupational groupings. How are the complex and specialist arguments about benefit, risk and proof conveyed through the different conventions of commentary, interview and film sequence? What symbolic associations does the visual language of television bring to portrayals of the issue? And how do viewers make sense of various and conflicting accounts, connecting what they see and hear on the screen with their pre-existing knowledge, experience and 'civic' expectations. The authors examine some of the contrasting forms and themes which have been used by programme makers to explain and persuade, and then give a sustained analysis of the nature and sources of viewers' own accounts. 'Nuclear Reactions' inquires into the public meanings surrounding energy and the environment, spelling out in its conclusion some of the implications for future media treatments of this issue. It is also a key contribution to the international literature on 'television knowledge' and the processes of active viewing. (author)

  4. Analysis of kinetic reaction mechanisms

    CERN Document Server

    Turányi, Tamás

    2014-01-01

    Chemical processes in many fields of science and technology, including combustion, atmospheric chemistry, environmental modelling, process engineering, and systems biology, can be described by detailed reaction mechanisms consisting of numerous reaction steps. This book describes methods for the analysis of reaction mechanisms that are applicable in all these fields. Topics addressed include: how sensitivity and uncertainty analyses allow the calculation of the overall uncertainty of simulation results and the identification of the most important input parameters, the ways in which mechanisms can be reduced without losing important kinetic and dynamic detail, and the application of reduced models for more accurate engineering optimizations. This monograph is invaluable for researchers and engineers dealing with detailed reaction mechanisms, but is also useful for graduate students of related courses in chemistry, mechanical engineering, energy and environmental science and biology.

  5. Accessory stimulus modulates executive function during stepping task.

    Science.gov (United States)

    Watanabe, Tatsunori; Koyama, Soichiro; Tanabe, Shigeo; Nojima, Ippei

    2015-07-01

    When multiple sensory modalities are simultaneously presented, reaction time can be reduced while interference enlarges. The purpose of this research was to examine the effects of task-irrelevant acoustic accessory stimuli simultaneously presented with visual imperative stimuli on executive function during stepping. Executive functions were assessed by analyzing temporal events and errors in the initial weight transfer of the postural responses prior to a step (anticipatory postural adjustment errors). Eleven healthy young adults stepped forward in response to a visual stimulus. We applied a choice reaction time task and the Simon task, which consisted of congruent and incongruent conditions. Accessory stimuli were randomly presented with the visual stimuli. Compared with trials without accessory stimuli, the anticipatory postural adjustment error rates were higher in trials with accessory stimuli in the incongruent condition and the reaction times were shorter in trials with accessory stimuli in all the task conditions. Analyses after division of trials according to whether anticipatory postural adjustment error occurred or not revealed that the reaction times of trials with anticipatory postural adjustment errors were reduced more than those of trials without anticipatory postural adjustment errors in the incongruent condition. These results suggest that accessory stimuli modulate the initial motor programming of stepping by lowering decision threshold and exclusively under spatial incompatibility facilitate automatic response activation. The present findings advance the knowledge of intersensory judgment processes during stepping and may aid in the development of intervention and evaluation tools for individuals at risk of falls. Copyright © 2015 the American Physiological Society.

  6. Development of a new microtiter plate format for clinically relevant assays.

    Science.gov (United States)

    Piletska, Elena V; Piletsky, Stanislav S; Whitcombe, Michael J; Chianella, Iva; Piletsky, Sergey A

    2012-02-21

    A new format for the microtiter plate-based assays was proposed. The novelty involves the use of disk-shaped inserts for immobilization of biological and chemical reagents. The internal opening of the disks allows measurements of the reactions by standard microtiter plate readers without any additional steps involving liquid handling. Ideally the plate end-users just have to add the sample and take the measurement without any need of multiple reagent additions or transfer of the liquid to a different plate. The novel assay format also allows handling of reagents which are not soluble in an aqueous environment. As a proof of concept we describe here several model reactions which are compatible with microtiter plate format, such as monitoring enzymatic reactions catalyzed by glucose oxidase (GOx) and urease, measurements of proteins by BCA assay, analysis of pH, and concentration of antioxidants. The "mix and match" approach in the disk-shape format allows multiplexing and could be particularly useful for high throughput screening. One of the potential application areas for this novel assay format could be in a multianalyte system for measurement of clinically relevant analytes in primary care.

  7. Spallation reactions; Reactions de spallation

    Energy Technology Data Exchange (ETDEWEB)

    Cugon, J.

    1996-12-31

    Spallation reactions dominate the interactions of hadrons with nuclei in the GeV range (from {approx} 0.1 to {approx} 10 GeV). They correspond to a sometimes important ejection of light particles leaving most of the time a residue of mass commensurate with the target mass. The main features of the experimental data are briefly reviewed. The most successful theoretical model, namely the intranuclear cascade + evaporation model, is presented. Its physical content, results and possible improvements are critically discussed. Alternative approaches are shortly reviewed. (author). 84 refs.

  8. HTSC-Josephson step contacts

    International Nuclear Information System (INIS)

    Herrmann, K.

    1994-03-01

    In this work the properties of josephson step contacts are investigated. After a short introduction into Josephson step contacts the structure, properties and the Josphson contacts of YBa 2 Cu 3 O 7-x high-T c superconductors is presented. The fabrication of HTSC step contacts and the microstructure is discussed. The electric properties of these contacts are measured together with the Josephson emission and the magnetic field dependence. The temperature dependence of the stationary transport properties is given. (WL)

  9. The NIST Step Class Library (Step Into the Future)

    Science.gov (United States)

    1990-09-01

    Figure 6. Excerpt from a STEP exclange file based on the Geometry model 1be NIST STEP Class Libary Page 13 An issue of concern in this...Scheifler, R., Gettys, J., and Newman, P., X Window System: C Library and Protocol Reference. Digital Press, Bedford, Mass, 1988. [Schenck90] Schenck, D

  10. Step-by-Step Visual Manuals: Design and Development

    Science.gov (United States)

    Urata, Toshiyuki

    2004-01-01

    The types of handouts and manuals that are used in technology training vary. Some describe procedures in a narrative way without graphics; some employ step-by-step instructions with screen captures. According to Thirlway (1994), a training manual should be like a tutor that permits a student to learn at his own pace and gives him confidence for…

  11. On the Convexity of Step out - Step in Sequencing Games

    NARCIS (Netherlands)

    Musegaas, Marieke; Borm, Peter; Quant, Marieke

    2016-01-01

    The main result of this paper is the convexity of Step out - Step in (SoSi) sequencing games, a class of relaxed sequencing games first analyzed by Musegaas, Borm, and Quant (2015). The proof makes use of a polynomial time algorithm determining the value and an optimal processing order for an

  12. Valve cam design using numerical step-by-step method

    OpenAIRE

    Vasilyev, Aleksandr; Bakhracheva, Yuliya; Kabore, Ousman; Zelenskiy, Yuriy

    2014-01-01

    This article studies the numerical step-by-step method of cam profile design. The results of the study are used for designing the internal combustion engine valve gear. This method allows to profile the peak efficiency of cams in view of many restrictions, connected with valve gear serviceability and reliability.

  13. The bounded proof property via step algebras and step frames

    NARCIS (Netherlands)

    Bezhanishvili, N.; Ghilardi, Silvio

    2013-01-01

    We develop a semantic criterion for a specific rule-based calculus Ax axiomatizing a given logic L to have the so-called bounded proof property. This property is a kind of an analytic subformula property limiting the proof search space. Our main tools are one-step frames and one-step algebras. These

  14. Leading Change Step-by-Step: Tactics, Tools, and Tales

    Science.gov (United States)

    Spiro, Jody

    2010-01-01

    "Leading Change Step-by-Step" offers a comprehensive and tactical guide for change leaders. Spiro's approach has been field-tested for more than a decade and proven effective in a wide variety of public sector organizations including K-12 schools, universities, international agencies and non-profits. The book is filled with proven tactics for…

  15. ReactionPredictor: prediction of complex chemical reactions at the mechanistic level using machine learning.

    Science.gov (United States)

    Kayala, Matthew A; Baldi, Pierre

    2012-10-22

    Proposing reasonable mechanisms and predicting the course of chemical reactions is important to the practice of organic chemistry. Approaches to reaction prediction have historically used obfuscating representations and manually encoded patterns or rules. Here we present ReactionPredictor, a machine learning approach to reaction prediction that models elementary, mechanistic reactions as interactions between approximate molecular orbitals (MOs). A training data set of productive reactions known to occur at reasonable rates and yields and verified by inclusion in the literature or textbooks is derived from an existing rule-based system and expanded upon with manual curation from graduate level textbooks. Using this training data set of complex polar, hypervalent, radical, and pericyclic reactions, a two-stage machine learning prediction framework is trained and validated. In the first stage, filtering models trained at the level of individual MOs are used to reduce the space of possible reactions to consider. In the second stage, ranking models over the filtered space of possible reactions are used to order the reactions such that the productive reactions are the top ranked. The resulting model, ReactionPredictor, perfectly ranks polar reactions 78.1% of the time and recovers all productive reactions 95.7% of the time when allowing for small numbers of errors. Pericyclic and radical reactions are perfectly ranked 85.8% and 77.0% of the time, respectively, rising to >93% recovery for both reaction types with a small number of allowed errors. Decisions about which of the polar, pericyclic, or radical reaction type ranking models to use can be made with >99% accuracy. Finally, for multistep reaction pathways, we implement the first mechanistic pathway predictor using constrained tree-search to discover a set of reasonable mechanistic steps from given reactants to given products. Webserver implementations of both the single step and pathway versions of Reaction

  16. Redox reactions in food fermentations

    DEFF Research Database (Denmark)

    Hansen, Egon Bech

    2018-01-01

    involves oxidative steps in the early part of the pathways whereas a multitude of different reactions are used as compensating reductions. Much of the diversity seen between food fermentations arise from the different routes and the different electron acceptors used by microorganisms to counterbalance...... and this contributes to the diversity in flavor, color, texture, and shelf life. The review concludes that these reactions are still only incompletely understood and that they represent an interesting area for fundamental research and also represent a fertile field for product development through a more conscious use...... of the redox properties of strains used to compose food cultures....

  17. Atmospherically Relevant Radicals Derived from the Oxidation of Dimethyl Sulfide.

    Science.gov (United States)

    Mardyukov, Artur; Schreiner, Peter R

    2018-02-20

    The large number and amounts of volatile organosulfur compounds emitted to the atmosphere and the enormous variety of their reactions in various oxidation states make experimental measurements of even a small fraction of them a daunting task. Dimethyl sulfide (DMS) is a product of biological processes involving marine phytoplankton, and it is estimated to account for approximately 60% of the total natural sulfur gases released to the atmosphere. Ocean-emitted DMS has been suggested to play a role in atmospheric aerosol formation and thereby cloud formation. The reaction of ·OH with DMS is known to proceed by two independent channels: abstraction and addition. The oxidation of DMS is believed to be initiated by the reaction with ·OH and NO 3 · radicals, which eventually leads to the formation of sulfuric acid (H 2 SO 4 ) and methanesulfonic acid (CH 3 SO 3 H). The reaction of DMS with NO 3 · appears to proceed exclusively by hydrogen abstraction. The oxidation of DMS consists of a complex sequence of reactions. Depending on the time of the day or altitude, it may take a variety of pathways. In general, however, the oxidation proceeds via chains of radical reactions. Dimethyl sulfoxide (DMSO) has been reported to be a major product of the addition channel. Dimethyl sulfone (DMSO 2 ), SO 2 , CH 3 SO 3 H, and methanesulfinic acid (CH 3 S(O)OH) have been observed as products of further oxidation of DMSO. Understanding the details of DMS oxidation requires in-depth knowledge of the elementary steps of this seemingly simple transformation, which in turn requires a combination of experimental and theoretical methods. The methylthiyl (CH 3 S·), methylsulfinyl (CH 3 SO·), methylsulfonyl (CH 3 SO 2 ·), and methylsulfonyloxyl (CH 3 SO 3 ·) radicals have been postulated as intermediates in the oxidation of DMS. Therefore, studying the chemistry of sulfur-containing free radicals in the laboratory also is the basis for understanding the mechanism of DMS oxidation in the

  18. Nuclear Waste Vitrification Efficiency: Cold Cap Reactions

    International Nuclear Information System (INIS)

    Kruger, A.A.; Hrma, P.R.; Pokorny, R.

    2011-01-01

    The cost and schedule of nuclear waste treatment and immobilization are greatly affected by the rate of glass production. Various factors influence the performance of a waste-glass melter. One of the most significant, and also one of the least understood, is the process of batch melting. Studies are being conducted to gain fundamental understanding of the batch reactions, particularly those that influence the rate of melting, and models are being developed to link batch makeup and melter operation to the melting rate. Batch melting takes place within the cold cap, i.e., a batch layer floating on the surface of molten glass. The conversion of batch to glass consists of various chemical reactions, phase transitions, and diffusion-controlled processes. These include water evaporation (slurry feed contains as high as 60% water), gas evolution, the melting of salts, the formation of borate melt, reactions of borate melt with molten salts and with amorphous oxides (Fe 2 O 3 and Al 2 O 3 ), the formation of intermediate crystalline phases, the formation of a continuous glass-forming melt, the growth and collapse of primary foam, and the dissolution of residual solids. To this list we also need to add the formation of secondary foam that originates from molten glass but accumulates on the bottom of the cold cap. This study presents relevant data obtained for a high-level-waste melter feed and introduces a one-dimensional (1D) mathematical model of the cold cap as a step toward an advanced three-dimensional (3D) version for a complete model of the waste glass melter. The 1D model describes the batch-to-glass conversion within the cold cap as it progresses in a vertical direction. With constitutive equations and key parameters based on measured data, and simplified boundary conditions on the cold-cap interfaces with the glass melt and the plenum space of the melter, the model provides sensitivity analysis of the response of the cold cap to the batch makeup and melter

  19. A small step for mankind

    NARCIS (Netherlands)

    Huizing, C.; Koymans, R.L.C.; Kuiper, R.; Dams, D.; Hannemann, U.; Steffen, M.

    2010-01-01

    For many programming languages, the only formal semantics published is an SOS big-step semantics. Such a semantics is not suited for investigations that observe intermediate states, such as invariant techniques. In this paper, a construction is proposed that generates automatically a small-step SOS

  20. Grief: Difficult Times, Simple Steps.

    Science.gov (United States)

    Waszak, Emily Lane

    This guide presents techniques to assist others in coping with the loss of a loved one. Using the language of 9 layperson, the book contains more than 100 tips for caregivers or loved ones. A simple step is presented on each page, followed by reasons and instructions for each step. Chapters include: "What to Say"; "Helpful Things to Do"; "Dealing…

  1. Chain reaction

    International Nuclear Information System (INIS)

    Balogh, Brian.

    1991-01-01

    Chain Reaction is a work of recent American political history. It seeks to explain how and why America came to depend so heavily on its experts after World War II, how those experts translated that authority into political clout, and why that authority and political discretion declined in the 1970s. The author's research into the internal memoranda of the Atomic Energy Commission substantiates his argument in historical detail. It was not the ravages of American anti-intellectualism, as so many scholars have argued, that brought the experts back down to earth. Rather, their decline can be traced to the very roots of their success after World War II. The need to over-state anticipated results in order to garner public support, incessant professional and bureaucratic specialization, and the sheer proliferation of expertise pushed arcane and insulated debates between experts into public forums at the same time that a broad cross section of political participants found it easier to gain access to their own expertise. These tendencies ultimately undermined the political influence of all experts. (author)

  2. Single-Step Access to Long-Chain α,ω-Dicarboxylic Acids by Isomerizing Hydroxycarbonylation of Unsaturated Fatty Acids

    KAUST Repository

    Goldbach, Verena; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Mecking, Stefan

    2016-01-01

    active Pd hydride species. Theoretical calculations identified the hydrolysis as the rate-determining step. A low nucleophile concentration in the reaction mixture in combination with this high energetic barrier limits the potential of this reaction

  3. Monochloramine Cometabolism by Nitrifying Biofilm Relevant ...

    Science.gov (United States)

    Recently, biological monochloramine removal (i.e., cometabolism) by a pure culture ammonia–oxidizing bacteria, Nitrosomonas europaea, and a nitrifying mixed–culture have been shown to increase monochloramine demand. Although important, these previous suspended culture batch kinetic experiments were not representative of drinking water distribution systems where bacteria grow predominantly as biofilm attached to pipe walls or sediments and physiological differences may exist between suspension and biofilm growth. Therefore, the current research was an important next step in extending the previous results to investigate monochloramine cometabolism by biofilm grown in annular reactors under drinking water relevant conditions. Estimated monochloramine cometabolism kinetics were similar to those of ammonia metabolism, and monochloramine cometabolism was a significant loss mechanism (25–40% of the observed monochloramine loss). These results demonstrated that monochloramine cometabolism occurred in drinking water relevant nitrifying biofilm; thus, cometabolism may be a significant contribution to monochloramine loss during nitrification episodes in distribution systems. Investigate whether or not nitrifying biofilm can biologically transform monochloramine under drinking water relevant conditions.

  4. A Networks Approach to Modeling Enzymatic Reactions.

    Science.gov (United States)

    Imhof, P

    2016-01-01

    Modeling enzymatic reactions is a demanding task due to the complexity of the system, the many degrees of freedom involved and the complex, chemical, and conformational transitions associated with the reaction. Consequently, enzymatic reactions are not determined by precisely one reaction pathway. Hence, it is beneficial to obtain a comprehensive picture of possible reaction paths and competing mechanisms. By combining individually generated intermediate states and chemical transition steps a network of such pathways can be constructed. Transition networks are a discretized representation of a potential energy landscape consisting of a multitude of reaction pathways connecting the end states of the reaction. The graph structure of the network allows an easy identification of the energetically most favorable pathways as well as a number of alternative routes. © 2016 Elsevier Inc. All rights reserved.

  5. Relevance Vector Machine for Prediction of Soil Properties | Samui ...

    African Journals Online (AJOL)

    One of the first, most important steps in geotechnical engineering is site characterization. The ultimate goal of site characterization is to predict the in-situ soil properties at any half-space point for a site based on limited number of tests and data. In the present study, relevance vector machine (RVM) has been used to develop ...

  6. Microprocessor controller for stepping motors

    International Nuclear Information System (INIS)

    Strait, B.G.; Thuot, M.E.

    1977-01-01

    A new concept for digital computer control of multiple stepping motors which operate in a severe electromagnetic pulse environment is presented. The motors position mirrors in the beam-alignment system of a 100-kJ CO 2 laser. An asynchronous communications channel of a computer is used to send coded messages, containing the motor address and stepping-command information, to the stepping-motor controller in a bit serial format over a fiber-optics communications link. The addressed controller responds by transmitting to the computer its address and other motor information, thus confirming the received message. Each controller is capable of controlling three stepping motors. The controller contains the fiber-optics interface, a microprocessor, and the stepping-motor driven circuits. The microprocessor program, which resides in an EPROM, decodes the received messages, transmits responses, performs the stepping-motor sequence logic, maintains motor-position information, and monitors the motor's reference switch. For multiple stepping-motor application, the controllers are connected in a daisy chain providing control of many motors from one asynchronous communications channel of the computer

  7. Nuclear structure in deep-inelastic reactions

    International Nuclear Information System (INIS)

    Rehm, K.E.

    1986-01-01

    The paper concentrates on recent deep inelastic experiments conducted at Argonne National Laboratory and the nuclear structure effects evident in reactions between super heavy nuclei. Experiments indicate that these reactions evolve gradually from simple transfer processes which have been studied extensively for lighter nuclei such as 16 O, suggesting a theoretical approach connecting the one-step DWBA theory to the multistep statistical models of nuclear reactions. This transition between quasi-elastic and deep inelastic reactions is achieved by a simple random walk model. Some typical examples of nuclear structure effects are shown. 24 refs., 9 figs

  8. Investigation to biodiesel production by the two-step homogeneous base-catalyzed transesterification.

    Science.gov (United States)

    Ye, Jianchu; Tu, Song; Sha, Yong

    2010-10-01

    For the two-step transesterification biodiesel production made from the sunflower oil, based on the kinetics model of the homogeneous base-catalyzed transesterification and the liquid-liquid phase equilibrium of the transesterification product, the total methanol/oil mole ratio, the total reaction time, and the split ratios of methanol and reaction time between the two reactors in the stage of the two-step reaction are determined quantitatively. In consideration of the transesterification intermediate product, both the traditional distillation separation process and the improved separation process of the two-step reaction product are investigated in detail by means of the rigorous process simulation. In comparison with the traditional distillation process, the improved separation process of the two-step reaction product has distinct advantage in the energy duty and equipment requirement due to replacement of the costly methanol-biodiesel distillation column. Copyright 2010 Elsevier Ltd. All rights reserved.

  9. Human Papilloma Virus-Dependent HMGA1 Expression Is a Relevant Step in Cervical Carcinogenesis1

    Science.gov (United States)

    Mellone, Massimiliano; Rinaldi, Christian; Massimi, Isabella; Petroni, Marialaura; Veschi, Veronica; Talora, Claudio; Truffa, Silvia; Stabile, Helena; Frati, Luigi; Screpanti, Isabella; Gulino, Alberto; Giannini, Giuseppe

    2008-01-01

    HMGA1 is a member of a small family of architectural transcription factors involved in the coordinate assembly of multiprotein complexes referred to as enhanceosomes. In addition to their role in cell proliferation, differentiation, and development, high-mobility group proteins of the A type (HMGA) family members behave as transforming protoncogenes either in vitro or in animal models. Recent reports indicated that HMGA1 might counteract p53 pathway and provided an interesting hint on the mechanisms determining HMGA's transforming potential. HMGA1 expression is deregulated in a very large array of human tumors, including cervical cancer, but very limited information is available on the molecular mechanisms leading to HMGA1 deregulation in cancer cells. Here, we report that HMGA1 expression is sustained by human papilloma virus (HPV) E6/E7 proteins in cervical cancer, as demonstrated by either E6/E7 overexpression or by repression through RNA interference. Knocking down HMGA1 expression by means of RNA interference, we also showed that it is involved in cell proliferation and contributes to p53 inactivation in this type of neoplasia. Finally, we show that HMGA1 is necessary for the full expression of HPV18 E6 and E7 oncoproteins thus establishing a positive autoregulatory loop between HPV E6/E7 and HMGA1 expression. PMID:18670638

  10. Making Real Analysis Relevant to Secondary Teachers: Building up from and Stepping down to Practice

    Science.gov (United States)

    Wasserman, Nicholas H.; Fukawa-Connelly, Timothy; Villanueva, Matthew; Mejia-Ramos, Juan Pablo; Weber, Keith

    2017-01-01

    Future teachers often claim that advanced undergraduate courses, even those that attempt to connect to school mathematics, are not useful for their teaching. This paper proposes a new way of designing advanced undergraduate content courses for secondary teachers. The model involves beginning with an analysis of the curriculum and practices of…

  11. Adsorption-induced step formation

    DEFF Research Database (Denmark)

    Thostrup, P.; Christoffersen, Ebbe; Lorensen, Henrik Qvist

    2001-01-01

    Through an interplay between density functional calculations, Monte Carlo simulations and scanning tunneling microscopy experiments, we show that an intermediate coverage of CO on the Pt(110) surface gives rise to a new rough equilibrium structure with more than 50% step atoms. CO is shown to bind...... so strongly to low-coordinated Pt atoms that it can break Pt-Pt bonds and spontaneously form steps on the surface. It is argued that adsorption-induced step formation may be a general effect, in particular at high gas pressures and temperatures....

  12. A computational study of pyrolysis reactions of lignin model compounds

    Science.gov (United States)

    Thomas Elder

    2010-01-01

    Enthalpies of reaction for the initial steps in the pyrolysis of lignin have been evaluated at the CBS-4m level of theory using fully substituted b-O-4 dilignols. Values for competing unimolecular decomposition reactions are consistent with results previously published for phenethyl phenyl ether models, but with lowered selectivity. Chain propagating reactions of free...

  13. The primary steps of photosynthesis

    International Nuclear Information System (INIS)

    Fleming, G.R.; Van Grondelle, R.

    1996-01-01

    The two important initial steps of photosynthesis-electron transfer and energy transfer occur with great speed and efficiency. New techniques in laser optics and genetic engineering age helping us to understand why. (author). 24 refs. 8 figs

  14. 7 Steps to Aging Well

    Science.gov (United States)

    ... Issue Past Issues Special Section 7 Steps to Aging Well Past Issues / Winter 2007 Table of Contents ... Exercise: A Guide from the National Institute on Aging is a publication from NIA that has strength, ...

  15. Profiles of Dialogue for Relevance

    Directory of Open Access Journals (Sweden)

    Douglas Walton

    2016-12-01

    Full Text Available This paper uses argument diagrams, argumentation schemes, and some tools from formal argumentation systems developed in artificial intelligence to build a graph-theoretic model of relevance shown to be applicable (with some extensions as a practical method for helping a third party judge issues of relevance or irrelevance of an argument in real examples. Examples used to illustrate how the method works are drawn from disputes about relevance in natural language discourse, including a criminal trial and a parliamentary debate.

  16. Relevance theory: pragmatics and cognition.

    Science.gov (United States)

    Wearing, Catherine J

    2015-01-01

    Relevance Theory is a cognitively oriented theory of pragmatics, i.e., a theory of language use. It builds on the seminal work of H.P. Grice(1) to develop a pragmatic theory which is at once philosophically sensitive and empirically plausible (in both psychological and evolutionary terms). This entry reviews the central commitments and chief contributions of Relevance Theory, including its Gricean commitment to the centrality of intention-reading and inference in communication; the cognitively grounded notion of relevance which provides the mechanism for explaining pragmatic interpretation as an intention-driven, inferential process; and several key applications of the theory (lexical pragmatics, metaphor and irony, procedural meaning). Relevance Theory is an important contribution to our understanding of the pragmatics of communication. © 2014 John Wiley & Sons, Ltd.

  17. Clinical relevance in anesthesia journals

    DEFF Research Database (Denmark)

    Lauritsen, Jakob; Møller, Ann M

    2006-01-01

    The purpose of this review is to present the latest knowledge and research on the definition and distribution of clinically relevant articles in anesthesia journals. It will also discuss the importance of the chosen methodology and outcome of articles.......The purpose of this review is to present the latest knowledge and research on the definition and distribution of clinically relevant articles in anesthesia journals. It will also discuss the importance of the chosen methodology and outcome of articles....

  18. Chemical kinetics and reaction mechanism

    International Nuclear Information System (INIS)

    Jung, Ou Sik; Park, Youn Yeol

    1996-12-01

    This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.

  19. On the importance of hydrogen bonding in the promotion of Diels-Alder reactions of unactivated aldehydes: a computational study

    Science.gov (United States)

    Chemouri, Hafida; Mekelleche, Sidi Mohamed

    2014-03-01

    The kinetic solvent effects on the Diels-Alder (DA) reaction of N,N-dimethylamino-3-trimethylsilyl butadiene with p-anisaldehyde are studied by density functional calculations at the B3LYP/6-31C(d) level of theory. Experimentally, it has been found that the acceleration of this reaction is not due to the increase of the polarity of the solvent but it is rather due to hydrogen bonding (HB). Intrinsic reaction coordinate calculations combined with electron localisation function analysis show that this reaction follows a one-step two-stage mechanism with a highly asynchronous sigma bond formation process. The calculations, performed using an explicit solvent model based on the coordination of the carbonyl group with one molecule of the solvent, show a considerable decrease of the activation energy when going from the gas phase (ɛ = 1) to solution phase and this diminution is found to be more important in isopropyl alcohol (ɛ = 18.3) in comparison with acetonitrile (ɛ = 37.5). Our calculations also show that the acceleration of this DA reaction is due to the increase of the electrophilicity power of the solvated carbonyl compound and consequently the increase of the polarity of the reaction in the presence of protic solvents. The obtained results put in evidence the relevance of HB in the promotion of DA reactions of unactivated ketones as experimentally expected.

  20. Microsoft® Office Access™ 2007 Step by Step

    CERN Document Server

    Lambert, Steve; Lambert, Joan

    2009-01-01

    Experience learning made easy-and quickly teach yourself how to build database solutions with Access 2007. With Step By Step, you set the pace-building and practicing the skills you need, just when you need them! Build databases from scratch or from templatesExchange data with other databases and Office documentsCreate forms to simplify data entryUse filters and queries to find and analyze informationDesign rich reports that help make your data meaningfulHelp prevent data corruption and unauthorized access Your all-in-one learning experience includes: Files for building skills and practic

  1. Microsoft Windows Sharepoint Services 3.0 Step by Step

    CERN Document Server

    Londer, Olga; Bleeker, Todd; Coventry, Penelope

    2007-01-01

    Experience learning made easy-and quickly teach yourself how to use Windows SharePoint Services to enable effective team collaboration. With Step By Step, you set the pace-building and practicing the skills you need, just when you need them! Build your own SharePoint site with easy-to-use templatesCreate lists and libraries to store informationAdd discussion boards, wikis, and blogsSet up Document and Meeting Workspaces for easy collaborationShare calendars, contacts, and data from Microsoft Office programsCustomize your pages with Web Parts Your all-in-one learning experience includes: Fi

  2. Linear, Step by Step Managerial Performance, versus Exponential Performance

    Directory of Open Access Journals (Sweden)

    George MOLDOVEANU

    2011-04-01

    Full Text Available The paper proposes the transition from the potential management concept, which its authors approached by determining its dimension (Roşca, Moldoveanu, 2009b, to the linear, step by step performance concept, as an objective result of management process. In this way, we “answer” the theorists and practitioners, who support exponential management performance. The authors, as detractors of the exponential performance, are influenced by the current crisis (Roşca, Moldoveanu, 2009a, by the lack of organizational excellence in many companies, particularly in Romanian ones and also reaching “the finality” in the evolved companies, developed into an uncontrollable speed.

  3. Microsoft Office SharePoint Designer 2007 Step by Step

    CERN Document Server

    Coventry, Penelope

    2008-01-01

    The smart way to learn Office SharePoint Designer 2007-one step at a time! Work at your own pace through the easy numbered steps, practice files on CD, helpful hints, and troubleshooting tips to master the fundamentals of building customized SharePoint sites and applications. You'll learn how to work with Windows® SharePoint Services 3.0 and Office SharePoint Server 2007 to create Web pages complete with Cascading Style Sheets, Lists, Libraries, and customized Web parts. Then, make your site really work for you by adding data sources, including databases, XML data and Web services, and RSS fe

  4. A step-by-step methodology for enterprise interoperability projects

    Science.gov (United States)

    Chalmeta, Ricardo; Pazos, Verónica

    2015-05-01

    Enterprise interoperability is one of the key factors for enhancing enterprise competitiveness. Achieving enterprise interoperability is an extremely complex process which involves different technological, human and organisational elements. In this paper we present a framework to help enterprise interoperability. The framework has been developed taking into account the three domains of interoperability: Enterprise Modelling, Architecture and Platform and Ontologies. The main novelty of the framework in comparison to existing ones is that it includes a step-by-step methodology that explains how to carry out an enterprise interoperability project taking into account different interoperability views, like business, process, human resources, technology, knowledge and semantics.

  5. One step beyond: Different step-to-step transitions exist during continuous contact brachiation in siamangs

    Directory of Open Access Journals (Sweden)

    Fana Michilsens

    2012-02-01

    In brachiation, two main gaits are distinguished, ricochetal brachiation and continuous contact brachiation. During ricochetal brachiation, a flight phase exists and the body centre of mass (bCOM describes a parabolic trajectory. For continuous contact brachiation, where at least one hand is always in contact with the substrate, we showed in an earlier paper that four step-to-step transition types occur. We referred to these as a ‘point’, a ‘loop’, a ‘backward pendulum’ and a ‘parabolic’ transition. Only the first two transition types have previously been mentioned in the existing literature on gibbon brachiation. In the current study, we used three-dimensional video and force analysis to describe and characterize these four step-to-step transition types. Results show that, although individual preference occurs, the brachiation strides characterized by each transition type are mainly associated with speed. Yet, these four transitions seem to form a continuum rather than four distinct types. Energy recovery and collision fraction are used as estimators of mechanical efficiency of brachiation and, remarkably, these parameters do not differ between strides with different transition types. All strides show high energy recoveries (mean  = 70±11.4% and low collision fractions (mean  = 0.2±0.13, regardless of the step-to-step transition type used. We conclude that siamangs have efficient means of modifying locomotor speed during continuous contact brachiation by choosing particular step-to-step transition types, which all minimize collision fraction and enhance energy recovery.

  6. High accuracy step gauge interferometer

    Science.gov (United States)

    Byman, V.; Jaakkola, T.; Palosuo, I.; Lassila, A.

    2018-05-01

    Step gauges are convenient transfer standards for the calibration of coordinate measuring machines. A novel interferometer for step gauge calibrations implemented at VTT MIKES is described. The four-pass interferometer follows Abbe’s principle and measures the position of the inductive probe attached to a measuring head. The measuring head of the instrument is connected to a balanced boom above the carriage by a piezo translation stage. A key part of the measuring head is an invar structure on which the inductive probe and the corner cubes of the measuring arm of the interferometer are attached. The invar structure can be elevated so that the probe is raised without breaking the laser beam. During probing, the bending of the probe and the interferometer readings are recorded and the measurement face position is extrapolated to zero force. The measurement process is fully automated and the face positions of the steps can be measured up to a length of 2 m. Ambient conditions are measured continuously and the refractive index of air is compensated for. Before measurements the step gauge is aligned with an integrated 2D coordinate measuring system. The expanded uncertainty of step gauge calibration is U=\\sqrt{{{(64 nm)}2}+{{(88× {{10}-9}L)}2}} .

  7. FIRST STEP towards ICF commercialization

    International Nuclear Information System (INIS)

    Saylor, W.W.; Pendergrass, J.H.; Dudziak, D.J.

    1984-01-01

    Production of tritium for weapons and fusion R and D programs and successful development of Inertial Confinement Fusion (ICF) technologies are important national goals. A conceptual design for an ICF facility to meet these goals is presented. FIRST STEP (Fusion, Inertial, Reduced-Requirements Systems Test for Special Nuclear Material, Tritium, and Energy Production) is a concept for a plant to produce SNM, tritium, and energy while serving as a test bed for ICF technology development. A credible conceptual design for an ICF SNM and tritium production facility that competes favorably with fission technology on the bases of cost, production quality, and safety was sought. FIRST STEP is also designed to be an engineering test facility that integrates systems required for an ICF power plant and that is intermediate in scale between proof-of-principle experiment and commercial power plant. FIRST STEP driver and pellet performance requirements are moderate and represent reasonable intermediate goals in an R and D plan for ICF commercialization. Repetition rate requirements for FIRST STEP are similar to those of commercial size plants and FIRST STEP can be used to integrate systems under realistic ICF conditions

  8. From raw material to dish: pasta quality step by step.

    Science.gov (United States)

    Sicignano, Angelo; Di Monaco, Rossella; Masi, Paolo; Cavella, Silvana

    2015-10-01

    Pasta is a traditional Italian cereal-based food that is popular worldwide because of its convenience, versatility, sensory and nutritional value. The aim of this review is to present a step-by-step guide to facilitate the understanding of the most important events that can affect pasta characteristics, directing the reader to the appropriate production steps. Owing to its unique flavor, color, composition and rheological properties, durum wheat semolina is the best raw material for pasta production. Although pasta is traditionally made from only two ingredients, sensory quality and chemical/physical characteristics of the final product may vary greatly. Starting from the same ingredients, there are a lot of different events in each step of pasta production that can result in the development of varieties of pasta with different characteristics. In particular, numerous studies have demonstrated the importance of temperature and humidity conditions of the pasta drying operation as well as the significance of the choice of raw material and operating conditions on pasta quality. © 2015 Society of Chemical Industry.

  9. Step by step parallel programming method for molecular dynamics code

    International Nuclear Information System (INIS)

    Orii, Shigeo; Ohta, Toshio

    1996-07-01

    Parallel programming for a numerical simulation program of molecular dynamics is carried out with a step-by-step programming technique using the two phase method. As a result, within the range of a certain computing parameters, it is found to obtain parallel performance by using the level of parallel programming which decomposes the calculation according to indices of do-loops into each processor on the vector parallel computer VPP500 and the scalar parallel computer Paragon. It is also found that VPP500 shows parallel performance in wider range computing parameters. The reason is that the time cost of the program parts, which can not be reduced by the do-loop level of the parallel programming, can be reduced to the negligible level by the vectorization. After that, the time consuming parts of the program are concentrated on less parts that can be accelerated by the do-loop level of the parallel programming. This report shows the step-by-step parallel programming method and the parallel performance of the molecular dynamics code on VPP500 and Paragon. (author)

  10. DEPENDENCE OF X-RAY BURST MODELS ON NUCLEAR REACTION RATES

    Energy Technology Data Exchange (ETDEWEB)

    Cyburt, R. H.; Keek, L.; Schatz, H. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Amthor, A. M. [Department of Physics and Astronomy, Bucknell University, Lewisburg, PA 17837 (United States); Heger, A.; Meisel, Z.; Smith, K. [Joint Institute for Nuclear Astrophysics (JINA), Michigan State University, East Lansing, MI 48824 (United States); Johnson, E. [Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States)

    2016-10-20

    X-ray bursts are thermonuclear flashes on the surface of accreting neutron stars, and reliable burst models are needed to interpret observations in terms of properties of the neutron star and the binary system. We investigate the dependence of X-ray burst models on uncertainties in (p, γ ), ( α , γ ), and ( α , p) nuclear reaction rates using fully self-consistent burst models that account for the feedbacks between changes in nuclear energy generation and changes in astrophysical conditions. A two-step approach first identified sensitive nuclear reaction rates in a single-zone model with ignition conditions chosen to match calculations with a state-of-the-art 1D multi-zone model based on the Kepler stellar evolution code. All relevant reaction rates on neutron-deficient isotopes up to mass 106 were individually varied by a factor of 100 up and down. Calculations of the 84 changes in reaction rate with the highest impact were then repeated in the 1D multi-zone model. We find a number of uncertain reaction rates that affect predictions of light curves and burst ashes significantly. The results provide insights into the nuclear processes that shape observables from X-ray bursts, and guidance for future nuclear physics work to reduce nuclear uncertainties in X-ray burst models.

  11. Thermodynamic approach and comparison of two-step and single step DME (dimethyl ether) syntheses with carbon dioxide utilization

    International Nuclear Information System (INIS)

    Chen, Wei-Hsin; Hsu, Chih-Liang; Wang, Xiao-Dong

    2016-01-01

    DME (Dimethyl ether) synthesis from syngas with CO_2 utilization through two-step and single step processes is analyzed thermodynamically. The influences of reaction temperature, H_2/CO molar ratio, and CO_2/CO molar ratio on CO and CO_2 conversions, DME selectivity and yield, and thermal behavior are evaluated. Particular attention is paid to the comparison of the performance of DME synthesis between the two different methods. In the two-step method, the addition of CO_2 suppresses the CO conversion during methanol synthesis. An increase in CO_2/CO ratio decreases the CO_2 conversion (negative effect), but increases the total consumption amount of CO_2 (positive effect). At a given reaction temperature with H_2/CO = 4, the maximum DME yield develops at CO_2/CO = 1. In the single step method, over 98% of CO can be converted and the DME yield can be as high as 0.52 mol (mol CO)"−"1 at CO_2/CO = 2. The comparison of the single step and two-step processes indicates that the maximum CO conversion, DME selectivity, and DME yield in the former are higher than those in the latter, whereas an opposite result in the maximum CO_2 conversion is observed. These results reveal that the single step process has lower thermodynamic limitation and is a better option for DME synthesis. From CO_2 utilization point of view, the operation with low temperature, high H_2/CO ratio, and low CO_2/CO ratio results in higher CO_2 conversion, irrespective of two-step or single step DME synthesis. - Highlights: • DME (Dimethyl ether) synthesis with CO_2 utilization is analyzed thermodynamically. • Single step and two-step DME syntheses are studied and compared with each other. • CO_2 addition suppresses CO conversion in MeOH synthesis but increases MeOH yield. • The performance of the single step DME synthesis is better than that of the two-step one. • Increase CO_2/CO ratio decreases CO_2 conversion but increases CO_2 consumption amount.

  12. Measurement of the 209Bi(n ,4 n )206Bi and 169Tm(n ,3 n )167Tm cross sections between 23.5 and 30.5 MeV relevant to reaction-in-flight neutron studies at the National Ignition Facility

    Science.gov (United States)

    Gooden, M. E.; Bredeweg, T. A.; Champine, B.; Combs, D. C.; Finch, S.; Hayes-Sterbenz, A.; Henry, E.; Krishichayan, Rundberg, R.; Tornow, W.; Wilhelmy, J.; Yeamans, C.

    2017-08-01

    At the National Ignition Facility, experiments are being performed to measure charged-particle stopping powers in the previously unexplored warm dense plasma regime. These measurements are done using reaction-in-flight (RIF) neutrons from an inertial confinement fusion system. RIF neutrons are produced with a continuum of energies up to 30 MeV. By making activation measurements utilizing threshold reactions for neutrons in the energy range of 15 reaction has been used. However, in an effort to provide a secondary complimentary measurement, efforts are underway to make use of the 209Bi(n ,4 n )206Bi reaction, with a threshold of 22.5 MeV. The cross sections were measured at the 10 MV tandem Van De Graaff accelerator at the Triangle Universities Nuclear Laboratory with quasimonoenergetic neutrons between 23.5 and 30.5 MeV, where few previous measurements have been made. Cross-section data are compared to calculations and other available measurements.

  13. Step-by-step phacoemulsification training program for ophthalmology residents

    Directory of Open Access Journals (Sweden)

    Wang Yulan

    2013-01-01

    Full Text Available Aims: The aim was to analyze the learning curve of phacoemulsification (phaco performed by residents without experience in performing extra-capsular cataract extraction (ECCE in a step-by-step training program (SBSTP. Materials and Methods: Consecutive surgical records of phaco performed from March 2009 to Sept 2011 by four residents without previous ECCE experience were retrospectively reviewed. The completion rate of the first 30 procedures by each resident was calculated. The main intraoperative phaco parameter records for the first 30 surgeries by each resident were compared with those for their last 30 surgeries. Intraoperative complications in the residents′ procedures were also recorded and analyzed. Results: A total of 1013 surgeries were performed by residents. The completion rate for the first 30 phaco procedures was 79.2 μ 5.8%. The main reasons for halting the procedure were as follows: Anterior capsule tear, inability to crack the nucleus, and posterior capsular rupture during phaco or cortex removal. Cumulative dissipated energy of phaco power used during the surgeries was significantly less in the last 30 cases compared with the first 30 cases (30.10 μ 17.58 vs. 55.41 μ 37.59, P = 0.021. Posterior capsular rupture rate was 2.5 μ 1.2% in total (10.8 μ 4.2% in the first 30 cases and 1.7 μ 1.9% in the last 30 cases, P = 0.008; a statistically significant difference. Conclusion:The step-by-step training program might be a necessary process for a resident to transit from dependence to a self-supported operator. It is also an essential middle step between wet lab training to performing the entire phaco procedure on the patient both effectively and safely.

  14. Modeling of uncertainties in biochemical reactions.

    Science.gov (United States)

    Mišković, Ljubiša; Hatzimanikatis, Vassily

    2011-02-01

    Mathematical modeling is an indispensable tool for research and development in biotechnology and bioengineering. The formulation of kinetic models of biochemical networks depends on knowledge of the kinetic properties of the enzymes of the individual reactions. However, kinetic data acquired from experimental observations bring along uncertainties due to various experimental conditions and measurement methods. In this contribution, we propose a novel way to model the uncertainty in the enzyme kinetics and to predict quantitatively the responses of metabolic reactions to the changes in enzyme activities under uncertainty. The proposed methodology accounts explicitly for mechanistic properties of enzymes and physico-chemical and thermodynamic constraints, and is based on formalism from systems theory and metabolic control analysis. We achieve this by observing that kinetic responses of metabolic reactions depend: (i) on the distribution of the enzymes among their free form and all reactive states; (ii) on the equilibrium displacements of the overall reaction and that of the individual enzymatic steps; and (iii) on the net fluxes through the enzyme. Relying on this observation, we develop a novel, efficient Monte Carlo sampling procedure to generate all states within a metabolic reaction that satisfy imposed constrains. Thus, we derive the statistics of the expected responses of the metabolic reactions to changes in enzyme levels and activities, in the levels of metabolites, and in the values of the kinetic parameters. We present aspects of the proposed framework through an example of the fundamental three-step reversible enzymatic reaction mechanism. We demonstrate that the equilibrium displacements of the individual enzymatic steps have an important influence on kinetic responses of the enzyme. Furthermore, we derive the conditions that must be satisfied by a reversible three-step enzymatic reaction operating far away from the equilibrium in order to respond to

  15. Time step MOTA thermostat simulation

    International Nuclear Information System (INIS)

    Guthrie, G.L.

    1978-09-01

    The report details the logic, program layout, and operating procedures for the time-step MOTA (Materials Open Test Assembly) thermostat simulation program known as GYRD. It will enable prospective users to understand the operation of the program, run it, and interpret the results. The time-step simulation analysis was the approach chosen to determine the maximum value gain that could be used to minimize steady temperature offset without risking undamped thermal oscillations. The advantage of the GYRD program is that it directly shows hunting, ringing phenomenon, and similar events. Programs BITT and CYLB are faster, but do not directly show ringing time

  16. A mechanism for leader stepping

    Science.gov (United States)

    Ebert, U.; Carlson, B. E.; Koehn, C.

    2013-12-01

    The stepping of negative leaders is well observed, but not well understood. A major problem consists of the fact that the streamer corona is typically invisible within a thunderstorm, but determines the evolution of a leader. Motivated by recent observations of streamer and leader formation in the laboratory by T.M.P. Briels, S. Nijdam, P. Kochkin, A.P.J. van Deursen et al., by recent simulations of these processes by J. Teunissen, A. Sun et al., and by our theoretical understanding of the process, we suggest how laboratory phenomena can be extrapolated to lightning leaders to explain the stepping mechanism.

  17. Ten steps to conducting health professional education research.

    Science.gov (United States)

    Scott, Karen; Caldwell, Patrina; Schuwirth, Lambert

    2015-08-01

    The approaches used to educate future clinicians must be continually improved through evidence-based methods. Clinicians interested in conducting education research need to understand the terminology and conventions of health professional education, in the same way that health professional educators from education backgrounds need to be aware of clinical practices and scientific mores and jargon. This article provides clinicians with 10 steps to conducting health professional education research, and encourages collaboration between clinicians interested in education and health professional educators. The basic steps in conducting education research are introduced, beginning with literature searches, using appropriate terminology and writing conventions, and finding research collaborators. We encourage researchers to ask themselves, 'So what?' about their research idea to ensure it is interesting and relevant to a journal's readers. The nuts and bolts of educational research are then presented, including research questions and methodologies, outcome measures, theoretical frameworks and epistemologies. The final two steps aim to foster internationally relevant and well-designed research studies. Conducting and publishing education research is often difficult for clinicians, who struggle with what is required. Yet clinicians who teach are ideally placed to identify the knowledge gaps about how we can more effectively educate future clinicians. These 10 steps provide clinicians with guidance on how to conduct education research so relevant research findings can inform the education of future clinicians. Conducting and publishing education research is often difficult for clinicians. © 2015 John Wiley & Sons Ltd.

  18. Energetics and kinetics of ferrocyanide and nitrate/nitrite reactions

    International Nuclear Information System (INIS)

    Scheele, R.D.; Burger, L.L.; Sell, R.L.

    1994-01-01

    During the 1950's, radiocesium scavenging at the Hanford site resulted in radioactive waste sludges containing ferrocyanide, nitrate, and nitrite. These waters are a concern since certain mixtures of ferrocyanide and nitrate and/or nitrite are known to explode when heated. The authors have used differential scanning calorimetry, thermogravimetric analysis, isothermal calorimetry and gravimetry, and accelerating rate calorimetry to measure the thermal behavior, the reaction enthalpies, and selected kinetic parameters for reactions between sodium nickel ferrocyanide, the suspected ferrocyanide form in Hanford wastes, and nitrate and/or nitrite. These studies indicate that the oxidation proceeds via multiple steps, the initial reaction begins near 200 degrees C, the initial step has a high activation energy (>200 kJ/mole-K), succeeding reaction steps have activation energies ranging from 90 to 160 kJ/mole-K, and that the oxidation yields about 50% of the theoretical heat of reaction for the most energetic reaction

  19. Explore the reaction mechanism of the Maillard reaction: a density functional theory study.

    Science.gov (United States)

    Ren, Ge-Rui; Zhao, Li-Jiang; Sun, Qiang; Xie, Hu-Jun; Lei, Qun-Fang; Fang, Wen-Jun

    2015-05-01

    The mechanism of Maillard reaction has been investigated by means of density functional theory calculations in the gaseous phase and aqueous solution. The Maillard reaction is a cascade of consecutive and parallel reaction. In the present model system study, glucose and glycine were taken as the initial reactants. On the basis of previous experimental results, the mechanisms of Maillard reaction have been proposed, and the possibility for the formation of different compounds have been evaluated through calculating the relative energy changes for different steps of reaction under different pH conditions. Our calculations reveal that the TS3 in Amadori rearrangement reaction is the rate-determining step of Maillard reaction with the activation barriers of about 66.7 and 68.8 kcal mol(-1) in the gaseous phase and aqueous solution, respectively. The calculation results are in good agreement with previous studies and could provide insights into the reaction mechanism of Maillard reaction, since experimental evaluation of the role of intermediates in the Maillard reaction is quite complicated.

  20. Shippingport: A relevant decommissioning project

    International Nuclear Information System (INIS)

    Crimi, F.P.

    1988-01-01

    Because of Shippingport's low electrical power rating (72 MWe), there has been some misunderstanding on the relevancy of the Shippingport Station Decommissioning Project (SSDP) to a modern 1175 MWe commercial pressurized water reactor (PWR) power station. This paper provides a comparison of the major components of the reactor plant of the 72 MWe Shippingport Atomic Power Station and an 1175 MWe nuclear plant and the relevancy of the Shippingport decommissioning as a demonstration project for the nuclear industry. For the purpose of this comparison, Portland General Electric Company's 1175 MWe Trojan Nuclear Plant at Rainier, Oregon, has been used as the reference nuclear power plant. 2 refs., 2 figs., 1 tab

  1. Combustion kinetics and reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Klemm, R.B.; Sutherland, J.W. [Brookhaven National Laboratory, Upton, NY (United States)

    1993-12-01

    This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.

  2. Driver training in steps (DTS).

    NARCIS (Netherlands)

    2010-01-01

    For some years now, it has been possible in the Netherlands to follow a Driver Training in Steps (DTS) as well as the regular driver training. The DTS is a structured training method with clear training objectives which are categorized in four modules. Although the DTS is considerably better than

  3. Biphasic kinetics in the reaction between amino acids or glutathione and the chromium acetate cluster, [Cr3O(OAc)6]+.

    Science.gov (United States)

    Chaudhary, Shveta; Van Horn, J David

    2006-11-07

    Kinetics for the breakdown of the trinuclear chromium acetate cluster with a series of monoprotic and diprotic amino acid ligands and with glutathione in aqueous media have been investigated spectrophotometrically at pH 3.5-5.5 and in a temperature range of 45-60 degrees C. Under pseudo-first-order conditions, reactions with these ligands exhibited biphasic kinetic behavior that can be accounted for by a consecutive two-step reaction, A-->B-->C, where A is assumed to be a forced ion pair, B an intermediate and C is the product; experimental data fit to a biexponential equation for the transformation. Rates for k(short), k(long), and k(obs) were determined by manual extrapolation of absorbance data or curve-fitting routines; associated activation parameters for each step of the reaction were calculated using the Eyring equation. Rates for the first and second steps of the reaction are on the order of approximately 10(-4) and approximately 10(-5)s(-1), respectively. The large negative values of DeltaS++ and smaller DeltaH++ in the first step indicate an associative step, while high positive values of DeltaS(double dagger) in the second step indicate dissociation. To account for the results mechanistically, the results are interpreted to be a first step of ligand exchange with a pseudo-axial aqua ligand, followed by a dissociative step involving acetate or oxo ligand displacement. The dissociative step is the rate determining step, with k(obs) approximately k(long). The results demonstrate reaction pathways that are available to the Cr(III) metal centers that may be physiologically relevant in the ligand-rich environment of biological systems. Under general conditions Cr(III) clusters may be expected to be broken down, unless some unique biological environment stabilizes the cluster. The present study has application to the processes related to Cr(III) transport and excretion, to potential mechanisms of Cr(III) action in a biological setting, and to the

  4. The relevance of 7-day patch test reading.

    Science.gov (United States)

    Higgins, Eleanor; Collins, Paul

    2013-01-01

    Patch test readings are usually performed on day 2 (48 hours) and day 4 (96 hours). However, reports in the literature identify delayed allergy to metals, corticosteroids, antibiotics, some preservatives, acrylic and methacrylic monomers and p-phenylenediamine. The aim of our study was to identify the benefit of performing a day 7 (168 hours) reading to identify relevant late positive reactions. Two hundred three consecutive patients were patch tested to the British Society for Cutaneous Allergy standard series with additional test series selected according to clinical history and applied at the same time. Twenty-six patients (12.8%) had new positive reactions on day 7 (168 hours), with 28 relevant positive reactions to 21 allergens. These included mercury 0.5% (2/26); cobalt chloride 1% (2/26); colophony 20% (2/26); disperse blue mix 106/124 1% (2/26); preservatives (4/26) that included Methylchloroisothiazolinone/methylisothiazolinone, sodium metabisulfite, and diazolidinyl urea; fragrances (7/26); and gentamycin sulfate 20% (1/26). These results confirm findings in the literature and support the argument for performing a day 7 reading (168 hours) to identify relevant late positive reactions.

  5. Reactions of butadiyne. 1: The reaction with hydrogen atoms

    Science.gov (United States)

    Schwanebeck, W.; Warnatz, J.

    1984-01-01

    The reaction of hydrogen (H) atoms with butadiene (C4H2) was studied at room temperature in a pressure range between w mbar and 10 mbar. The primary step was an addition of H to C4H2 which is in its high pressure range at p 1 mbar. Under these conditions the following addition of a second H atom lies in the transition region between low and high pressure range. Vibrationally excited C4H4 can be deactivated to form buten-(1)-yne-(3)(C4H4) or decomposes into two C2H2 molecules. The rate constant at room temperature for primary step is given. The second order rate constant for the consumption of buten-(1)-yne-(3) is an H atom excess at room temperature is given.

  6. Theoretical studies of chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Schatz, G.C. [Argonne National Laboratory, IL (United States)

    1993-12-01

    This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.

  7. Dramatic lives and relevant becomings

    DEFF Research Database (Denmark)

    Henriksen, Ann-Karina; Miller, Jody

    2012-01-01

    of marginality into positions of relevance. The analysis builds on empirical data from Copenhagen, Denmark, gained through ethnographic fieldwork with the participation of 20 female informants aged 13–22. The theoretical contribution proposes viewing conflicts as multi-linear, multi-causal and non...

  8. Regularization in Matrix Relevance Learning

    NARCIS (Netherlands)

    Schneider, Petra; Bunte, Kerstin; Stiekema, Han; Hammer, Barbara; Villmann, Thomas; Biehl, Michael

    A In this paper, we present a regularization technique to extend recently proposed matrix learning schemes in learning vector quantization (LVQ). These learning algorithms extend the concept of adaptive distance measures in LVQ to the use of relevance matrices. In general, metric learning can

  9. Is impaired control of reactive stepping related to falls during inpatient stroke rehabilitation?

    Science.gov (United States)

    Mansfield, Avril; Inness, Elizabeth L; Wong, Jennifer S; Fraser, Julia E; McIlroy, William E

    2013-01-01

    Individuals with stroke fall more often than age-matched controls. Although many focus on the multifactorial nature of falls, the fundamental problem is likely the ability for an individual to generate reactions to recover from a loss of balance. Stepping reactions to recover balance are particularly important to balance recovery, and individuals with stroke have difficulty executing these responses to prevent a fall following a loss of balance. The purpose of this study is to determine if characteristics of balance recovery steps are related to falls during inpatient stroke rehabilitation. We conducted a retrospective review of individuals with stroke attending inpatient rehabilitation (n = 136). Details of falls experienced during inpatient rehabilitation were obtained from incident reports, nursing notes, and patient interviews. Stepping reactions were evoked using a "release-from-lean" postural perturbation. Poisson regression was used to determine characteristics of stepping reactions that were related to increased fall frequency relative to length of stay. In all, 20 individuals experienced 29 falls during inpatient rehabilitation. The characteristics of stepping reactions significantly related to increased fall rates were increased frequency of external assistance to prevent a fall to the floor, increased frequency of no-step responses, increased frequency of step responses with inadequate foot clearance, and delayed time to initiate stepping responses. Impaired control of balance recovery steps is related to increased fall rates during inpatient stroke rehabilitation. This study informs the specific features of stepping reactions that can be targeted with physiotherapy intervention during inpatient rehabilitation to improve dynamic stability control and potentially prevent falls.

  10. Energetics of highly kinked step edges

    NARCIS (Netherlands)

    Zandvliet, Henricus J.W.

    2010-01-01

    We have determined the step edge free energy, the step edge stiffness and dimensionless inverse step edge stiffness of the highly kinked < 010> oriented step on a (001) surface of a simple square lattice within the framework of a solid-on-solid model. We have found an exact expression for the step

  11. A Step-by-Step Framework on Discrete Events Simulation in Emergency Department; A Systematic Review.

    Science.gov (United States)

    Dehghani, Mahsa; Moftian, Nazila; Rezaei-Hachesu, Peyman; Samad-Soltani, Taha

    2017-04-01

    To systematically review the current literature of simulation in healthcare including the structured steps in the emergency healthcare sector by proposing a framework for simulation in the emergency department. For the purpose of collecting the data, PubMed and ACM databases were used between the years 2003 and 2013. The inclusion criteria were to select English-written articles available in full text with the closest objectives from among a total of 54 articles retrieved from the databases. Subsequently, 11 articles were selected for further analysis. The studies focused on the reduction of waiting time and patient stay, optimization of resources allocation, creation of crisis and maximum demand scenarios, identification of overcrowding bottlenecks, investigation of the impact of other systems on the existing system, and improvement of the system operations and functions. Subsequently, 10 simulation steps were derived from the relevant studies after an expert's evaluation. The 10-steps approach proposed on the basis of the selected studies provides simulation and planning specialists with a structured method for both analyzing problems and choosing best-case scenarios. Moreover, following this framework systematically enables the development of design processes as well as software implementation of simulation problems.

  12. Theoretical aspects of several successive two-step redox mechanisms in protein-film cyclic staircase voltammetry

    International Nuclear Information System (INIS)

    Gulaboski, Rubin; Kokoškarova, Pavlinka; Mitrev, Saša

    2012-01-01

    Highlights: ► Theoretical models for 2e− successive mechanisms are considered. ► The models are compatible for various metal-containing redox proteins. ► Diagnostic criteria are provided to recognize the particular redox mechanism. - Abstract: Protein-film voltammetry (PFV) is a versatile tool designed to provide insight into the enzymes physiological functions by studying the redox properties of various oxido-reductases with suitable voltammetric technique. The determination of the thermodynamic and kinetic parameters relevant to protein's physiological properties is achieved via methodologies established from theoretical considerations of various mechanisms in PFV. So far, the majority of the mathematical models in PFV have been developed for redox proteins undergoing a single-step electron transfer reactions. However, there are many oxido-reductases containing quinone moieties or polyvalent ions of transition metals like Mo, Mn, W, Fe or Co as redox centers, whose redox chemistry can be described only via mathematical models considering successive two-step electron transformation. In this work we consider theoretically the protein-film redox mechanisms of the EE (Electrochemical–Electrochemical), ECE (Electrochemical–Chemical–Electrochemical), and EECat (Electrochemical–Electrochemical–Catalytic) systems under conditions of cyclic staircase voltammetry. We also propose methodologies to determine the kinetics of electron transfer steps by all considered mechanisms. The experimentalists working with PFV can get large benefits from the simulated voltammograms given in this work.

  13. Continuum spectra in light-ion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Tamura, T.; Udagawa, T. [Texas Univ., Austin (USA). Dept. of Physics; Ikegami, H.; Muraoka, M [eds.

    1980-01-01

    Recent developments in the use of multi-step direct reaction method, to fit continuum cross sections of light-ion reactions, are reviewed. There has been a long-standing difficulty in reproducing sufficiently large (p, p') continuum cross section, but it has now been all but removed. It will be discussed in some detail, how this was achieved. Analyses of very recent data on analyzing powers in the continuum of (p, p') and (p, ..cap alpha..) reactions will also be discussed. Finally, analysis of the breakup of h into d and p will be presented.

  14. Ethylene dissociation on flat and stepped Ni(111): A combined STM and DFT study

    DEFF Research Database (Denmark)

    Vang, R.T.; Honkala, Johanna Karoliina; Dahl, S.

    2006-01-01

    The dissociative adsorption of ethylene (C(2)H(4)) on Ni(111) was studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The STM studies reveal that ethylene decomposes exclusively at the step edges at room temperature. However, the step edge sites...... are poisoned by the reaction products and thus only a small brim of decomposed ethylene is formed. At 500 K decomposition on the (111) facets leads to a continuous growth of carbidic islands, which nucleate along the step edges. DFT calculations were performed for several intermediate steps...... in the decomposition of ethylene on both Ni(111) and the stepped Ni(211) surface. In general the Ni(211) surface is found to have a higher reactivity than the Ni(111) surface. Furthermore, the calculations show that the influence of step edge atoms is very different for the different reaction pathways. In particular...

  15. DEFORMATION DEPENDENT TUL MULTI-STEP DIRECT MODEL

    International Nuclear Information System (INIS)

    WIENKE, H.; CAPOTE, R.; HERMAN, M.; SIN, M.

    2007-01-01

    The Multi-Step Direct (MSD) module TRISTAN in the nuclear reaction code EMPIRE has been extended in order to account for nuclear deformation. The new formalism was tested in calculations of neutron emission spectra emitted from the 232 Th(n,xn) reaction. These calculations include vibration-rotational Coupled Channels (CC) for the inelastic scattering to low-lying collective levels, ''deformed'' MSD with quadrupole deformation for inelastic scattering to the continuum, Multi-Step Compound (MSC) and Hauser-Feshbach with advanced treatment of the fission channel. Prompt fission neutrons were also calculated. The comparison with experimental data shows clear improvement over the ''spherical'' MSD calculations and JEFF-3.1 and JENDL-3.3 evaluations

  16. Deformation dependent TUL multi-step direct model

    International Nuclear Information System (INIS)

    Wienke, H.; Capote, R.; Herman, M.; Sin, M.

    2008-01-01

    The Multi-Step Direct (MSD) module TRISTAN in the nuclear reaction code EMPIRE has been extended to account for nuclear deformation. The new formalism was tested in calculations of neutron emission spectra emitted from the 232 Th(n,xn) reaction. These calculations include vibration-rotational Coupled Channels (CC) for the inelastic scattering to low-lying collective levels, 'deformed' MSD with quadrupole deformation for inelastic scattering to the continuum, Multi-Step Compound (MSC) and Hauser-Feshbach with advanced treatment of the fission channel. Prompt fission neutrons were also calculated. The comparison with experimental data shows clear improvement over the 'spherical' MSD calculations and JEFF-3.1 and JENDL-3.3 evaluations. (authors)

  17. Liquid-phase reforming and hydrodeoxygenation as a two-step route to aromatics from lignin

    NARCIS (Netherlands)

    Jongerius, A.L.; Bruijnincx, P.C.A.; Weckhuysen, B.M.

    2013-01-01

    A two-step approach to the conversion of organosolv, kraft and sugarcane bagasse lignin to monoaromatic compounds of low oxygen content is presented. The first step consists of lignin depolymerization in a liquid phase reforming (LPR) reaction over a 1 wt% Pt/γ-Al2O3 catalyst at 225 °C in alkaline

  18. Step 2: Know Your Diabetes ABCs

    Science.gov (United States)

    ... please turn JavaScript on. Feature: Type 2 Diabetes Step 2: Know Your Diabetes ABCs Past Issues / Fall ... 2 Diabetes" Articles Diabetes Is Serious But Manageable / Step 1: Learn About Diabetes / Step 2: Know Your ...

  19. Microchemical Plant in a Liquid Droplet: Plasmonic Liquid Marble for Sequential Reactions and Attomole Detection of Toxin at Microliter Scale.

    Science.gov (United States)

    Han, Xuemei; Koh, Charlynn Sher Lin; Lee, Hiang Kwee; Chew, Wee Shern; Ling, Xing Yi

    2017-11-15

    Miniaturizing the continuous multistep operations of a factory into a microchemical plant offers a safe and cost-effective approach to promote high-throughput screening in drug development and enforcement of industrial/environmental safety. While particle-assembled microdroplets in the form of liquid marble are ideal as microchemical plant, these platforms are mainly restricted to single-step reactions and limited to ex situ reaction monitoring. Herein, we utilize plasmonic liquid marble (PLM), formed by encapsulating liquid droplet with Ag nanocubes, to address these issues and demonstrate it as an ideal microchemical plant to conduct reaction-and-detection sequences on-demand in a nondisruptive manner. Utilizing a two-step azo-dye formation as our model reaction, our microchemical plant allows rapid and efficient diazotization of nitroaniline to form diazonium nitrobenzene, followed by the azo coupling of this intermediate with target aromatic compound to yield azo-dye. These molecular events are tracked in situ via SERS measurement through the plasmonic shell and further verified with in silico investigation. Furthermore, we apply our microchemical plant for ultrasensitive SERS detection and quantification of bisphenol A (BPA) with detection limit down to 10 amol, which is 50 000-fold lower than the BPA safety limit. Together with the protections offered by plasmonic shell against external environments, these collective advantages empower PLM as a multifunctional microchemical plant to facilitate small-volume testing and optimization of processes relevant in industrial and research contexts.

  20. Exposure of nickel and the relevance of nickel sensitivity among hospital cleaners

    Energy Technology Data Exchange (ETDEWEB)

    Clemmensen, O J; Menne, T; Kaaber, K; Solgaard, P

    1981-01-01

    The nickel content of water specimens from consecutive stages during the cleaning process in a Danish hospital was analyzed. Statistically significant increases of the nickel concentrations were found from step to step of the cleaning, eventually exceeding the theoretical sensitizing safety limit. The relevance of the findings in relation to hand eczema is discussed.

  1. Reaction rate of propene pyrolysis.

    Science.gov (United States)

    Han, Peipei; Su, Kehe; Liu, Yan; Wang, Yanli; Wang, Xin; Zeng, Qingfeng; Cheng, Laifei; Zhang, Litong

    2011-10-01

    The reaction rate of propene pyrolysis was investigated based on the elementary reactions proposed in Qu et al., J Comput Chem 2009, 31, 1421. The overall reaction rate was developed with the steady-state approximation and the rate constants of the elementary reactions were determined with the variational transition state theory. For the elementary reaction having transition state, the vibrational frequencies of the selected points along the minimum energy path were calculated with density functional theory at B3PW91/6-311G(d,p) level and the energies were improved with the accurate model chemistry method G3(MP2). For the elementary reaction without transition state, the frequencies were calculated with CASSCF/6-311G(d,p) and the energies were refined with the multireference configuration interaction method MRCISD/6-311G(d,p). The rate constants were evaluated within 200-2000 K and the fitted three-parameter expressions were obtained. The results are consistent with those in the literatures in most cases. For the overall rate, it was found that the logarithm of the rate and the reciprocal temperature have excellent linear relationship above 400 K, predicting that the rate follows a typical first-order law at high temperatures of 800-2000 K, which is also consistent with the experiments. The apparent activation energy in 800-2000 K is 317.3 kJ/mol from the potential energy surface of zero Kelvin. This value is comparable with the energy barriers, 365.4 and 403.7 kJ/mol, of the rate control steps. However, the apparent activation energy, 215.7 kJ/mol, developed with the Gibbs free energy surface at 1200 K is consistent with the most recent experimental result 201.9 ± 0.6 kJ/mol. Copyright © 2011 Wiley Periodicals, Inc.

  2. Effect of Heterogeneous Chemical Reactions on the Köhler Activation of Aqueous Organic Aerosols.

    Science.gov (United States)

    Djikaev, Yuri S; Ruckenstein, Eli

    2018-05-03

    We study some thermodynamic aspects of the activation of aqueous organic aerosols into cloud droplets considering the aerosols to consist of liquid solution of water and hydrophilic and hydrophobic organic compounds, taking into account the presence of reactive species in the air. The hydrophobic (surfactant) organic molecules on the surface of such an aerosol can be processed by chemical reactions with some atmospheric species; this affects the hygroscopicity of the aerosol and hence its ability to become a cloud droplet either via nucleation or via Köhler activation. The most probable pathway of such processing involves atmospheric hydroxyl radicals that abstract hydrogen atoms from hydrophobic organic molecules located on the aerosol surface (first step), the resulting radicals being quickly oxidized by ubiquitous atmospheric oxygen molecules to produce surface-bound peroxyl radicals (second step). These two reactions play a crucial role in the enhancement of the Köhler activation of the aerosol and its evolution into a cloud droplet. Taking them and a third reaction (next in the multistep chain of relevant heterogeneous reactions) into account, one can derive an explicit expression for the free energy of formation of a four-component aqueous droplet on a ternary aqueous organic aerosol as a function of four independent variables of state of a droplet. The results of numerical calculations suggest that the formation of cloud droplets on such (aqueous hydrophilic/hydrophobic organic) aerosols is most likely to occur as a Köhler activation-like process rather than via nucleation. The model allows one to determine the threshold parameters of the system necessary for the Köhler activation of such aerosols, which are predicted to be very sensitive to the equilibrium constant of the chain of three heterogeneous reactions involved in the chemical aging of aerosols.

  3. Determining Annealing Temperatures for Polymerase Chain Reaction

    Science.gov (United States)

    Porta, Angela R.; Enners, Edward

    2012-01-01

    The polymerase chain reaction (PCR) is a common technique used in high school and undergraduate science teaching. Students often do not fully comprehend the underlying principles of the technique and how optimization of the protocol affects the outcome and analysis. In this molecular biology laboratory, students learn the steps of PCR with an…

  4. Statistical theory of neutron-nuclear reactions

    International Nuclear Information System (INIS)

    Moldauer, P.A.

    1981-01-01

    In addition to the topics dealt with by the author in his lectures at the Joint IAEA/ICTP Course held at Trieste in 1978, recent developments in the statistical theory of multistep reactions are reviewed as well as the transport theory and intranuclear cascade approaches to the description of nuclear multi-step processes. (author)

  5. The Improved Relevance Voxel Machine

    DEFF Research Database (Denmark)

    Ganz, Melanie; Sabuncu, Mert; Van Leemput, Koen

    The concept of sparse Bayesian learning has received much attention in the machine learning literature as a means of achieving parsimonious representations of features used in regression and classification. It is an important family of algorithms for sparse signal recovery and compressed sensing....... Hence in its current form it is reminiscent of a greedy forward feature selection algorithm. In this report, we aim to solve the problems of the original RVoxM algorithm in the spirit of [7] (FastRVM).We call the new algorithm Improved Relevance Voxel Machine (IRVoxM). Our contributions...... and enables basis selection from overcomplete dictionaries. One of the trailblazers of Bayesian learning is MacKay who already worked on the topic in his PhD thesis in 1992 [1]. Later on Tipping and Bishop developed the concept of sparse Bayesian learning [2, 3] and Tipping published the Relevance Vector...

  6. Reverse transcriptase-quantitative polymerase chain reaction (RT ...

    African Journals Online (AJOL)

    zino

    2014-02-05

    Feb 5, 2014 ... ecological studies - A review ... The objective of this review is to assess the importance of RT-qPCR in soil related ... phenol extraction step with heat inactivation of the added .... Real time polymerase chain reaction (PCR).

  7. Synthesis of conformationally constrained peptidomimetics using multicomponent reactions

    NARCIS (Netherlands)

    Scheffelaar, R.; Klein Nijenhuis, R.A.; Paravidino, M.; Lutz, M.; Spek, A.L.; Ehlers, A.W.; de Kanter, F.J.J.; Groen, M.B.; Orru, R.V.A.; Ruijter, E.

    2009-01-01

    A novel modular synthetic approach toward constrained peptidomimetics is reported. The approach involves a highly efficient three-step sequence including two multicomponent reactions, thus allowing unprecedented diversification of both the peptide moieties and the turn-inducing scaffold. The

  8. Step-By-Step: Life Cycle Radioactive Waste Management

    International Nuclear Information System (INIS)

    2014-01-01

    Radioactive waste is an unavoidable by-product when nuclear technologies are used for electricity production and for beneficial practices in medicine, agriculture, research and industry. When the radioactivity of the waste is above a certain threshold, the waste requires special disposal methods. Through extensive research, standards and approaches have been developed for safely and securely preparing for and managing radioactive waste disposal. In the course of its journey from the point of generation to disposal, radioactive waste undergoes a number of predisposal management treatment steps to transform it into a safe, stable and manageable form suitable for transport, storage and disposal

  9. Blogging business step-by-step startup guide

    CERN Document Server

    magazine, Entrepreneur

    2014-01-01

    This kit includes: Essential industry and business-specific startup steps with worksheets, calculators, checklists and more. Entrepreneur Editors' Start Your Own Business, a guide to starting any business and surviving the first three years. Downloadable, customizable business letters, sales letters, and other sample documents. Entrepreneur's Small Business Legal Toolkit. Blogs are still one of the internet's fastest-growing phenomena–and one of the best and easiest ways to make money online. Packed with the latest blog tools, tricks, and up-and-coming trends, this fully revised edition teache

  10. Improving Urogenital Function with Step Training after Spinal Cord Injury

    Science.gov (United States)

    2016-10-01

    closed with suture, the skin closed with Michel clips, and topical antibiotic applied. Animals were single housed on a 12 : 12 light : dark cycle. 2.2...dysfunction are among the highest priorities after injury, yet few studies are being done. Our study uses a clinically relevant chronic SCI animal ...participants that step training can have beneficial outcomes on bladder maintenance, including polyuria (over- production of urine resulting in the need to

  11. Robotic retroperitoneal partial nephrectomy: a step-by-step guide.

    Science.gov (United States)

    Ghani, Khurshid R; Porter, James; Menon, Mani; Rogers, Craig

    2014-08-01

    To describe a step-by-step guide for successful implementation of the retroperitoneal approach to robotic partial nephrectomy (RPN) PATIENTS AND METHODS: The patient is placed in the flank position and the table fully flexed to increase the space between the 12th rib and iliac crest. Access to the retroperitoneal space is obtained using a balloon-dilating device. Ports include a 12-mm camera port, two 8-mm robotic ports and a 12-mm assistant port placed in the anterior axillary line cephalad to the anterior superior iliac spine, and 7-8 cm caudal to the ipsilateral robotic port. Positioning and port placement strategies for successful technique include: (i) Docking robot directly over the patient's head parallel to the spine; (ii) incision for camera port ≈1.9 cm (1 fingerbreadth) above the iliac crest, lateral to the triangle of Petit; (iii) Seldinger technique insertion of kidney-shaped balloon dilator into retroperitoneal space; (iv) Maximising distance between all ports; (v) Ensuring camera arm is placed in the outer part of the 'sweet spot'. The retroperitoneal approach to RPN permits direct access to the renal hilum, no need for bowel mobilisation and excellent visualisation of posteriorly located tumours. © 2014 The Authors. BJU International © 2014 BJU International.

  12. Mechanisms of inorganic and organometallic reactions

    CERN Document Server

    The purpose of this series is to provide a continuing critical review of the literature concerned with mechanistic aspects of inorganic and organo­ metallic reactions in solution, with coverage being complete in each volume. The papers discussed are selected on the basis of relevance to the elucidation of reaction mechanisms and many include results of a nonkinetic nature when useful mechanistic information can be deduced. The period of literature covered by this volume is July 1982 through December 1983, and in some instances papers not available for inclusion in the previous volume are also included. Numerical results are usually reported in the units used by the original authors, except where data from different papers are com­ pared and conversion to common units is necessary. As in previous volumes material included covers the major areas of redox processes, reactions of the nonmetallic elements, reaction of inert and labile metal complexes and the reactions of organometallic compounds. While m...

  13. Modeling the reactions catalyzed by coenzyme B12-dependent enzymes.

    Science.gov (United States)

    Sandala, Gregory M; Smith, David M; Radom, Leo

    2010-05-18

    Enzymes accelerate chemical reactions with an exceptional selectivity that makes life itself possible. Understanding the factors responsible for this efficient catalysis is of utmost importance in our quest to harness the tremendous power of enzymes. Computational chemistry has emerged as an important adjunct to experimental chemistry and biochemistry in this regard, because it provides detailed insights into the relationship between structure and function in a systematic and straightforward manner. In this Account, we highlight our recent high-level theoretical investigations toward this end in studying the radical-based reactions catalyzed by enzymes dependent on coenzyme B(12) (or adenosylcobalamin, AdoCbl). In addition to their fundamental position in biology, the AdoCbl-dependent enzymes represent a valuable framework within which to understand Nature's method of efficiently handling high-energy species to execute very specific reactions. The AdoCbl-mediated reactions are characterized by the interchange of a hydrogen atom and a functional group on adjacent carbon atoms. Our calculations are consistent with the conclusion that the main role of AdoCbl is to provide a source of radicals, thus moving the 1,2-rearrangements onto the radical potential energy surface. Our studies also show that the radical rearrangement step is facilitated by partial proton transfer involving the substrate. Specifically, we observe that the energy requirements for radical rearrangement are reduced dramatically with appropriate partial protonation or partial deprotonation or sometimes (synergistically) both. Such interactions are particularly relevant to enzyme catalysis, because it is likely that the local amino acid environment in the active site of an enzyme can function in this capacity through hydrogen bonding. Finally, our calculations indicate that the intervention of a very stable radical along the reaction pathway may inactivate the enzyme, demonstrating that sustained

  14. Improved predictions of nuclear reaction rates with the TALYS reaction code for astrophysical applications

    International Nuclear Information System (INIS)

    Goriely, S.; Hilaire, S.; Koning, A.J

    2008-01-01

    Context. Nuclear reaction rates of astrophysical applications are traditionally determined on the basis of Hauser-Feshbach reaction codes. These codes adopt a number of approximations that have never been tested, such as a simplified width fluctuation correction, the neglect of delayed or multiple-particle emission during the electromagnetic decay cascade, or the absence of the pre-equilibrium contribution at increasing incident energies. Aims. The reaction code TALYS has been recently updated to estimate the Maxwellian-averaged reaction rates that are of astrophysical relevance. These new developments enable the reaction rates to be calculated with increased accuracy and reliability and the approximations of previous codes to be investigated. Methods. The TALYS predictions for the thermonuclear rates of relevance to astrophysics are detailed and compared with those derived by widely-used codes for the same nuclear ingredients. Results. It is shown that TALYS predictions may differ significantly from those of previous codes, in particular for nuclei for which no or little nuclear data is available. The pre-equilibrium process is shown to influence the astrophysics rates of exotic neutron-rich nuclei significantly. For the first time, the Maxwellian- averaged (n, 2n) reaction rate is calculated for all nuclei and its competition with the radiative capture rate is discussed. Conclusions. The TALYS code provides a new tool to estimate all nuclear reaction rates of relevance to astrophysics with improved accuracy and reliability. (authors)

  15. Multicomponent Reactions in Ligation and Bioconjugation Chemistry.

    Science.gov (United States)

    Reguera, Leslie; Méndez, Yanira; Humpierre, Ana R; Valdés, Oscar; Rivera, Daniel G

    2018-05-25

    Multicomponent reactions (MCRs) encompass an exciting class of chemical transformations that have proven success in almost all fields of synthetic organic chemistry. These convergent procedures incorporate three or more reactants into a final product in one pot, thus combining high levels of complexity and diversity generation with low synthetic cost. Striking applications of these processes are found in heterocycle, peptidomimetic, and natural product syntheses. However, their potential in the preparation of large macro- and biomolecular constructs has been realized just recently. This Account describes the most relevant results of our group in the utilization of MCRs for ligation/conjugation of biomolecules along with significant contributions from other laboratories that validate the utility of this special class of bioconjugation process. Thus, MCRs have proven to be efficient in the ligation of lipids to peptides and oligosaccharides as well as the ligation of steroids, carbohydrates, and fluorescent and affinity tags to peptides and proteins. In the field of glycolipids, we highlight the power of isocyanide-based MCRs with the one-pot double lipidation of glycan fragments functionalized as either the carboxylic acid or amine. In peptide chemistry, the versatility of the multicomponent ligation strategy is demonstrated in both solution-phase lipidation protocols and solid-phase procedures enabling the simultaneous lipidation and biotinylation of peptides. In addition, we show that MCRs are powerful methods for synchronized lipidation/labeling and macrocyclization of peptides, thus accomplishing in one step what usually requires long sequences. In the realm of protein bioconjugation, MCRs have also proven to be effective in labeling, site-selective modification, immobilization, and glycoconjugation processes. For example, we illustrate a successful application of multicomponent polysaccharide-protein conjugation with the preparation of multivalent

  16. Reaction dynamics in polyatomic molecular systems

    Energy Technology Data Exchange (ETDEWEB)

    Miller, W.H. [Lawrence Berkeley Laboratory, CA (United States)

    1993-12-01

    The goal of this program is the development of theoretical methods and models for describing the dynamics of chemical reactions, with specific interest for application to polyatomic molecular systems of special interest and relevance. There is interest in developing the most rigorous possible theoretical approaches and also in more approximate treatments that are more readily applicable to complex systems.

  17. Microdosing: Concept, application and relevance

    Directory of Open Access Journals (Sweden)

    Tushar Tewari

    2010-01-01

    Full Text Available The use of microdose pharmacokinetic studies as an essential tool in drug development is still to catch on. While this approach promises potential cost savings and a quantum leap in efficiencies of the drug development process, major hurdles still need to be overcome before the technique becomes commonplace and part of routine practice. Clear regulations in Europe and the USA have had an enabling effect. The lack of enabling provisions for microdosing studies in Indian regulation, despite low risk and manifest relevance for the local drug development industry, is inconsistent with the country′s aspirations to be among the leaders in pharmaceutical research.

  18. Steps in Researching the Music in Therapy

    DEFF Research Database (Denmark)

    Bonde, Lars Ole

    2007-01-01

    The chapter introduces a generic flowchart + step-by-step guide for microanalysis of music (compositions and improvisations) in music therapy.......The chapter introduces a generic flowchart + step-by-step guide for microanalysis of music (compositions and improvisations) in music therapy....

  19. Nuclear Astrophysics and Neutron Induced Reactions: Quasi-Free Reactions and RIBs

    International Nuclear Information System (INIS)

    Cherubini, S.; Spitaleri, C.; Crucilla, V.; Gulino, M.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Puglia, S.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Coc, A.; Kubono, S.; Binh, D. N.; Hayakawa, S.; Wakabayashi, Y.; Yamaguchi, H.; Burjan, V.; Kroha, V.; De Sereville, N.

    2010-01-01

    The use of quasi-free reactions in studying nuclear reactions between charged particles of astrophysical interest has received much attention over the last two decades. The Trojan Horse Method is based on this approach and it has been used to study a number of reactions relevant for Nuclear Astrophysics. Recently we applied this method to the study of nuclear reactions that involve radioactive species, namely to the study of the 18 F+p→ 15 O+α process at temperatures corresponding to the energies available in the classical novae scenario. Quasi-free reactions can also be exploited to study processes induced by neutrons. This technique is particularly interesting when applied to reaction induced by neutrons on unstable short-lived nuclei. Such processes are very important in the nucleosynthesis of elements in the sand r-processes scenarios and this technique can give hints for solving key questions in nuclear astrophysics where direct measurements are practically impossible.

  20. Sub-step methodology for coupled Monte Carlo depletion and thermal hydraulic codes

    International Nuclear Information System (INIS)

    Kotlyar, D.; Shwageraus, E.

    2016-01-01

    Highlights: • Discretization of time in coupled MC codes determines the results’ accuracy. • The error is due to lack of information regarding the time-dependent reaction rates. • The proposed sub-step method considerably reduces the time discretization error. • No additional MC transport solutions are required within the time step. • The reaction rates are varied as functions of nuclide densities and TH conditions. - Abstract: The governing procedure in coupled Monte Carlo (MC) codes relies on discretization of the simulation time into time steps. Typically, the MC transport solution at discrete points will generate reaction rates, which in most codes are assumed to be constant within the time step. This assumption can trigger numerical instabilities or result in a loss of accuracy, which, in turn, would require reducing the time steps size. This paper focuses on reducing the time discretization error without requiring additional MC transport solutions and hence with no major computational overhead. The sub-step method presented here accounts for the reaction rate variation due to the variation in nuclide densities and thermal hydraulic (TH) conditions. This is achieved by performing additional depletion and TH calculations within the analyzed time step. The method was implemented in BGCore code and subsequently used to analyze a series of test cases. The results indicate that computational speedup of up to a factor of 10 may be achieved over the existing coupling schemes.

  1. The relevance of "non-relevant metabolites" from plant protection products (PPPs) for drinking water: the German view.

    Science.gov (United States)

    Dieter, Hermann H

    2010-03-01

    evaluation of a "non-relevant metabolite", its HRIV is either set as 1.0 microg/l (HRIV(a)) or as 3.0 microg/l (HRIV(b)) for lifelong exposure. In case a HRIV would be exceeded, UBA recommends to keep on a precautionary action value (PAV) of 10 microg/l for each "non-relevant metabolite". The HRIV(b) is similar to the maximal value derived by application of the TTC-concept for Cramer Class III (4.5 microg/l). The HRIV(a) and the PAV are similar to values in the EU-guidance document for assessing "non-relevant metabolites" in ground water, with the important difference that the drinking water PAV is not intended to be tolerated for permanent exposure. Drinking water containing "non-relevant metabolites" below the respective HRIVs can also be considered as being sufficiently protective against toxicologically relevant oxidative transformation products which may be formed from "non-relevant metabolites" during drinking water treatment with ozone. However, even drinking water where one or several "non-relevant metabolites" are detected above substance-specific HRIVs is suited for human consumption without health risks. Only in special cases (relatively high "non-relevant metabolite" - concentrations), it could be indicated to examine the finished water for transformation products after treatment with ozone if there are no further treatment steps to eliminate or degrade polar compounds. UBA's "non-relevant metabolite-Recommendation" from April 2008 was positively picked up in 2009 by four important stakeholders in the domain of drinking water management as part of a voluntary cooperation agreement. The aim of such cooperation is to limit the transport of "non-relevant metabolites" into the drinking water to the functionally (and agriculturally) unavoidable extent and insofar to meet special precautionary demands. (c) 2009 Elsevier Inc. All rights reserved.

  2. Atomic Step Formation on Sapphire Surface in Ultra-precision Manufacturing

    Science.gov (United States)

    Wang, Rongrong; Guo, Dan; Xie, Guoxin; Pan, Guoshun

    2016-01-01

    Surfaces with controlled atomic step structures as substrates are highly relevant to desirable performances of materials grown on them, such as light emitting diode (LED) epitaxial layers, nanotubes and nanoribbons. However, very limited attention has been paid to the step formation in manufacturing process. In the present work, investigations have been conducted into this step formation mechanism on the sapphire c (0001) surface by using both experiments and simulations. The step evolutions at different stages in the polishing process were investigated with atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM). The simulation of idealized steps was constructed theoretically on the basis of experimental results. It was found that (1) the subtle atomic structures (e.g., steps with different sawteeth, as well as steps with straight and zigzag edges), (2) the periodicity and (3) the degree of order of the steps were all dependent on surface composition and miscut direction (step edge direction). A comparison between experimental results and idealized step models of different surface compositions has been made. It has been found that the structure on the polished surface was in accordance with some surface compositions (the model of single-atom steps: Al steps or O steps). PMID:27444267

  3. Lateral step initiation behavior in older adults

    OpenAIRE

    Sparto, Patrick J; Jennings, J Richard; Furman, Joseph M; Redfern, Mark S

    2013-01-01

    Older adults have varied postural responses during induced and voluntary lateral stepping. The purpose of the research was to quantify the occurrence of different stepping strategies during lateral step initiation in older adults and to relate the stepping responses to retrospective history of falls. Seventy community-ambulating older adults (mean age 76 y, range 70–94 y) performed voluntary lateral steps as quickly as possible to the right or left in response to a visual cue, in a blocked de...

  4. Competition Between Hydrotreating and Polymerization Reactions During Pyrolysis Oil Hydrodeoxygenation

    NARCIS (Netherlands)

    Mercader, F. De Miguel; Koehorst, P. J. J.; Heeres, H. J.; Kersten, S. R. A.; Hogendoorn, J. A.

    2011-01-01

    Hydrodeoxygenation (HDO) of pyrolysis oil is an upgrading step that allows further coprocessing of the oil product in (laboratory-scale) standard refinery units to produce advanced biofuels. During HDO, desired hydrotreating reactions are in competition with polymerization reactions that can lead to

  5. Unconventional Passerini Reaction toward α-Aminoxy-amides

    NARCIS (Netherlands)

    Chandgude, Ajay L; Dömling, Alexander

    2016-01-01

    The Passerini multicomponent reaction (P-3CR) toward the one-step synthesis of α-aminoxy-amide, by employing for the first time a N-hydroxamic acid component, has been reported. The sonication-accelerated, catalyst-free, simple, fast, and highly efficient Passerini reaction is used for the synthesis

  6. Propargylamine-isothiocyanate reaction: efficient conjugation chemistry in aqueous media

    DEFF Research Database (Denmark)

    Viart, Helene Marie-France; Larsen, T. S.; Tassone, Chiara

    2014-01-01

    A coupling reaction between secondary propargyl amines and isothiocyanates in aqueous media is described. The reaction is high-yielding and affords cyclized products within 2-24 h. A functionalized ether lipid was synthesized in 8 steps, formulated as liposomes with POPC and conjugated to FITC un...

  7. Biomechanical influences on balance recovery by stepping.

    Science.gov (United States)

    Hsiao, E T; Robinovitch, S N

    1999-10-01

    Stepping represents a common means for balance recovery after a perturbation to upright posture. Yet little is known regarding the biomechanical factors which determine whether a step succeeds in preventing a fall. In the present study, we developed a simple pendulum-spring model of balance recovery by stepping, and used this to assess how step length and step contact time influence the effort (leg contact force) and feasibility of balance recovery by stepping. We then compared model predictions of step characteristics which minimize leg contact force to experimentally observed values over a range of perturbation strengths. At all perturbation levels, experimentally observed step execution times were higher than optimal, and step lengths were smaller than optimal. However, the predicted increase in leg contact force associated with these deviations was substantial only for large perturbations. Furthermore, increases in the strength of the perturbation caused subjects to take larger, quicker steps, which reduced their predicted leg contact force. We interpret these data to reflect young subjects' desire to minimize recovery effort, subject to neuromuscular constraints on step execution time and step length. Finally, our model predicts that successful balance recovery by stepping is governed by a coupling between step length, step execution time, and leg strength, so that the feasibility of balance recovery decreases unless declines in one capacity are offset by enhancements in the others. This suggests that one's risk for falls may be affected more by small but diffuse neuromuscular impairments than by larger impairment in a single motor capacity.

  8. Assessing the relevance of ecotoxicological studies for regulatory decision making.

    Science.gov (United States)

    Rudén, Christina; Adams, Julie; Ågerstrand, Marlene; Brock, Theo Cm; Poulsen, Veronique; Schlekat, Christian E; Wheeler, James R; Henry, Tala R

    2017-07-01

    Regulatory policies in many parts of the world recognize either the utility of or the mandate that all available studies be considered in environmental or ecological hazard and risk assessment (ERA) of chemicals, including studies from the peer-reviewed literature. Consequently, a vast array of different studies and data types need to be considered. The first steps in the evaluation process involve determining whether the study is relevant to the ERA and sufficiently reliable. Relevance evaluation is typically performed using existing guidance but involves application of "expert judgment" by risk assessors. In the present paper, we review published guidance for relevance evaluation and, on the basis of the practical experience within the group of authors, we identify additional aspects and further develop already proposed aspects that should be considered when conducting a relevance assessment for ecotoxicological studies. From a regulatory point of view, the overarching key aspect of relevance concerns the ability to directly or indirectly use the study in ERA with the purpose of addressing specific protection goals and ultimately regulatory decision making. Because ERA schemes are based on the appropriate linking of exposure and effect estimates, important features of ecotoxicological studies relate to exposure relevance and biological relevance. Exposure relevance addresses the representativeness of the test substance, environmental exposure media, and exposure regime. Biological relevance deals with the environmental significance of the test organism and the endpoints selected, the ecological realism of the test conditions simulated in the study, as well as a mechanistic link of treatment-related effects for endpoints to the protection goal identified in the ERA. In addition, uncertainties associated with relevance should be considered in the assessment. A systematic and transparent assessment of relevance is needed for regulatory decision making. The relevance

  9. Microbial reactions in coal and coal relevant structures. Part project: fungal and enzymatic depolarisation of brown coal for the production of low-molecular compounds. Interim report; Mikrobielle Umsetzung an Kohle und kohlenrelevanten Strukturen. Teilvorhaben: Pilzliche und enzymatische Depolymerisation von Braunkohle zur Gewinnung niedermolekularer Verbindungen. Zwischenbericht (Berichtszeitraum 01.01.1998 - 31.12.1998)

    Energy Technology Data Exchange (ETDEWEB)

    Ziegenhagen, D.; Bublitz, F.; Sorge, S.; Ullrich, R.; Hofrichter, M.; Fritsche, W.

    1999-04-29

    The present research project involved a study of the depolymerisation of brown coal constituents. The purpose of the depolymerisation experiments, which were carried out with fungi as well as their (acellular) enzymes, was to obtain products with a potential market value. Research focussed on one of the key enzymes of lignocellulose degradation, namely manganese (II) peroxidase (MnP). The effects of this enzyme on the depolymerisation of brown coal was studied in detail in acellular systems. The insights gained in this way then served as a basis for optimising the fungal and enzymatic depolymerisation processes for maximum yields of low-molecular products. The experiments carried out during the period under review were oriented to finding new types of lignolytically active organisms, isolating lignolytic enzymes and immobilising them on natural support materials, and further examining the action spectrum of MnP. Different model substrates were used in order to gain information on what bond types are MnP-cleavable and on possible reaction products. Substrates were either fixed to silica gel as support material or used without support material. The idea of using substrates fixed to support materials was motivated by the need to distinguish between intracellular and extracellular reactions involving the fungal mycelium. [Deutsch] Im Rahmen des Forschungsvorhabens wird die Depolymerisation von Braunkohle-Bestandteilen untersucht. Ziel der sowohl mit Pilzorganismen als auch mit deren Enzymen (zellfrei) durchgefuehrten Depolymerisationsversuche ist die Gewinnung von Produkten mit potentiellem Werkstoffcharakter. Im Mittelpunkt der Forschung steht eines der Schluesselenzyme des Ligninozellulose-Abbaus: Die Mangan(II)-Peroxidase (MnP). Die Wirkung dieses Enzyms bei der Depolymerisation von Braunkohle (Bk) in zellfreien Systemen wird weitergehend untersucht. Auf Grundlage der gewonnenen Erkenntnisse werden die pilzlichen und enzymatischen Depolymerisationsprozesse so

  10. Nuclear models relevant to evaluation

    International Nuclear Information System (INIS)

    Arthur, E.D.; Chadwick, M.B.; Hale, G.M.; Young, P.G.

    1991-01-01

    The widespread use of nuclear models continues in the creation of data evaluations. The reasons include extension of data evaluations to higher energies, creation of data libraries for isotopic components of natural materials, and production of evaluations for radiative target species. In these cases, experimental data are often sparse or nonexistent. As this trend continues, the nuclear models employed in evaluation work move towards more microscopically-based theoretical methods, prompted in part by the availability of increasingly powerful computational resources. Advances in nuclear models applicable to evaluation will be reviewed. These include advances in optical model theory, microscopic and phenomenological state and level density theory, unified models that consistently describe both equilibrium and nonequilibrium reaction mechanism, and improved methodologies for calculation of prompt radiation from fission. 84 refs., 8 figs

  11. The structure of stepped surfaces

    International Nuclear Information System (INIS)

    Algra, A.J.

    1981-01-01

    The state-of-the-art of Low Energy Ion Scattering (LEIS) as far as multiple scattering effects are concerned, is discussed. The ion fractions of lithium, sodium and potassium scattered from a copper (100) surface have been measured as a function of several experimental parameters. The ratio of the intensities of the single and double scattering peaks observed in ion scattering spectroscopy has been determined and ion scattering spectroscopy applied in the multiple scattering mode is used to determine the structure of a stepped Cu(410) surface. The average relaxation of the (100) terraces of this surface appears to be very small. The adsorption of oxygen on this surface has been studied with LEIS and it is indicated that oxygen absorbs dissociatively. (C.F.)

  12. A step toward nuclear sanity

    International Nuclear Information System (INIS)

    Gottfried, K.; Long, F.

    1988-01-01

    This paper reports that Reykjavik formally ended as a diplomatic failure, but it has begun an overdue revolution in perceptions. At long last, both superpowers have the in concrete terms that vastly smaller nuclear arsenals would make them safer. Implicitly, they are saying that nuclear weapons are not useful weapons. Those insights are a prerequisite to nuclear sanity. The United States has proposed to eliminate all strategic ballistic missiles, on land and submarines, in two five-year steps. During that period, we (and presumably the Soviet Union) would develop missile defenses to be deployed in ten years. The first part of this plan makes excellent sense. Ballistic missiles explode on their targets ten to thirty minutes after launch. Today's huge and accurate missile arsenals have forced both superpowers to adopt a hair-trigger stance: they might launch missiles simply on warning of attack

  13. Boris push with spatial stepping

    International Nuclear Information System (INIS)

    Penn, G; Stoltz, P H; Cary, J R; Wurtele, J

    2003-01-01

    The Boris push is commonly used in plasma physics simulations because of its speed and stability. It is second-order accurate, requires only one field evaluation per time step, and has good conservation properties. However, for accelerator simulations it is convenient to propagate particles in z down a changing beamline. A 'spatial Boris push' algorithm has been developed which is similar to the Boris push but uses a spatial coordinate as the independent variable, instead of time. This scheme is compared to the fourth-order Runge-Kutta algorithm, for two simplified muon beam lattices: a uniform solenoid field, and a 'FOFO' lattice where the solenoid field varies sinusoidally along the axis. Examination of the canonical angular momentum, which should be conserved in axisymmetric systems, shows that the spatial Boris push improves accuracy over long distances

  14. Treatment and Managing Reactions

    Science.gov (United States)

    ... of reactions. Learn more here. Milk Egg Peanut Tree Nuts Soy Wheat Fish Shellfish Sesame Other Food ... a severe reaction. Consider wearing an emergency medical identification (e.g., bracelet, other jewelry). What to Read ...

  15. Microfluidic chemical reaction circuits

    Science.gov (United States)

    Lee, Chung-cheng [Irvine, CA; Sui, Guodong [Los Angeles, CA; Elizarov, Arkadij [Valley Village, CA; Kolb, Hartmuth C [Playa del Rey, CA; Huang, Jiang [San Jose, CA; Heath, James R [South Pasadena, CA; Phelps, Michael E [Los Angeles, CA; Quake, Stephen R [Stanford, CA; Tseng, Hsian-rong [Los Angeles, CA; Wyatt, Paul [Tipperary, IE; Daridon, Antoine [Mont-Sur-Rolle, CH

    2012-06-26

    New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

  16. Preequilibrium Nuclear Reactions

    International Nuclear Information System (INIS)

    Strohmaier, B.

    1988-01-01

    After a survey on existing experimental data on precompound reactions and a description of preequilibrium reactions, theoretical models and quantum mechanical theories of preequilibrium emission are presented. The 25 papers of this meeting are analyzed separately

  17. Managing Your Emotional Reactions

    Science.gov (United States)

    ... Videos for Educators Search English Español Managing Your Emotional Reactions KidsHealth / For Teens / Managing Your Emotional Reactions ... Think about what you might do next time. Emotions 101 The skills we use to manage our ...

  18. Heavy ion transfer reactions

    Indian Academy of Sciences (India)

    array (CLARA), extensive investigations of nuclear structure and reaction dynamics have been carried out. In the present paper aspects of these studies will be presented, focussing more closely on the reaction mechanism, in particular on the ...

  19. Other relevant numerical modelling papers

    International Nuclear Information System (INIS)

    Chartier, M.

    1989-01-01

    The ocean modelling is a rapidly evolving science and a large number of results have been published. Several categories of papers are of particular interest for this review: the papers published by the international atomic institutions, such as the NEA (for the CRESP or Subseabed Programs), the IAEA (for example the Safety Series, the Technical Report Series or the TECDOC), and the ICRP, and the papers concerned by more fundamental research, which are published in specific scientific literature. This paper aims to list some of the most relevant publications for the CRESP purposes. It means by no way to be exhaustive, but informative on the incontestable progress recently achieved in that field. One should note that some of these papers are so recent that their final version has not yet been published

  20. Industrial relevance of thermophilic Archaea.

    Science.gov (United States)

    Egorova, Ksenia; Antranikian, Garabed

    2005-12-01

    The dramatic increase of newly isolated extremophilic microorganisms, analysis of their genomes and investigations of their enzymes by academic and industrial laboratories demonstrate the great potential of extremophiles in industrial (white) biotechnology. Enzymes derived from extremophiles (extremozymes) are superior to the traditional catalysts because they can perform industrial processes even under harsh conditions, under which conventional proteins are completely denatured. In particular, enzymes from thermophilic and hyperthermophilic Archaea have industrial relevance. Despite intensive investigations, our knowledge of the structure-function relationships of their enzymes is still limited. Information concerning the molecular properties of their enzymes and genes has to be obtained to be able to understand the mechanisms that are responsible for catalytic activity and stability at the boiling point of water.

  1. The Relevance of Hegel's Logic

    Directory of Open Access Journals (Sweden)

    John W Burbidge

    2007-12-01

    Full Text Available Hegel defines his Logic as the science that thinks about thinking.nbsp; But when we interpret that work as outlining what happens when we reason we are vulnerable to Fregersquo;s charge of psychologism.nbsp; I use Hegelrsquo;s tripartite distinction among understanding, dialectical and speculative reason as operations of pure thought to suggest how thinking can work with objective concepts.nbsp; In the last analysis, however, our ability to move from the subjective contingency of representations and ideas to the pure concepts we think develops from mechanical memory, which separates sign from sense so hat we can focus simply on the latter.nbsp; By becoming aware of the connections that underlie our thinking processes we may be able to both move beyond the abstractions of symbolic logic and clarify what informal logicians call relevance.

  2. A method for measuring light ion reaction cross sections

    International Nuclear Information System (INIS)

    Carlson, R.F.; Ingemarsson, A.; Lantz, M.

    2005-03-01

    An experimental procedure for measuring reaction cross sections of light ions in the energy range 20-50 MeV/nucleon, using a modified attenuation technique, is described. The detection method incorporates a forward detector that simultaneously measures the reaction cross sections for five different sizes of the solid angles in steps from 99.1 to 99.8% of the total solid angle. The final reaction cross section values are obtained by extrapolation to the full solid angle

  3. Step Prediction During Perturbed Standing Using Center Of Pressure Measurements

    Directory of Open Access Journals (Sweden)

    Milos R. Popovic

    2007-04-01

    Full Text Available The development of a sensor that can measure balance during quiet standing and predict stepping response in the event of perturbation has many clinically relevant applica- tions, including closed-loop control of a neuroprothesis for standing. This study investigated the feasibility of an algorithm that can predict in real-time when an able-bodied individual who is quietly standing will have to make a step to compensate for an external perturbation. Anterior and posterior perturbations were performed on 16 able-bodied subjects using a pul- ley system with a dropped weight. A linear relationship was found between the peak center of pressure (COP velocity and the peak COP displacement caused by the perturbation. This result suggests that one can predict when a person will have to make a step based on COP velocity measurements alone. Another important feature of this finding is that the peak COP velocity occurs considerably before the peak COP displacement. As a result, one can predict if a subject will have to make a step in response to a perturbation sufficiently ahead of the time when the subject is actually forced to make the step. The proposed instability detection algorithm will be implemented in a sensor system using insole sheets in shoes with minitur- ized pressure sensors by which the COPv can be continuously measured. The sensor system will be integrated in a closed-loop feedback system with a neuroprosthesis for standing in the near future.

  4. Chemical transport reactions

    CERN Document Server

    Schäfer, Harald

    2013-01-01

    Chemical Transport Reactions focuses on the processes and reactions involved in the transport of solid or liquid substances to form vapor phase reaction products. The publication first offers information on experimental and theoretical principles and the transport of solid substances and its special applications. Discussions focus on calculation of the transport effect of heterogeneous equilibria for a gas motion between equilibrium spaces; transport effect and the thermodynamic quantities of the transport reaction; separation and purification of substances by means of material transport; and

  5. Fluorination reaction uranium dioxide by fluorine

    International Nuclear Information System (INIS)

    Ogata, Shinji; Homma, Shunji; Koga, Jiro; Matsumoto, Shiro; Sasahira, Akira; Kawamura, Fumio

    2004-01-01

    Kinetics of the fluorination reaction of uranium dioxide is studied using un-reacted core model with shrinking particles. The model includes the film mass transfer of fluorine gas and its diffusion in the particle. The rate constants of the model are determined by fitting the experimental data for 370-450degC. The model successfully represents the fluorination in this temperature range. The rate control step is identified by examining the rate constants of the model for 300-1,800degC. For temperature range up to 900degC, the fluorination reaction is rate controlling. For over 900degC, both mechanisms of the mass transfer of fluorine and the fluorination reaction control the rate of the fluorination. With further increase of the temperature, however, the fluorination reaction becomes so fast that the mass transfer of fluorine eventually controls the rate of the fluorination. (author)

  6. Preimages for Step-Reduced SHA-2

    DEFF Research Database (Denmark)

    Aoki, Kazumaro; Guo, Jian; Matusiewicz, Krystian

    2009-01-01

    In this paper, we present preimage attacks on up to 43-step SHA-256 (around 67% of the total 64 steps) and 46-step SHA-512 (around 57.5% of the total 80 steps), which significantly increases the number of attacked steps compared to the best previously published preimage attack working for 24 steps....... The time complexities are 2^251.9, 2^509 for finding pseudo-preimages and 2^254.9, 2^511.5 compression function operations for full preimages. The memory requirements are modest, around 2^6 words for 43-step SHA-256 and 46-step SHA-512. The pseudo-preimage attack also applies to 43-step SHA-224 and SHA-384...

  7. Thermonuclear reaction rates. III

    International Nuclear Information System (INIS)

    Harris, M.J.; Fowler, W.A.; Caughlan, G.R.; Zimmerman, B.A.

    1983-01-01

    Stellar thermonuclear reaction rates are revised and updated, adding a number of new important reaction rates. Several reactions with large negative Q-values are included, and examples of them are discussed. The importance of the decay rates for Mg-26(p,n) exp 26 Al and Al-26(n,p) exp 26 Mg for stellar studies is emphasized. 19 references

  8. Maillard Reaction: review

    Directory of Open Access Journals (Sweden)

    Júlia d'Almeida Francisquini

    2017-11-01

    Full Text Available Maillard reaction is an important subject of study in food science and technology and different areas of knowledge are involved such as chemistry, food engineering, nutrition and food technology. The objective of this paper is to present the basic concepts of the Maillard reaction, such as the reaction stages, the main compounds producced and some technological consequences for dairy products.

  9. Resonant thermonuclear reaction rate

    International Nuclear Information System (INIS)

    Haubold, H.J.; Mathai, A.M.

    1986-01-01

    Basic physical principles for the resonant and nonresonant thermonuclear reaction rates are applied to find their standard representations for nuclear astrophysics. Closed-form representations for the resonant reaction rate are derived in terms of Meijer's G-function. Analytic representations of the resonant and nonresonant nuclear reaction rates are compared and the appearance of Meijer's G-function is discussed in physical terms

  10. Linking pedestrian flow characteristics with stepping locomotion

    Science.gov (United States)

    Wang, Jiayue; Boltes, Maik; Seyfried, Armin; Zhang, Jun; Ziemer, Verena; Weng, Wenguo

    2018-06-01

    While properties of human traffic flow are described by speed, density and flow, the locomotion of pedestrian is based on steps. To relate characteristics of human locomotor system with properties of human traffic flow, this paper aims to connect gait characteristics like step length, step frequency, swaying amplitude and synchronization with speed and density and thus to build a ground for advanced pedestrian models. For this aim, observational and experimental study on the single-file movement of pedestrians at different densities is conducted. Methods to measure step length, step frequency, swaying amplitude and step synchronization are proposed by means of trajectories of the head. Mathematical models for the relations of step length or frequency and speed are evaluated. The problem how step length and step duration are influenced by factors like body height and density is investigated. It is shown that the effect of body height on step length and step duration changes with density. Furthermore, two different types of step in-phase synchronization between two successive pedestrians are observed and the influence of step synchronization on step length is examined.

  11. Influence of step length and landing pattern on patellofemoral joint kinetics during running.

    Science.gov (United States)

    Willson, J D; Ratcliff, O M; Meardon, S A; Willy, R W

    2015-12-01

    Elevated patellofemoral joint kinetics during running may contribute to patellofemoral joint symptoms. The purpose of this study was to test for independent effects of foot strike pattern and step length on patellofemoral joint kinetics while running. Effects were tested relative to individual steps and also taking into account the number of steps required to run a kilometer with each step length. Patellofemoral joint reaction force and stress were estimated in 20 participants running at their preferred speed. Participants ran using a forefoot strike and rearfoot strike pattern during three different step length conditions: preferred step length, long (+10%) step length, and short (-10%) step length. Patellofemoral kinetics was estimated using a biomechanical model of the patellofemoral joint that accounted for cocontraction of the knee flexors and extensors. We observed independent effects of foot strike pattern and step length. Patellofemoral joint kinetics per step was 10-13% less during forefoot strike conditions and 15-20% less with a shortened step length. Patellofemoral joint kinetics per kilometer decreased 12-13% using a forefoot strike pattern and 9-12% with a shortened step length. To the extent that patellofemoral joint kinetics contribute to symptoms among runners, these running modifications may be advisable for runners with patellofemoral pain. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  12. Determination of the relevant market as a criterion of assessment of concentration effects in the practice of antitrust authorities

    Directory of Open Access Journals (Sweden)

    Daria Kostecka-Jurczyk

    2012-12-01

    Full Text Available Determining the relevant market is the first and the most important step in antimonopoly proceedings due to the fact that the market position of an enterprise is always determined from the relevant market perspective. In respect of mergers, establishing the relevant market is essential in analysing whether the aim of the concentration is to distort and limit competition on the market. The author of the article focuses on describing methods for determining the relevant market applied by antimonopoly authorities.

  13. Regulatory experiences from the spent fuel disposal step-wise implementation

    International Nuclear Information System (INIS)

    Heinonen, Jussi

    2016-01-01

    How to ensure regulatory readiness in different steps? Criteria for decision making: • Up-to-date safety requirements; • What is enough in this licensing step? Review strategy: • What is relevant in this licensing step?; • How to address (top-down or bottom-up review, own analysis, inspection)?Expertise: • Strategy for developing regulatory competences and resources; • Adapted to licensing step in question. Interaction with applicant: • important for mutual understanding; • Address main safety questions during pre-licensing – no surprises!

  14. Compiling the parallel programming language NestStep to the CELL processor

    OpenAIRE

    Holm, Magnus

    2010-01-01

    The goal of this project is to create a source-to-source compiler which will translate NestStep code to C code. The compiler's job is to replace NestStep constructs with a series of function calls to the NestStep runtime system. NestStep is a parallel programming language extension based on the BSP model. It adds constructs for parallel programming on top of an imperative programming language. For this project, only constructs extending the C language are relevant. The output code will compil...

  15. On the reaction of the nitroso group with olefins. Mechanisms of ene reactions

    International Nuclear Information System (INIS)

    Seymour, C.A.; Greene, F.D.

    1982-01-01

    Intra- and intermolecular isotope effects point to a two-step process for the reaction of pentafluoronitrosobenzene with tetramethylethylene to afford the ene product, rate-determining formation of an intermediate (for which the arizidine N-oxide is suggested) followed by C-H (or C-D) cleavage to the ene product

  16. Insights into the mechanisms on chemical reactions: reaction paths for chemical reactions

    International Nuclear Information System (INIS)

    Dunning, T.H. Jr.; Rosen, E.; Eades, R.A.

    1987-01-01

    We report reaction paths for two prototypical chemical reactions: Li + HF, an electron transfer reaction, and OH + H 2 , an abstraction reaction. In the first reaction we consider the connection between the energetic terms in the reaction path Hamiltonian and the electronic changes which occur upon reaction. In the second reaction we consider the treatment of vibrational effects in chemical reactions in the reaction path formalism. 30 refs., 9 figs

  17. One-step reduced kinetics for lean hydrogen-air deflagration

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez-Galisteo, D.; Sanchez, A.L. [Area de Mecanica de Fluidos, Univ. Carlos III de Madrid, Leganes 28911 (Spain); Linan, A. [ETSI Aeronauticos, Pl. Cardenal Cisneros 3, Madrid 28040 (Spain); Williams, F.A. [Dept. of Mechanical and Aerospace Engineering, University of California San Diego, La Jolla, CA 92093-0411 (United States)

    2009-05-15

    A short mechanism consisting of seven elementary reactions, of which only three are reversible, is shown to provide good predictions of hydrogen-air lean-flame burning velocities. This mechanism is further simplified by noting that over a range of conditions of practical interest, near the lean flammability limit all reaction intermediaries have small concentrations in the important thin reaction zone that controls the hydrogen-air laminar burning velocity and therefore follow a steady state approximation, while the main species react according to the global irreversible reaction 2H{sub 2} + O{sub 2} {yields} 2H{sub 2}O. An explicit expression for the non-Arrhenius rate of this one-step overall reaction for hydrogen oxidation is derived from the seven-step detailed mechanism, for application near the flammability limit. The one-step results are used to calculate flammability limits and burning velocities of planar deflagrations. Furthermore, implications concerning radical profiles in the deflagration and reasons for the success of the approximations are clarified. It is also demonstrated that adding only two irreversible direct recombination steps to the seven-step mechanism accurately reproduces burning velocities of the full detailed mechanism for all equivalence ratios at normal atmospheric conditions and that an eight-step detailed mechanism, constructed from the seven-step mechanism by adding to it the fourth reversible shuffle reaction, improves predictions of O and OH profiles. The new reduced-chemistry descriptions can be useful for both analytical and computational studies of lean hydrogen-air flames, decreasing required computation times. (author)

  18. Steps to Advanced CANDU 600

    International Nuclear Information System (INIS)

    Oh, Yongshick; Brooks, G. L.

    1988-01-01

    The CANDU nuclear power system was developed from merging of AECL heavy water reactor technology with Ontario Hydro electrical power station expertise. The original four units of Ontario Hydro's Pickering Generating Station are the first full-scale commercial application of the CANDU system. AECL and Ontario Hydro then moved to the next evolutionary step, a more advanced larger scale design for four units at the Bruce Generating Station. CANDU 600 followed as a single unit nuclear electric power station design derived from an amalgam of features of the multiple unit Pickering and Bruce designs. The design of the CANDU 600 nuclear steam supply system is based on the Pickering design with improvements derived from the Bruce design. For example, most CANDU 600 auxiliary systems are based on Bruce systems, whereas the fuel handling system is based on the Pickering system. Four CANDU 600 units are in operation, and five are under construction in Romania. For the additional four units at Pickering Generating Station 'B', Ontario Hydro selected a replica of the Pickering 'A' design with limited design changes to maintain a high level of standardization across all eight units. Ontario Hydro applied a similar policy for the additional four units at Bruce Generating Station 'B'. For the four unit Darlington station, Ontario Hydro selected a design based on Bruce with improvements derived from operating experience, the CANDU 600 design and development programs

  19. Vygotsky's Crisis: Argument, context, relevance.

    Science.gov (United States)

    Hyman, Ludmila

    2012-06-01

    Vygotsky's The Historical Significance of the Crisis in Psychology (1926-1927) is an important text in the history and philosophy of psychology that has only become available to scholars in 1982 in Russian, and in 1997 in English. The goal of this paper is to introduce Vygotsky's conception of psychology to a wider audience. I argue that Vygotsky's argument about the "crisis" in psychology and its resolution can be fully understood only in the context of his social and political thinking. Vygotsky shared the enthusiasm, widespread among Russian leftist intelligentsia in the 1920s, that Soviet society had launched an unprecedented social experiment: The socialist revolution opened the way for establishing social conditions that would let the individual flourish. For Vygotsky, this meant that "a new man" of the future would become "the first and only species in biology that would create itself." He envisioned psychology as a science that would serve this humanist teleology. I propose that The Crisis is relevant today insofar as it helps us define a fundamental problem: How can we systematically account for the development of knowledge in psychology? I evaluate how Vygotsky addresses this problem as a historian of the crisis. Copyright © 2011 Elsevier Ltd. All rights reserved.

  20. Are dinucleoside monophosphates relevant models for the study of DNA intrastrand cross-link lesions? The example of g[8-5m]T.

    Science.gov (United States)

    Garrec, Julian; Dumont, Elise

    2014-07-21

    Oxidatively generated tandem lesions such as G[8-5m]T pose a potent threat to genome integrity. Direct experimental studies of the kinetics and thermodynamics of a specific lesion within DNA are very challenging, mostly due to the variety of products that can be formed in oxidative conditions. Dinucleoside monophosphates (DM) involving only the reactive nucleobases in water represent appealing alternative models on which most physical chemistry and structural techniques can be applied. However, it is not yet clear how relevant these models are. Here, we present QM/MM MD simulations of the cyclization step involved in the formation of G[8-5m]T from the guanine-thymine (GpT) DM in water, with the aim of comparing our results to our previous investigation of the same reaction in DNA ( Garrec , J. , Patel , C. , Rothlisberger , U. , and Dumont , E. ( 2012 ) J. Am. Chem. Soc. 134 , 2111 - 2119 ). We show that, despite the different levels of preorganization of the two systems, the corresponding reactions share many energetic and structural characteristics. The main difference lies in the angle between the G and T bases, which is slightly higher in the transition state (TS) and product of the reaction in water than in the reaction in DNA. This effect is due to the Watson-Crick H-bonds, which are absent in the {GpT+water} system and restrain the relative positioning of the reactive nucleobases in DNA. However, since the lesion is accommodated easily in the DNA macromolecule, the induced energetic penalty is relatively small. The high similarity between the two reactions strongly supports the use of GpT in water as a model of the corresponding reaction in DNA.

  1. X-ray spectroscopic characterization of Co(IV) and metal–metal interactions in Co4O4: Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Hadt, Ryan G.; Hayes, Dugan; Brodsky, Casey N.; Ullman, Andrew M.; Casa, Diego M.; Upton, Mary H.; Nocera, Daniel G; Chen, Lin X.

    2016-08-12

    In this paper, the formation of high-valent states is a key factor in making highly active transition metal-based catalysts of the oxygen-evolving reaction (OER). These high oxidation states will be strongly influenced by the local geometric and electronic structures of the metal ion, which is difficult to study due to spectroscopically active and complex backgrounds, short lifetimes, and limited concentrations. Here, we use a wide range of complementary X-ray spectroscopies coupled to DFT calculations to study Co4O4 cubanes, which provide insight into the high-valent Co(IV) centers responsible for the activity of molecular and heterogeneous OER catalysts. The combination of X-ray absorption and 1s3p resonant inelastic X-ray scattering (Kβ RIXS) allow Co(IV) to be isolated and studied against a spectroscopically active Co(III) background. Co K- and L-edge X-ray absorption data allow for a detailed characterization of the 3d-manifold of effectively localized Co(IV) centers and provide a direct handle on the ligand field environment and covalency of the t2g-based redox active molecular orbital. Kβ RIXS is also shown to provide a powerful probe of Co(IV), and specific spectral features are sensitive to the degree of oxo-mediated metal-metal coupling across Co4O4. Guided by the data, calculations show electron-hole delocalization can actually oppose Co(IV) formation. Computational extension of Co4O4 to CoM3O4 structures (M = redox-inactive metal) defines electronic structure contri-butions to Co(IV) formation. Redox activity is shown to be linearly related to covalency, and M(III) oxo inductive effects on Co(IV) oxo bonding can tune the covalency of high-valent sites over a large range and thereby tune E0 over hundreds of mVs.

  2. Critical flux determination by flux-stepping

    DEFF Research Database (Denmark)

    Beier, Søren; Jonsson, Gunnar Eigil

    2010-01-01

    In membrane filtration related scientific literature, often step-by-step determined critical fluxes are reported. Using a dynamic microfiltration device, it is shown that critical fluxes determined from two different flux-stepping methods are dependent upon operational parameters such as step...... length, step height, and.flux start level. Filtrating 8 kg/m(3) yeast cell suspensions by a vibrating 0.45 x 10(-6) m pore size microfiltration hollow fiber module, critical fluxes from 5.6 x 10(-6) to 1.2 x 10(-5) m/s have been measured using various step lengths from 300 to 1200 seconds. Thus......, such values are more or less useless in itself as critical flux predictors, and constant flux verification experiments have to be conducted to check if the determined critical fluxes call predict sustainable flux regimes. However, it is shown that using the step-by-step predicted critical fluxes as start...

  3. Identification of developmentally toxic drinking water disinfection byproducts and evaluation of data relevant to mode of action

    International Nuclear Information System (INIS)

    Colman, Joan; Rice, Glenn E.; Wright, J. Michael; Hunter, E. Sidney; Teuschler, Linda K.; Lipscomb, John C.; Hertzberg, Richard C.; Simmons, Jane Ellen; Fransen, Margaret; Osier, Mark; Narotsky, Michael G.

    2011-01-01

    Reactions between chemicals used to disinfect drinking water and compounds present in source waters produce chemical mixtures containing hundreds of disinfection byproducts (DBPs). Although the results have been somewhat inconsistent, some epidemiological studies suggest associations may exist between DBP exposures and adverse developmental outcomes. The potencies of individual DBPs in rodent and rabbit developmental bioassays suggest that no individual DBP can account for the relative risk estimates reported in the positive epidemiologic studies, leading to the hypothesis that these outcomes could result from the toxicity of DBP mixtures. As a first step in a mixtures risk assessment for DBP developmental effects, this paper identifies developmentally toxic DBPs and examines data relevant to the mode of action (MOA) for DBP developmental toxicity. We identified 24 developmentally toxic DBPs and four adverse developmental outcomes associated with human DBP exposures: spontaneous abortion, cardiovascular defects, neural tube defects, and low birth weight infancy. A plausible MOA, involving hormonal disruption of pregnancy, is delineated for spontaneous abortion, which some epidemiologic studies associate with total trihalomethane and bromodichloromethane exposures. The DBP data for the other three outcomes were inadequate to define key MOA steps.

  4. Participants' Perceptions of a Violence Prevention Curriculum for Middle School Students: Was It Relevant and Useful?

    Science.gov (United States)

    Farrell, Albert D; Mehari, Krista; Mays, Sally; Sullivan, Terri N; Le, Anh-Thuy

    2015-08-01

    School-based youth violence prevention programs, particularly those focused on middle school students, have generally had limited effects that are often not sustained over time. Although many interventions focus on teaching social-cognitive skills, few studies have explored the extent to which students master these skills, actually use them, and find them effective in dealing with problem situations. This study examined these issues based on interviews with 141 students attending one county and two urban middle schools in classrooms where the Second Step violence prevention program had been implemented. We coded interviews to assess participants' general reactions to the interventions, use of skills, and effectiveness of skills. We also asked participants to describe outcomes they experienced when they used specific skills taught in the intervention in response to problem situations. Participants had generally positive reactions to the intervention. Their suggestions for improving the intervention primarily concerned improving its relevance. Participants described changes they had made based on the intervention, particularly controlling anger and improving relations with others. Their responses indicated that they sometimes misunderstood or misused specific intervention skills, especially problem solving and empathy. Students' descriptions of the outcomes they experienced when using intervention skills were not uniformly positive. This was especially true for situations involving peers such as peer pressure and bullying. These results underscore the need for more intensive efforts to ensure that students master intervention skills and are able to use them correctly. In addition, interventions should address the broader social context (e.g., peers, school) to maximize the effectiveness of skills.

  5. The dynamics of the Hg + Br2 reaction: elucidation of the reaction mechanism for the Br exchange reaction.

    Science.gov (United States)

    Jambrina, P G; Menéndez, M; Aoiz, F J

    2017-06-28

    In spite of its importance in the Hg atmospheric chemistry, the dynamics of the Hg + Br 2 → HgBr + Br reaction is poorly understood. In this article, we have carried out a comprehensive study of the reaction mechanism of this reaction by means of quasiclassical trajectories (QCTs) on an existing ab initio potential energy surface (PES). The reaction has a non trivial dynamics, as a consequence of its large endothermicity, the presence of a deep potential well, and the competition between the Br exchange and the collision induced dissociation processes. Our calculations demonstrate that insertion is only relevant at energies just above the reaction threshold and that, at energies above 2.3 eV, HgBr formation typically takes place via a sort of frustrated dissociation. In order to compare directly with the results obtained in extensive cross molecular beam experiments for the homologous reaction with I 2 , angular distributions in the laboratory frame for Hg + Br 2 have been simulated under similar experimental conditions. The lack of agreement at the highest energies considered suggests that either the two reactions have substantially different mechanisms or that calculations on a single PES cannot account for the dynamics at those energies.

  6. Step dynamics and terrace-width distribution on flame-annealed gold films: The effect of step-step interaction

    International Nuclear Information System (INIS)

    Shimoni, Nira; Ayal, Shai; Millo, Oded

    2000-01-01

    Dynamics of atomic steps and the terrace-width distribution within step bunches on flame-annealed gold films are studied using scanning tunneling microscopy. The distribution is narrower than commonly observed for vicinal planes and has a Gaussian shape, indicating a short-range repulsive interaction between the steps, with an apparently large interaction constant. The dynamics of the atomic steps, on the other hand, appear to be influenced, in addition to these short-range interactions, also by a longer-range attraction of steps towards step bunches. Both types of interactions promote self-ordering of terrace structures on the surface. When current is driven through the films a step-fingering instability sets in, reminiscent of the Bales-Zangwill instability

  7. Ten steps to successful software process improvement

    Science.gov (United States)

    Kandt, R. K.

    2003-01-01

    This paper identifies ten steps for managing change that address organizational and cultural issues. Four of these steps are critical, that if not done, will almost guarantee failure. This ten-step program emphasizes the alignment of business goals, change process goals, and the work performed by the employees of an organization.

  8. 7 CFR 65.230 - Production step.

    Science.gov (United States)

    2010-01-01

    ... 7 Agriculture 3 2010-01-01 2010-01-01 false Production step. 65.230 Section 65.230 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Standards..., PEANUTS, AND GINSENG General Provisions Definitions § 65.230 Production step. Production step means, in...

  9. Statistical significance versus clinical relevance.

    Science.gov (United States)

    van Rijn, Marieke H C; Bech, Anneke; Bouyer, Jean; van den Brand, Jan A J G

    2017-04-01

    In March this year, the American Statistical Association (ASA) posted a statement on the correct use of P-values, in response to a growing concern that the P-value is commonly misused and misinterpreted. We aim to translate these warnings given by the ASA into a language more easily understood by clinicians and researchers without a deep background in statistics. Moreover, we intend to illustrate the limitations of P-values, even when used and interpreted correctly, and bring more attention to the clinical relevance of study findings using two recently reported studies as examples. We argue that P-values are often misinterpreted. A common mistake is saying that P < 0.05 means that the null hypothesis is false, and P ≥0.05 means that the null hypothesis is true. The correct interpretation of a P-value of 0.05 is that if the null hypothesis were indeed true, a similar or more extreme result would occur 5% of the times upon repeating the study in a similar sample. In other words, the P-value informs about the likelihood of the data given the null hypothesis and not the other way around. A possible alternative related to the P-value is the confidence interval (CI). It provides more information on the magnitude of an effect and the imprecision with which that effect was estimated. However, there is no magic bullet to replace P-values and stop erroneous interpretation of scientific results. Scientists and readers alike should make themselves familiar with the correct, nuanced interpretation of statistical tests, P-values and CIs. © The Author 2017. Published by Oxford University Press on behalf of ERA-EDTA. All rights reserved.

  10. Traffic safety and step-by-step driving licence for young people

    DEFF Research Database (Denmark)

    Tønning, Charlotte; Agerholm, Niels

    2017-01-01

    presents a review of safety effects from step-by-step driving licence schemes. Most of the investigated schemes consist of a step-by-step driving licence with Step 1) various tests and education, Step 2) a period where driving is only allowed together with an experienced driver and Step 3) driving without...... companion is allowed but with various restrictions and, in some cases, additional driving education and tests. In general, a step-by-step driving licence improves traffic safety even though the young people are permitted to drive a car earlier on. The effects from driving with an experienced driver vary......Young novice car drivers are much more accident-prone than other drivers - up to 10 times that of their parents' generation. A central solution to improve the traffic safety for this group is implementation of a step-by-step driving licence. A number of countries have introduced a step...

  11. One-step production of biodiesel from Nannochloropsis sp. on solid base Mg-Zr catalyst

    International Nuclear Information System (INIS)

    Li, Yuesong; Lian, Shuang; Tong, Dongmei; Song, Ruili; Yang, Wenyan; Fan, Yong; Qing, Renwei; Hu, Changwei

    2011-01-01

    Nannochloropsis sp., one kind of green microalgae cultivated autotrophically and axenically in laboratory, is used as raw material to produce biodiesel by one-step method in an amended reactor. The effects of several reaction parameters on transesterification over Mg-Zr solid base catalyst were investigated through both conventional method and one-step method. One-step method could give a higher yield of methyl ester than conventional two-step method, which demonstrates that the present one-step method is suitable for biodiesel production from the microalgae Nannochloropsis sp. Moreover, the present one-step method realizes the convenient in situ separation of catalyst from microalgae residue which can be easily used consequently, reducing the procedure units as well as the overall costs.

  12. Does relevance matter in academic policy research?

    DEFF Research Database (Denmark)

    Dredge, Dianne

    2015-01-01

    A reflection on whether relevance matters in tourism policy research. A debate among tourism scholars.......A reflection on whether relevance matters in tourism policy research. A debate among tourism scholars....

  13. 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.

  14. Noncanonical Reactions of Flavoenzymes

    Directory of Open Access Journals (Sweden)

    Pablo Sobrado

    2012-11-01

    Full Text Available Enzymes containing flavin cofactors are predominantly involved in redox reactions in numerous cellular processes where the protein environment modulates the chemical reactivity of the flavin to either transfer one or two electrons. Some flavoenzymes catalyze reactions with no net redox change. In these reactions, the protein environment modulates the reactivity of the flavin to perform novel chemistries. Recent mechanistic and structural data supporting novel flavin functionalities in reactions catalyzed by chorismate synthase, type II isopentenyl diphosphate isomerase, UDP-galactopyranose mutase, and alkyl-dihydroxyacetonephosphate synthase are presented in this review. In these enzymes, the flavin plays either a direct role in acid/base reactions or as a nucleophile or electrophile. In addition, the flavin cofactor is proposed to function as a “molecular scaffold” in the formation of UDP-galactofuranose and alkyl-dihydroxyacetonephosphate by forming a covalent adduct with reaction intermediates.

  15. Spectromicroscopy of catalytic relevant processes with sub-micron resolution

    International Nuclear Information System (INIS)

    Guenther, S.; Esch, F.; Gregoratti, L.; Marsi, M.; Kiskinova, M.; Schubert, U. A.; Grotz, P.; Knoezinger, H.; Taglauer, E.; Schuetz, E.; Schaak, A.; Imbihl, R.

    2000-01-01

    The capabilities of the Scanning Photo Electron Microscope (SPEM) at ELETTRA as a unique probing tool in the field of catalysis and surface science are illustrated presenting results of two recent investigations. The lateral resolution and the high surface sensitivity of the SPEM has enabled imaging the initial steps of the spreading processes of MoO 3 crystals on an alumina support surface, a model system of a catalyst used in petrochemistry. In the second study the local adsorbate coverage inside a pulse of a chemical wave occurring in the catalytic NO+H 2 reaction on a Rh(110) single crystal surface has been determined. The microscope was used to monitor the sample surface in situ during the reaction and thus characterizing a temporal and spatial inhomogeneous system. The so-called excitation cycle of the pulse formation has been verified and the adsorbate gradient inside a chemical wave was measured

  16. Raman spectroscopic study of reaction dynamics

    Science.gov (United States)

    MacPhail, R. A.

    1990-12-01

    The Raman spectra of reacting molecules in liquids can yield information about various aspects of the reaction dynamics. The author discusses the analysis of Raman spectra for three prototypical unimolecular reactions, the rotational isomerization of n-butane and 1,2-difluoroethane, and the barrierless exchange of axial and equatorial hydrogens in cyclopentane via pseudorotation. In the first two cases the spectra are sensitive to torsional oscillations of the gauche conformer, and yield estimates of the torsional solvent friction. In the case of cyclopentane, the spectra can be used to discriminate between different stochastic models of the pseudorotation dynamics, and to determine the relevant friction coefficients.

  17. Nuclear reactions in ultra-magnetized supernovae

    International Nuclear Information System (INIS)

    Kondratyev, V.N.

    2002-06-01

    The statistical model is employed to investigate nuclear reactions in ultrastrong magnetic fields relevant for supernovae and neutron stars. For radiative capture processes the predominant mechanisms are argued to correspond to modifications of nuclear level densities, and γ-transition energies due to interactions of the field with magnetic moments of nuclei. The density of states reflects the nuclear structure and results in oscillations of reaction cross sections as a function of field strength, while magnetic interaction energy enhances radiative neutron capture process. Implications in the synthesis of r-process nuclei in supernova site are discussed. (author)

  18. Two-step rapid sulfur capture. Final report

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1994-04-01

    The primary goal of this program was to test the technical and economic feasibility of a novel dry sorbent injection process called the Two-Step Rapid Sulfur Capture process for several advanced coal utilization systems. The Two-Step Rapid Sulfur Capture process consists of limestone activation in a high temperature auxiliary burner for short times followed by sorbent quenching in a lower temperature sulfur containing coal combustion gas. The Two-Step Rapid Sulfur Capture process is based on the Non-Equilibrium Sulfur Capture process developed by the Energy Technology Office of Textron Defense Systems (ETO/TDS). Based on the Non-Equilibrium Sulfur Capture studies the range of conditions for optimum sorbent activation were thought to be: activation temperature > 2,200 K for activation times in the range of 10--30 ms. Therefore, the aim of the Two-Step process is to create a very active sorbent (under conditions similar to the bomb reactor) and complete the sulfur reaction under thermodynamically favorable conditions. A flow facility was designed and assembled to simulate the temperature, time, stoichiometry, and sulfur gas concentration prevalent in the advanced coal utilization systems such as gasifiers, fluidized bed combustors, mixed-metal oxide desulfurization systems, diesel engines, and gas turbines.

  19. Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.

    Science.gov (United States)

    Sad, María E; Neurock, Matthew; Iglesia, Enrique

    2011-12-21

    This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions. © 2011 American Chemical Society

  20. TRIMOLECULAR REACTIONS OF URANIUM HEXAFLUORIDE WITH WATER

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, M.; Becnel, J.; Garrison, S.

    2010-02-25

    The hydrolysis reaction of uranium hexafluoride (UF{sub 6}) is a key step in the synthesis of uranium dioxide (UO{sub 2}) powder for nuclear fuels. Mechanisms for the hydrolysis reactions are studied here with density functional theory and the Stuttgart small-core scalar relativistic pseudopotential and associated basis set for uranium. The reaction of a single UF{sub 6} molecule with a water molecule in the gas phase has been previously predicted to proceed over a relatively sizeable barrier of 78.2 kJ {center_dot} mol{sup -1}, indicating this reaction is only feasible at elevated temperatures. Given the observed formation of a second morphology for the UO{sub 2} product coupled with the observations of rapid, spontaneous hydrolysis at ambient conditions, an alternate reaction pathway must exist. In the present work, two trimolecular hydrolysis mechanisms are studied with density functional theory: (1) the reaction between two UF{sub 6} molecules and one water molecule, and (2) the reaction of two water molecules with a single UF{sub 6} molecule. The predicted reaction of two UF{sub 6} molecules with one water molecule displays an interesting 'fluorine-shuttle' mechanism, a significant energy barrier of 69.0 kJ {center_dot} mol{sup -1} to the formation of UF{sub 5}OH, and an enthalpy of reaction ({Delta}H{sub 298}) of +17.9 kJ {center_dot} mol{sup -1}. The reaction of a single UF{sub 6} molecule with two water molecules displays a 'proton-shuttle' mechanism, and is more favorable, having a slightly lower computed energy barrier of 58.9 kJ {center_dot} mol{sup -1} and an exothermic enthalpy of reaction ({Delta}H{sub 298}) of -13.9 kJ {center_dot} mol{sup -1}. The exothermic nature of the overall UF{sub 6} + 2 {center_dot} H{sub 2}O trimolecular reaction and the lowering of the barrier height with respect to the bimolecular reaction are encouraging; however, the sizable energy barrier indicates further study of the UF{sub 6} hydrolysis reaction

  1. Nuclear reaction studies

    International Nuclear Information System (INIS)

    Alexander, J.M.; Lacey, R.A.

    1994-01-01

    Research focused on the statistical and dynamical properties of ''hot'' nuclei formed in symmetric heavy-ion reactions. Theses included ''flow'' measurements and the mechanism for multifragment disassembly. Model calculations are being performed for the reactions C+C, Ne+Al, Ar+Sc, Kr+Nb, and Xe+La. It is planned to study 40 Ar reactions from 27 to 115 MeV/nucleon. 2 figs., 41 refs

  2. Knock-out reactions

    International Nuclear Information System (INIS)

    de Forest, T. Jr.

    1977-01-01

    It is pointed out that the primary motivation for performing high energy single nucleon knock-out reactions is based on the concept of quasi-elastic scattering. The validity of and corrections to the partial wave impulse approximation and kinematical invariance of knock-out reactions and tests of the reaction mechanism are treated. The effect of distortions on the momentum distribution in the effective momentum approximation for given parameters are plotted. 12 references

  3. Pressure modulates the self-cleavage step of the hairpin ribozyme

    Science.gov (United States)

    Schuabb, Caroline; Kumar, Narendra; Pataraia, Salome; Marx, Dominik; Winter, Roland

    2017-03-01

    The ability of certain RNAs, denoted as ribozymes, to not only store genetic information but also catalyse chemical reactions gave support to the RNA world hypothesis as a putative step in the development of early life on Earth. This, however, might have evolved under extreme environmental conditions, including the deep sea with pressures in the kbar regime. Here we study pressure-induced effects on the self-cleavage of hairpin ribozyme by following structural changes in real-time. Our results suggest that compression of the ribozyme leads to an accelerated transesterification reaction, being the self-cleavage step, although the overall process is retarded in the high-pressure regime. The results reveal that favourable interactions between the reaction site and neighbouring nucleobases are strengthened under pressure, resulting therefore in an accelerated self-cleavage step upon compression. These results suggest that properly engineered ribozymes may also act as piezophilic biocatalysts in addition to their hitherto known properties.

  4. Astrophysical reaction rate for α(αn,γ)9Be by photodisintegration

    International Nuclear Information System (INIS)

    Sumiyoshi, K.; Utsunomiya, H.; Goko, S.; Kajino, T.

    2002-01-01

    We study the astrophysical reaction rate for the formation of 9 Be through the three body reaction α(αn,γ). This reaction is one of the key reactions which could bridge the mass gap at A=8 nuclear systems to produce intermediate-to-heavy mass elements in alpha- and neutron-rich environments such as r-process nucleosynthesis in supernova explosions, s-process nucleosynthesis in asymptotic giant branch (AGB) stars, and primordial nucleosynthesis in baryon inhomogeneous cosmological models. To calculate the thermonuclear reaction rate in a wide range of temperatures, we numerically integrate the thermal average of cross sections assuming a two-steps formation through a metastable 8 Be, α+α[rlhar2] 8 Be(n,γ) 9 Be. Off-resonant and on-resonant contributions from the ground state in 8 Be are taken into account. As input cross section, we adopt the latest experimental data by photodisintegration of 9 Be with laser-electron photon beams, which covers all relevant resonances in 9 Be. Experimental data near the neutron threshold are added with γ-ray flux corrections and a new least-squares analysis is made to deduce resonance parameters in the Breit-Wigner formulation. Based on the photodisintegration cross section, we provide the reaction rate for α(αn,γ) 9 Be in the temperature range from T 9 =10 -3 to T 9 =10 1 (T 9 is the temperature in units of 10 9 K) both in the tabular form and in the analytical form for potential usage in nuclear reaction network calculations. The calculated reaction rate is compared with the reaction rates of the CF88 and the NACRE compilations. The CF88 rate, which is based on the photoneutron cross section for the 1/2 + state in 9 Be by Berman et al., is valid at T 9 >0.028 due to lack of the off-resonant contribution. The CF88 rate differs from the present rate by a factor of two in a temperature range T 9 ≥0.1. The NACRE rate, which adopted different sources of experimental information on resonance states in 9 Be, is 4-12 times

  5. A green Hunsdiecker reaction of cinnamic acids

    Energy Technology Data Exchange (ETDEWEB)

    Sodre, Leonardo R.; Esteves, Pierre M.; Mattos, Marcio C. S. de, E-mail: pesteves@iq.ufrj.br, E-mail: mmattos@iq.ufrj.br [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica. Departamento de Quimica

    2013-02-15

    Tribromo- and trichloroisocyanuric acids react with cinnamic acids in NaOH/H{sub 2}O/Et{sub 2}O at room temperature to produce (E)-2-halostyrenes regioselectively in 25-95% yield. Mechanism studies using Hammett correlations and DFT (density functional theory) calculations have shown that this reaction has as rate determining step the electrophilic addition of chlorine atom to the double bond. (author)

  6. Sugarcane bagasse gasification: Global reaction mechanism of syngas evolution

    International Nuclear Information System (INIS)

    Ahmed, I.I.; Gupta, A.K.

    2012-01-01

    Highlights: ► Gasification of sugarcane bagasse has been investigated using a semi batch reactor. ► Global reaction mechanism combining pyrolysis and gasification reactions is presented. ► High flow rates of syngas supported fragmentation and secondary reactions. ► CO flow rate increased at higher heating rates at the expense of CO 2 production. ► At high temperatures merger between pyrolysis and char gasification occurs. -- Abstract: Steam gasification of sugarcane bagasse has been investigated. A semi batch reactor with a fixed amount of sugarcane bagasse sample placed in steady flow of high temperature steam at atmospheric pressure has been used. The gasification of bagasse was examined at reactor and steam temperatures of 800, 900 and 1000 °C. The evolution of syngas flow rate and chemical composition has been monitored. The evolution of chemical composition and total flow rate of the syngas has been used to formulate a global reaction mechanism. The mechanism combines pyrolysis reaction mechanisms from the literature and steam gasification/reforming reactions. Steam gasification steps include steam–hydrocarbons reforming, char gasification and water gas shift reactions. Evidence of fragmentation, secondary ring opening reactions and tertiary reactions resulting in formation of gaseous hydrocarbons is supported by higher flow rates of syngas and hydrogen at high heating rates and high reactor temperatures. Increase in carbon monoxide flow rate at the expense of carbon dioxide flow rate with the increase in reactor temperature has been observed. This increase in the ratio of CO/CO 2 flow rate confirms the production of CO and CO 2 from the competing reaction routes. At 1000 °C gasification a total merging between the pyrolysis step and the char gasification step has been observed. This is attributed to acceleration of char gasification reactions and acceleration of steam–hydrocarbons reforming reactions. These hydrocarbons are the precursors to

  7. Gradiometry coexperiments to the gravity probe B and step missions

    International Nuclear Information System (INIS)

    Tapley, M.; Breakwell, J.; Everitt, C.W.F.; Vanpatten, R.; Worden, P.

    1990-01-01

    The Gravity Probe-B (GP-B) spacecraft, designed to test predictions of general relativity, will fly in the mid 1990s. It will carry four electrostatically suspended gyroscopes in a cryogenic environment and will have a drag-free control system to minimize disturbances on the gyroscopes. The Stanford Test of Equivalence Principle (STEP) spacecraft, to fly later, will carry a set of test masses under very similar conditions. The possibility of using differential measurements of the GP-B gyroscopes suspension forces and the STEP tests mass displacement readout to form single-axis gravity gradiometers is explored. It is shown that the noise in the suspension systems is sufficiently small in the relevant frequency range, and that enough information is collected to compensate for the spacecrafts' attitude motion. Finally, using Breakwell's flat-earth approximation, these experiments are compared to other geodesy experiments and predict the contribution they can make to the knowledge of the Earth's geopotential

  8. Stepping Stones: Evolving the Earth and Its Life

    Science.gov (United States)

    McKay, Christopher P.

    In recent years, science has begun to consider more system-level studies that cross disciplines. These studies challenge our traditional disciplinary training. It is no longer enough to be just a geologist when the problems of interest deal with an entire planet. Indeed, a knowledge of biology, geology astronomy, and myriad subfields is needed. In Stepping Stones, Stephen Drury steps up to the daunting task of writing a general treatment of the science of the entire Earth. He not only ranges through all of the relevant physical sciences but also reaches to economics and political theory. The material is presented at a general level with reading lists but no specific references. Equations have been minimized.

  9. Possibility of the Nonenzymatic Browning (Maillard) Reaction in the ISM

    Science.gov (United States)

    Jalbout, Abraham F.; Shipar, M. Abul Haider

    2008-04-01

    The possibility of the occurrence of the nonenzymatic browning reaction in the gaseous phase in the interstellar medium has been investigated by using Density Functional Theory computations. Mechanisms for the reactions between formaldehyde ( Fald) + glycine ( Gly), Fald + NH 3 and Fald + methylamine ( MeAm) have been proposed, and the possibility of the formation of different compounds in the proposed mechanisms has been evaluated through calculating the Gibb's free energy changes for different steps of the reaction, by following the total mass balance. The Fald + Gly reaction under basic conditions is found as the most favorable for producing 1-methyl-amino methene or 1-methyl-amino methelene ( MAM). The reaction under acidic conditions is found to be the least favorable for producing MAM. The Fald + NH 3 reaction is found to be plausible for the production of MeAm, which can participate by reaction with Fald, resulting in the formation of MAM.

  10. Reaction kinetics of polybutylene terephthalate polycondensation reaction

    NARCIS (Netherlands)

    Darda, P. J.; Hogendoorn, J. A.; Versteeg, G. F.; Souren, F.

    2005-01-01

    The kinetics of the forward polycondensation reaction of polybutylene terephthalate (PBT) has been investigated using thermogravimetric analysis (TGA). PBT - prepolymer with an initial degree of polymerization of 5.5 was used as starting material. The PBT prepolymer was prepared from dimethyl

  11. Science and the struggle for relevance

    NARCIS (Netherlands)

    Hessels, L.K.|info:eu-repo/dai/nl/304832863

    2010-01-01

    This thesis deals with struggles for relevance of university researchers, their efforts to make their work correspond with ruling standards of relevance and to influence these standards. Its general research question is: How to understand changes in the struggle for relevance of Dutch academic

  12. The Personal Relevance of the Social Studies.

    Science.gov (United States)

    VanSickle, Ronald L.

    1990-01-01

    Conceptualizes a personal-relevance framework derived from Ronald L. VanSickle's five areas of life integrated with four general motivating goals from Abraham Maslow's hierarchy of needs and Richard and Patricia Schmuck's social motivation theory. Illustrates ways to apply the personal relevance framework to make social studies more relevant to…

  13. The Development of Relevance in Information Retrieval

    Directory of Open Access Journals (Sweden)

    Mu-hsuan Huang

    1997-12-01

    Full Text Available This article attempts to investigate the notion of relevance in information retrieval. It discusses various definitions for relevance from historical viewpoints and the characteristics of relevance judgments. Also, it introduces empirical results of important related researches.[Article content in Chinese

  14. Thermonuclear reaction listing

    International Nuclear Information System (INIS)

    Fukai, Yuzo

    1993-01-01

    The following 10 elements, including T, are well known as nuclear fusion fuels: p, D, T, 3 He, 4 He, 6 Li, 7 Li, 9 Be, 10 B, 11 B, ( 12 C, 13 C), where 12 C and 13 C are considered only in the calculation of Q value. Accordingly the number of the thermonuclear reactions is 55, and 78, if including carbon elements. The reactions have some branches. For the branches having two and three reaction products, the reaction products, Q value and threshold energy are calculated by using a computer. We have investigated those of the branches having more than three products from the papers of Ajzenberg-Selove and so on. And also, by the same papers, we check whether the above mentioned branch has been observed or not. The results are as follows: (I) the number of reactions which have Q 0 branches only with γ ray production, and Q 0 and neutron production is 36(17), and (IV) that of reactions whose branch with Q > 0 does not produce neutrons is 9(3). The value in the parentheses shows the number of the case of the carbon elements. For 55 thermonuclear reactions induced by lighter nuclides than 11 B, the reaction products, the values of Q and threshold energy, and the papers with reaction cross section data are presented in the tables. (author)

  15. Sleeve reaction chamber system

    Science.gov (United States)

    Northrup, M Allen [Berkeley, CA; Beeman, Barton V [San Mateo, CA; Benett, William J [Livermore, CA; Hadley, Dean R [Manteca, CA; Landre, Phoebe [Livermore, CA; Lehew, Stacy L [Livermore, CA; Krulevitch, Peter A [Pleasanton, CA

    2009-08-25

    A chemical reaction chamber system that combines devices such as doped polysilicon for heating, bulk silicon for convective cooling, and thermoelectric (TE) coolers to augment the heating and cooling rates of the reaction chamber or chambers. In addition the system includes non-silicon-based reaction chambers such as any high thermal conductivity material used in combination with a thermoelectric cooling mechanism (i.e., Peltier device). The heat contained in the thermally conductive part of the system can be used/reused to heat the device, thereby conserving energy and expediting the heating/cooling rates. The system combines a micromachined silicon reaction chamber, for example, with an additional module/device for augmented heating/cooling using the Peltier effect. This additional module is particularly useful in extreme environments (very hot or extremely cold) where augmented heating/cooling would be useful to speed up the thermal cycling rates. The chemical reaction chamber system has various applications for synthesis or processing of organic, inorganic, or biochemical reactions, including the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction.

  16. Tattoo reaction: Case series

    Directory of Open Access Journals (Sweden)

    Muneer Mohamed

    2018-04-01

    Full Text Available Tattoo is going to be a very common practice especially among young people and we are witnessing a gradual increase of numerous potential complications to tattoo placement which are often seen by physicians, but generally unknown to the public. The most common skin reactions to tattoo include a transient acute inflammatory reaction due to trauma of the skin with needles and medical complications such as superficial and deep local infections, systemic infections, allergic contact dermatitis, photodermatitis, granulomatous and lichenoid reactions, and skin diseases localized on tattooed area (eczema, psoriasis, lichen, and morphea. In this series we present three cases of tattoo reaction.

  17. First steps in random walks from tools to applications

    CERN Document Server

    Klafter, J

    2011-01-01

    The name ""random walk"" for a problem of a displacement of a point in a sequence of independent random steps was coined by Karl Pearson in 1905 in a question posed to readers of ""Nature"". The same year, a similar problem was formulated by Albert Einstein in one of his Annus Mirabilis works. Even earlier such a problem was posed by Louis Bachelier in his thesis devoted to the theory of financial speculations in 1900. Nowadays the theory of random walks has proved useful in physics andchemistry (diffusion, reactions, mixing in flows), economics, biology (from animal spread to motion of subcel

  18. The multi-step prompt particle emission from fission fragments

    International Nuclear Information System (INIS)

    Zhivopistsev, A.; Oprea, C.; Oprea, I.

    2003-01-01

    The purpose of this work is the study of non-equilibrium high-energy gamma emission from 252 Cf. In the framework of the formalism of statistical multi-step compound processes in nuclear reactions. A relation was found between the shape of the high-energy part of the gamma spectrum and different mechanisms of excitation of the fission fragments. Agreement with experimental data for different groups of fission fragments was obtained. The analysis of the experimental high-energy part of gamma spectra yields information about the mechanism of excitation of fission fragments. The influence of dissipation of the deformation excess on intrinsic excitation of fission fragments was studied. (authors)

  19. Information sharing during diagnostic assessments: what is relevant for parents?

    Science.gov (United States)

    Klein, Sheryl; Wynn, Kerry; Ray, Lynne; Demeriez, Lori; LaBerge, Patricia; Pei, Jacqueline; St Pierre, Cherie

    2011-05-01

    ABSTRACT This descriptive qualitative study facilitates the application of family-centered care within a tertiary care interdisciplinary neurodevelopmental diagnostic assessment clinic by furthering an understanding of parent perceptions of the relevance of diagnostic information provision. An interdisciplinary assessment team completed an open-ended questionnaire to describe parent information provision. Parents from 9 families completed in-depth parent interviews following clinic attendance to discuss perceptions of information received. Interviews were audiotaped, transcribed, and coded by related themes. Parents did not perceive the information in the way professionals expected. Parents acknowledged receipt of comprehensive information relevant to the diagnosis but indicated that not all their needs were met. During the interviews, parents described the assessment process, preassessment information, and "steps in their journey." They noted that a strength-based approach and a focus on parental competency would support their coping efforts. Results underscore the need for professionals to be attentive to parents' individualized needs.

  20. A Data-Driven Sparse-Learning Approach to Model Reduction in Chemical Reaction Networks

    OpenAIRE

    Harirchi, Farshad; Khalil, Omar A.; Liu, Sijia; Elvati, Paolo; Violi, Angela; Hero, Alfred O.

    2017-01-01

    In this paper, we propose an optimization-based sparse learning approach to identify the set of most influential reactions in a chemical reaction network. This reduced set of reactions is then employed to construct a reduced chemical reaction mechanism, which is relevant to chemical interaction network modeling. The problem of identifying influential reactions is first formulated as a mixed-integer quadratic program, and then a relaxation method is leveraged to reduce the computational comple...