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)

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

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

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.

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)

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...

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

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...

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.

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

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.

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.)

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

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.)

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.

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

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.

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.

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.

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.

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

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...

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

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

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

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…

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...

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.

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

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.

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)

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.

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

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.

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

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.

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

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...

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.

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)

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.

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.

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.

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

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

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.

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.

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

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....

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

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.

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.

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?

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.

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

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)

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/.

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...

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.

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.

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

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)

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.

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

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.

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

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.

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.

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.

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.

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.

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

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)

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.

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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…

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)

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.

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)

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.

[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

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.

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.

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.

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).

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.

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.

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%.

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.

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.

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

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.

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...

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

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.

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.

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

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.

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.

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.

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.

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

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.

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.

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.

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.

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

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.

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

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)

Unexpected Reaction Pathway for butyrylcholinesterase-catalyzed inactivation of “hunger hormone” ghrelin

Science.gov (United States)

Yao, Jianzhuang; Yuan, Yaxia; Zheng, Fang; Zhan, Chang-Guo

2016-02-01

Extensive computational modeling and simulations have been carried out, in the present study, to uncover the fundamental reaction pathway for butyrylcholinesterase (BChE)-catalyzed hydrolysis of ghrelin, demonstrating that the acylation process of BChE-catalyzed hydrolysis of ghrelin follows an unprecedented single-step reaction pathway and the single-step acylation process is rate-determining. The free energy barrier (18.8 kcal/mol) calculated for the rate-determining step is reasonably close to the experimentally-derived free energy barrier (~19.4 kcal/mol), suggesting that the obtained mechanistic insights are reasonable. The single-step reaction pathway for the acylation is remarkably different from the well-known two-step acylation reaction pathway for numerous ester hydrolysis reactions catalyzed by a serine esterase. This is the first time demonstrating that a single-step reaction pathway is possible for an ester hydrolysis reaction catalyzed by a serine esterase and, therefore, one no longer can simply assume that the acylation process must follow the well-known two-step reaction pathway.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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)

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.

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.

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...

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.

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)

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.

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.

Can use of walkers or canes impede lateral compensatory stepping movements?

Science.gov (United States)

Bateni, Hamid; Heung, Evelyn; Zettel, John; McLlroy, William E; Maki, Brian E

2004-08-01

Although assistive devices, such as walkers and canes are often prescribed to aid in balance control, recent studies have suggested that such devices may actually increase risk of falling. In this study, we investigated one possible mechanism: the potential for walkers or canes to interfere with, or constrain, lateral movement of the feet and thereby impede execution of compensatory stepping reactions during lateral loss of balance. Lateral stepping reactions were evoked, in 10 healthy young adults (ages 22-27 years), by means of sudden unpredictable medio-lateral support surface translation. Subjects were tested while holding and loading a standard pickup walker or single-tip cane or while using no assistive device (hands free or holding an object). Results supported the hypothesis that using a walker or cane can interfere with compensatory stepping. Collisions between the swing-foot and mobility aid were remarkably frequent when using the walker (60% of stepping reactions) and also occurred in cane trials (11% of stepping reactions). Furthermore, such collisions were associated with a significant reduction (26-37%) in lateral step length. It appeared that subjects were sometimes able to avoid collision by increasing the forward or backward displacement of the swing-foot or by moving the cane; however, attempts to lift the walker out of the way occurred rarely and were usually impeded due to collision between the contralateral walker post and stance foot. The fact that compensatory stepping behavior was altered significantly in such a healthy cohort clearly demonstrates some of the safety limitations inherent to these assistive devices, as currently designed. Copyright 2003 Elsevier B.V.

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.

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.

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.

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.

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

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

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)

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.

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.

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

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

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

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) .

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

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

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

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

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

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.

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.

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.

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

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.

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.

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

Modified Two-Step Dimethyl Ether (DME Synthesis Simulation from Indonesian Brown Coal

Directory of Open Access Journals (Sweden)

Dwiwahju Sasongko

2016-08-01

Full Text Available A theoretical study was conducted to investigate the performance of dimethyl ether (DME synthesis from coal. This paper presents a model for two-step DME synthesis from brown coal represented by the following processes: drying, gasification, water-gas reaction, acid gas removal, and DME synthesis reactions. The results of the simulation suggest that a feedstock ratio of coal : oxygen : steam of 1 : 0.13 : 0.821 produces the highest DME concentration. The water-gas reactor simulation at a temperature of 400°C and a pressure of 20 bar gave the ratio of H2/CO closest to 2, the optimal value for two-step DME synthesis. As for the DME synthesis reactor simulation, high pressure and low temperature promote a high DME concentration. It is predicted that a temperature of 300°C and a pressure of 140 bar are the optimum conditions for the DME synthesis reaction. This study also showed that the DME concentration produced by the two-step route is higher than that produced by one-step DME synthesis, implying that further improvement and research are needed to apply two-step DME synthesis to production of this liquid fuel.

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

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.

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...

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

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...

Kinetic concepts of thermally stimulated reactions in solids

Science.gov (United States)

Vyazovkin, Sergey

Historical analysis suggests that the basic kinetic concepts of reactions in solids were inherited from homogeneous kinetics. These concepts rest upon the assumption of a single-step reaction that disagrees with the multiple-step nature of solid-state processes. The inadequate concepts inspire such unjustified anticipations of kinetic analysis as evaluating constant activation energy and/or deriving a single-step reaction mechanism for the overall process. A more adequate concept is that of the effective activation energy, which may vary with temperature and extent of conversion. The adequacy of this concept is illustrated by literature data as well as by experimental data on the thermal dehydration of calcium oxalate monohydrate and thermal decomposition of calcium carbonate, ammonium nitrate and 1,3,5,7- tetranitro-1,3,5,7-tetrazocine.

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)

Efficient Hydrolysis of Rice Straw into Xylose and Glucose by a Two-step Process

Directory of Open Access Journals (Sweden)

YAN Lu-lu

2016-07-01

Full Text Available The hydrolysis of rice straw into xylose and glucose in dilute sulfuric acid aqueous solution was studied with a two-step process in batch autoclave reactor. The results showed that compared with the traditional one-step acid hydrolysis, both xylose and glucose could be produced in high yields from rice straw by using the two-step acid hydrolysis process. The effects of reaction temperature, reaction time, the amount of rice straw and acid concentration on the hydrolysis of rice straw were systematically studied, and showed that except initial rice straw loading amount, the other parameters had remarkable influence on the products distribution and yields. In the first-step of the hydrolysis process, a high xylose yield of 162.6 g·kg-1 was obtained at 140℃ after 120 min reaction time. When the solid residues from the first step were subjected to a second-step hydrolysis, a glucose yield as high as 216.5 g·kg-1 could be achieved at 180℃ after 120 min. This work provides a promising strategy for the efficient and value-added utilization of agricultural wastes such as rice straw.

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.

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!

The water decomposition reactions on boron-doped diamond electrodes

International Nuclear Information System (INIS)

Suffredini, Hugo B.; Machado, Sergio A.S; Avaca, Luis A.

2004-01-01

The electrochemical processes occurring at both edges of the wide electrochemical window of the boron doped diamond (BDD) electrode were studied by polarization curves experiments to evaluate the apparent energy of activation for the rate determining step in each reaction. It was found that the hydrogen evolution reaction occurs by a Volmer-Heyrovsky mechanism with the first step being the RDS. Moreover, the apparent energy of activation calculated from the Tafel plots presented a value as high as 150 kJ mol -1 , indicating the formation of the M-H intermediate that is characteristic for the Volmer step. On the other hand, the apparent energy of activation for the oxygen evolution reaction was found to be 106 kJ mol -1 suggesting that the RDS in this mechanism is the initial adsorption step. In this way, it was demonstrated that the interaction between water molecules and the electrode surface is strongly inhibited on BDD thus justifying the extended potential window observed for this material. (author)

The water decomposition reactions on boron-doped diamond electrodes

Directory of Open Access Journals (Sweden)

Suffredini Hugo B

2004-01-01

Full Text Available The electrochemical processes occurring at both edges of the wide electrochemical window of the boron doped diamond (BDD electrode were studied by polarization curves experiments to evaluate the apparent energy of activation for the rate determining step in each reaction. It was found that the hydrogen evolution reaction occurs by a Volmer-Heyrovsky mechanism with the first step being the RDS. Moreover, the apparent energy of activation calculated from the Tafel plots presented a value as high as 150 kJ mol-1, indicating the formation of the M-H intermediate that is characteristic for the Volmer step. On the other hand, the apparent energy of activation for the oxygen evolution reaction was found to be 106 kJ mol-1 suggesting that the RDS in this mechanism is the initial adsorption step. In this way, it was demonstrated that the interaction between water molecules and the electrode surface is strongly inhibited on BDD thus justifying the extended potential window observed for this material.

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.

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...

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.

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.)

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.

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

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.

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)

Modelling of the spallation reaction: analysis and testing of nuclear models

International Nuclear Information System (INIS)

Toccoli, C.

2000-01-01

The spallation reaction is considered as a 2-step process. First a very quick stage (10 -22 , 10 -29 s) which corresponds to the individual interaction between the incident projectile and nucleons, this interaction is followed by a series of nucleon-nucleon collisions (intranuclear cascade) during which fast particles are emitted, the nucleus is left in a strongly excited level. Secondly a slower stage (10 -18 , 10 -19 s) during which the nucleus is expected to de-excite completely. This de-excitation is performed by evaporation of light particles (n, p, d, t, 3 He, 4 He) or/and fission or/and fragmentation. The HETC code has been designed to simulate spallation reactions, this simulation is based on the 2-steps process and on several models of intranuclear cascades (Bertini model, Cugnon model, Helder Duarte model), the evaporation model relies on the statistical theory of Weiskopf-Ewing. The purpose of this work is to evaluate the ability of the HETC code to predict experimental results. A methodology about the comparison of relevant experimental data with results of calculation is presented and a preliminary estimation of the systematic error of the HETC code is proposed. The main problem of cascade models originates in the difficulty of simulating inelastic nucleon-nucleon collisions, the emission of pions is over-estimated and corresponding differential spectra are badly reproduced. The inaccuracy of cascade models has a great impact to determine the excited level of the nucleus at the end of the first step and indirectly on the distribution of final residual nuclei. The test of the evaporation model has shown that the emission of high energy light particles is under-estimated. (A.C.)

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...

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.

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.

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

Research on the quantum multistep theory for pre-equilibrium nuclear reaction

CERN Document Server

Su Zong Di; Abdurixit, A; Wang Shu Nuan; Li Bao Xian; Huang Zhong; Liu Jian Feng; Zhang Benai; Zhu Yao Yin; Li Zhi Wen

2002-01-01

The Feshbach-Kerman-Koonin (FKK) quantum multistep theory of the pre-equilibrium reaction is further improved and perfected. A unified description for the multistep compound (MSC) process of the pre-equilibrium reaction and the compound nucleus (CN) process of full equilibrium reaction can be presented. This formula can integrate MSC and CN theories with the optical model and Hauser-Feshbach formula, and can get self-consistent expression. In multistep direct (MSD) process of the pre-equilibrium reaction, the mu-step cross section can be expressed by the convolution of mu one-step cross section. And the one step cross section for continuum can be written as the product of an averaged DWBA matrix element and the state density. For calculating the multistep direct reaction cross section, two methods, the state densities and full microscopic model, are used and compared. Some typical experiments are analyzed by using the work mentioned above. The calculated results are reasonable and in good agreement with the e...

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

Two steps hydrothermal growth and characterisations of BaTiO3 films composed of nanowires

Science.gov (United States)

Zawawi, Che Zaheerah Najeehah Che Mohd; Salleh, Shahril; Oon Jew, Lee; Tufail Chaudhary, Kashif; Helmi, Mohamad; Safwan Aziz, Muhammad; Haider, Zuhaib; Ali, Jalil

2018-05-01

Barium titanate (BaTiO3) films composed of nanowires have gained considerable research interest due to their lead-free composition and strong energy conversion efficiency. BaTiO3 films can be developed with a simple two steps hydrothermal reactions, which are low cost effective. In this research, BaTiO3 films were fabricated on titanium foil through two steps hydrothermal method namely, the growth of TiO2 and followed by BaTiO3 films. The structural evolutions and the dielectric properties of the films were investigated as well. The structural evolutions of titanium dioxide (TiO2) and BaTiO3 nanowires were characterized using X-ray diffraction and scanning electron microscopy. First step of hydrothermal reaction, TiO2 nanowires were prepared in varied temperatures of 160 °C, 200 °C and 250 °C respectively. Second step of hydrothermal reaction was performed to produce a layer of BaTiO3 films.

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

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...

Improved predictions of nuclear reaction rates for astrophysics applications with the TALYS reaction code

International Nuclear Information System (INIS)

Goriely, S.; Hilaire, S.; Koning, A.J.

2008-01-01

Nuclear reaction rates for astrophysics applications are traditionally determined on the basis of Hauser-Feshbach reaction codes, like MOST. These codes use simplified schemes to calculate the capture reaction cross section on a given target nucleus, not only in its ground state but also on the different thermally populated states of the stellar plasma at a given temperature. Such schemes include a number of approximations that have never been tested, such as an approximate width fluctuation correction, the neglect of delayed particle emission during the electromagnetic decay cascade or the absence of the pre-equilibrium contribution at increasing incident energies. New developments have been brought to the reaction code TALYS to estimate the Maxwellian-averaged reaction rates of astrophysics relevance. These new developments give us the possibility to calculate with an improved accuracy the reaction cross sections and the corresponding astrophysics rates. The TALYS predictions for the thermonuclear rates of astrophysics relevance are presented and compared with those obtained with the MOST code on the basis of the same nuclear ingredients for nuclear structure properties, optical model potential, nuclear level densities and γ-ray strength. It is shown that, in particular, the pre-equilibrium process significantly influences the astrophysics rates of exotic neutron-rich nuclei. The reciprocity theorem traditionally used in astrophysics to determine photo-rates is also shown no to be valid for exotic nuclei. The predictions obtained with different nuclear inputs are also analyzed to provide an estimate of the theoretical uncertainties still affecting the reaction rate prediction far away from the experimentally known regions. (authors)

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)

Composition of single-step media used for human embryo culture.

Science.gov (United States)

Morbeck, Dean E; Baumann, Nikola A; Oglesbee, Devin

2017-04-01

To determine compositions of commercial single-step culture media and test with a murine model whether differences in composition are biologically relevant. Experimental laboratory study. University-based laboratory. Inbred female mice were superovulated and mated with outbred male mice. Amino acid, organic acid, and ions content were determined for single-step culture media: CSC, Global, G-TL, and 1-Step. To determine whether differences in composition of these media are biologically relevant, mouse one-cell embryos were cultured for 96 hours in each culture media at 5% and 20% oxygen in a time-lapse incubator. Compositions of four culture media were analyzed for concentrations of 30 amino acids, organic acids, and ions. Blastocysts at 96 hours of culture and cell cycle timings were calculated, and experiments were repeated in triplicate. Of the more than 30 analytes, concentrations of glucose, lactate, pyruvate, amino acids, phosphate, calcium, and magnesium varied in concentrations. Mouse embryos were differentially affected by oxygen in G-TL and 1-Step. Four single-step culture media have compositions that vary notably in pyruvate, lactate, and amino acids. Blastocyst development was affected by culture media and its interaction with oxygen concentration. Copyright © 2017 American Society for Reproductive Medicine. Published by Elsevier Inc. All rights reserved.

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.

Structure and Reaction Mechanism of Pyrrolysine Synthase (PylD)

KAUST Repository

Quitterer, Felix; Beck, Philipp; Bacher, Adelbert; Groll, Michael

2013-01-01

The final step in the biosynthesis of the 22nd genetically encoded amino acid, pyrrolysine, is catalyzed by PylD, a structurally and mechanistically unique dehydrogenase. This catalyzed reaction includes an induced-fit mechanism achieved by major structural rearrangements of the N-terminal helix upon substrate binding. Different steps of the reaction trajectory are visualized by complex structures of PylD with substrate and product. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure and Reaction Mechanism of Pyrrolysine Synthase (PylD)

KAUST Repository

Quitterer, Felix

2013-05-29

The final step in the biosynthesis of the 22nd genetically encoded amino acid, pyrrolysine, is catalyzed by PylD, a structurally and mechanistically unique dehydrogenase. This catalyzed reaction includes an induced-fit mechanism achieved by major structural rearrangements of the N-terminal helix upon substrate binding. Different steps of the reaction trajectory are visualized by complex structures of PylD with substrate and product. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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.

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.

Mining chemical reactions using neighborhood behavior and condensed graphs of reactions approaches.

Science.gov (United States)

de Luca, Aurélie; Horvath, Dragos; Marcou, Gilles; Solov'ev, Vitaly; Varnek, Alexandre

2012-09-24

This work addresses the problem of similarity search and classification of chemical reactions using Neighborhood Behavior (NB) and Condensed Graphs of Reaction (CGR) approaches. The CGR formalism represents chemical reactions as a classical molecular graph with dynamic bonds, enabling descriptor calculations on this graph. Different types of the ISIDA fragment descriptors generated for CGRs in combination with two metrics--Tanimoto and Euclidean--were considered as chemical spaces, to serve for reaction dissimilarity scoring. The NB method has been used to select an optimal combination of descriptors which distinguish different types of chemical reactions in a database containing 8544 reactions of 9 classes. Relevance of NB analysis has been validated in generic (multiclass) similarity search and in clustering with Self-Organizing Maps (SOM). NB-compliant sets of descriptors were shown to display enhanced mapping propensities, allowing the construction of better Self-Organizing Maps and similarity searches (NB and classical similarity search criteria--AUC ROC--correlate at a level of 0.7). The analysis of the SOM clusters proved chemically meaningful CGR substructures representing specific reaction signatures.

A two-step acid-catalyzed process for the production of biodiesel from rice bran oil

Energy Technology Data Exchange (ETDEWEB)

Zullaikah, S.; Lai, Chao Chin; Vali, S.R.; Ju, Yi Hsu [National Taiwan Univ. of Science and Technology, Taipei (China). Dept. of Chemical Engineering

2005-11-15

A study was undertaken to examine the effect of temperature, moisture and storage time on the accumulation of free fatty acid in the rice bran. Rice bran stored at room temperature showed that most triacylglyceride was hydrolyzed and free fatty acid (FFA) content was raised up to 76% in six months. A two-step acid-catalyzed methanolysis process was employed for the efficient conversion of rice bran oil into fatty acid methyl ester (FAME). The first step was carried out at 60 {sup o}C. Depending on the initial FFA content of oil, 55-90% FAME content in the reaction product was obtained. More than 98% FFA and less than 35% of TG were reacted in 2 h. The organic phase of the first step reaction product was used as the substrate for a second acid-catalyzed methanolysis at 100 {sup o}C. By this two-step methanolysis reaction, more than 98% FAME in the product can be obtained in less than 8 h. Distillation of reaction product gave 99.8% FAME (biodiesel) with recovery of more than 96%. The residue contains enriched nutraceuticals such as {gamma}-oryzanol (16-18%), mixture of phytosterol, tocol and steryl ester (19-21%). (author)

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

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.

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.

Reaction mechanisms of ruthenium tetroxide mediated oxidations of organic compounds

Energy Technology Data Exchange (ETDEWEB)

Froehaug, Astrid Elisabeth

1995-12-31

This thesis reports a study of the mechanism of ruthenium tetroxide mediated oxidations of saturated hydrocarbons, ethers, alkenes and alcohols. Several methods were used. The RuO{sub 4}-mediated oxidations of adamantane and cis-decalin were studied in CCl{sub 4}-CH{sub 3}CN-H{sub 2}O and in acetone-water. The rate of reaction was found to be moderately influenced by the polarity of the solvent. Solvent properties other than the polarity were also found to influence the reaction rates. From the oxidations of adamantane and adamantane-1,3,5,7-d{sub 4} two primary kinetic deuterium isotope effects were found. These were comparable with the deuterium isotope effects found for the analogous oxidations of cis-decalin and cis-decalin-d{sub 18}. The results seem to exclude both a one step hydride abstraction reaction mechanism and a one step concerted mechanism, as well as a scheme where two such mechanisms compete. The observations may be explained by a two step reaction mechanism consisting of a pre-equilibrium with formation of a substrate-RuO{sub 4} complex followed by a concerted rate determining reaction. The RuO{sub 4}-mediated oxidation of ethers was of kinetic second order with a small enthalpy of activation and a large negative entropy of activation. Oxidation of cyclopropylmethyl methyl ether gave methyl cyclopropanecarboxylate, no rearranged products were observed. On RuO{sub 4} oxidations in CCl{sub 4} with NaIO{sub 4} as stoichiometric oxidant, no chlorinated products were observed. Several observations not in agreement with a hydride or a hydrogen abstraction mechanism may be explained by assuming that the reaction proceeds by either a concerted reaction or by a reversible oxidative addition of the ether to RuO{sub 4} followed by a slow concerted step. 228 refs., 9 figs., 27 tabs.

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.

(4+2) Cycloaddition reactions with inverse electron demand of nitrogen bearing, heteroaromatic cations

International Nuclear Information System (INIS)

Ritzberger-Baumgartner, W.

1996-06-01

Three cationic, heteroaromatic diene-systems (1, 2, 3, 4-tetramethoxycarbonyl-quinolizinium-tetrafluoroborate (M), 8, 9, 10, 11-tetrarnethoxycarbonylpyrido[2,1-a]-isoquinolinium-TFB and triazolo[1,5-b]isoquinolinium-TFBs) and a cationic, non-aromatic diene (2,5,5-trimethyl-3-oxo-1, 2, 4-triazolium-TFB) were synthesized. The dienes were employed successfully in cycloaddition reactions with a number ofconjugated dienophiles (including norbornene). The mechanism underlying these cycloaddition reactions was discussed in the theoretical section. At first quantumchemical calculations of the frontier orbital energies provided the proof, that the reactions followed the pattern of reactions with inverse electron demand. Calculation of the charge distribution and of the orbital coefficients led to the conclusion, that these reactions are mainly orbital controlled. Two mechanistic variants were in discussion. Either the reactions proceed in a concerted manner resembling the Diels-Alder reaction with inverse electron demand or in two distinct steps with the formation of a cationic intermediate following the attack of the heterodienes acting as weak electrophiles at the dienophiles being weak nucleophiles. Calculations of a possible transition state of these cycloaddition reactions revealed a pronounced preference for the formation of the bond between the logical reaction centers in the first step of a two-step reaction. However, experimental and theoretical findings led to the conviction, that cationic polar cycloaddition reactions proceed exactly along the crossroad between a concerted and a two-step mechanism and depending on the electrophilic strength of the diene and the nucleophilic strength of the dienophile these reactions show more characteristics of one of the two mechanistic possibilities. The high regioselectivity as well as the high stereoselectivity could be explained satisfactory with the help of the calculated orbital coefficients. (author)

Possibilities and scope of the double isotope effect method in the elucidation of mechanisms of enzyme catalyzed reactions

Energy Technology Data Exchange (ETDEWEB)

Schmidt, H L; Medina, R [Technische Univ. Muenchen, Freising (Germany, F.R.). Lehrstuhl fuer Allgemeine Chemie und Biochemie

1991-01-01

Kinetic isotope effects on enzyme catalyzed reactions are indicative for the first irreversible in a sequence of individual steps. Hints on the relative velocities of other steps can only be obtained from the partitioning factor R and its dependence on external reaction conditions. In general, the experimental data needed are obtained from isotope abundance measurements in a defined position of the substrate or product as a function of turnover. This method does not reveal events dealing with neighbour atoms or preceding the main isotope sensitive step. In the method presented here, the analytical measurement is extended to the second atom involved in a bond fission of formation (Double Isotope Effect Method). It is shown that the additional results obtained support the identification of the main isotopically sensitive step and its relative contribution to the overall reaction rate, the identification of other kinetically significant steps and the differentiation between stepwise and concerted reaction mechanisms. The method and its advantages are demonstrated on reactions comprising C-N-bond splitting (urease and arginase reaction), C-C-bound fission (reactions catalyzed by pyruvate-dehydrogenase, pyruvate-formiate-lyase and lactate-oxidase), C-O-bound formation (ribulose-bisphosphate-oxygenase reaction), and N-O-bond fission (nitrate- and nitrite-reductase reactions). (orig.).

One- and two-dimensional infrared spectroscopic studies of solution-phase homogeneous catalysis and spin-forbidden reactions

Energy Technology Data Exchange (ETDEWEB)

Sawyer, Karma Rae [Univ. of California, Berkeley, CA (United States)

2008-12-01

Understanding chemical reactions requires the knowledge of the elementary steps of breaking and making bonds, and often a variety of experimental techniques are needed to achieve this goal. The initial steps occur on the femto- through picosecond time-scales, requiring the use of ultrafast spectroscopic methods, while the rate-limiting steps often occur more slowly, requiring alternative techniques. Ultrafast one and two-dimensional infrared and step-scan FTIR spectroscopies are used to investigate the photochemical reactions of four organometallic complexes. The analysis leads to a detailed understanding of mechanisms that are general in nature and may be applicable to a variety of reactions.

Identifying Understudied Nuclear Reactions by Text-mining the EXFOR Experimental Nuclear Reaction Library

Energy Technology Data Exchange (ETDEWEB)

Hirdt, J.A. [Department of Mathematics and Computer Science, St. Joseph' s College, Patchogue, NY 11772 (United States); Brown, D.A., E-mail: dbrown@bnl.gov [National Nuclear Data Center, Brookhaven National Laboratory, Upton, NY 11973-5000 (United States)

2016-01-15

The EXFOR library contains the largest collection of experimental nuclear reaction data available as well as the data's bibliographic information and experimental details. We text-mined the REACTION and MONITOR fields of the ENTRYs in the EXFOR library in order to identify understudied reactions and quantities. Using the results of the text-mining, we created an undirected graph from the EXFOR datasets with each graph node representing a single reaction and quantity and graph links representing the various types of connections between these reactions and quantities. This graph is an abstract representation of the connections in EXFOR, similar to graphs of social networks, authorship networks, etc. We use various graph theoretical tools to identify important yet understudied reactions and quantities in EXFOR. Although we identified a few cross sections relevant for shielding applications and isotope production, mostly we identified charged particle fluence monitor cross sections. As a side effect of this work, we learn that our abstract graph is typical of other real-world graphs.

Identifying Understudied Nuclear Reactions by Text-mining the EXFOR Experimental Nuclear Reaction Library

International Nuclear Information System (INIS)

Hirdt, J.A.; Brown, D.A.

2016-01-01

The EXFOR library contains the largest collection of experimental nuclear reaction data available as well as the data's bibliographic information and experimental details. We text-mined the REACTION and MONITOR fields of the ENTRYs in the EXFOR library in order to identify understudied reactions and quantities. Using the results of the text-mining, we created an undirected graph from the EXFOR datasets with each graph node representing a single reaction and quantity and graph links representing the various types of connections between these reactions and quantities. This graph is an abstract representation of the connections in EXFOR, similar to graphs of social networks, authorship networks, etc. We use various graph theoretical tools to identify important yet understudied reactions and quantities in EXFOR. Although we identified a few cross sections relevant for shielding applications and isotope production, mostly we identified charged particle fluence monitor cross sections. As a side effect of this work, we learn that our abstract graph is typical of other real-world graphs.

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...

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.

Mechanistic insights into the dehalogenation reaction of fluoroacetate/fluoroacetic acid

Science.gov (United States)

Miranda-Rojas, Sebastián; Toro-Labbé, Alejandro

2015-05-01

Fluoroacetate is a toxic compound whose environmental accumulation may represent an important contamination problem, its elimination is therefore a challenging issue. Fluoroacetate dehalogenase catalyzes its degradation through a two step process initiated by an SN2 reaction in which the aspartate residue performs a nucleophilic attack on the carbon bonded to the fluorine; the second step is hydrolysis that releases the product as glycolate. In this paper, we present a study based on density functional theory calculations of the SN2 initiation reaction modeled through the interaction between the substrate and the propionate anion as the nucleophile. Results are analyzed within the framework of the reaction force and using the reaction electronic flux to identify and characterize the electronic activity that drives the reaction. Our results reveal that the selective protonation of the substrate catalyzes the reaction by decreasing the resistance of the structural and electronic reorganization needed to reach the transition state. Finally, the reaction energy is modulated by the degree of stabilization of the fluoride anion formed after the SN2 reaction. In this way, a site-induced partial protonation acts as a chemical switch in a key process that determines the output of the reaction.

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.

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).

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.

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.

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.

One-step preparation of antimicrobial silver nanoparticles in polymer matrix

Energy Technology Data Exchange (ETDEWEB)

Lyutakov, O., E-mail: lyutakoo@vscht.cz; Kalachyova, Y. [Institute of Chemical Technology, Department of Solid State Engineering (Czech Republic); Solovyev, A. [Institute of Chemical Process Fundamentals of the ASCR (Czech Republic); Vytykacova, S. [Institute of Chemical Technology, Department of Glass and Ceramics (Czech Republic); Svanda, J.; Siegel, J. [Institute of Chemical Technology, Department of Solid State Engineering (Czech Republic); Ulbrich, P. [Institute of Chemical Technology, Department of Biochemistry and Microbiology (Czech Republic); Svorcik, V. [Institute of Chemical Technology, Department of Solid State Engineering (Czech Republic)

2015-03-15

Simple one-step procedure for in situ preparation of silver nanoparticles (AgNPs) in the polymer thin films is described. Nanoparticles (NPs) were prepared by reaction of N-methyl pyrrolidone with silver salt in semi-dry polymer film and characterized by transmission electron microscopy, XPS, and UV–Vis spectroscopy techniques. Direct synthesis of NPs in polymer has several advantages; even though it avoids time-consuming NPs mixing with polymer matrix, uniform silver distribution in polymethylmethacrylate (PMMA) films is achieved without necessity of additional stabilization. The influence of the silver concentration, reaction temperature and time on reaction conversion rate, and the size and size-distribution of the AgNPs was investigated. Polymer films doped with AgNPs were tested for their antibacterial activity on Gram-negative bacteria. Antimicrobial properties of AgNPs/PMMA films were found to be depended on NPs concentration, their size and distribution. Proposed one-step synthesis of functional polymer containing AgNPs is environmentally friendly, experimentally simple and extremely quick. It opens up new possibilities in development of antimicrobial coatings with medical and sanitation applications.

One-step preparation of antimicrobial silver nanoparticles in polymer matrix

International Nuclear Information System (INIS)

Lyutakov, O.; Kalachyova, Y.; Solovyev, A.; Vytykacova, S.; Svanda, J.; Siegel, J.; Ulbrich, P.; Svorcik, V.

2015-01-01

Simple one-step procedure for in situ preparation of silver nanoparticles (AgNPs) in the polymer thin films is described. Nanoparticles (NPs) were prepared by reaction of N-methyl pyrrolidone with silver salt in semi-dry polymer film and characterized by transmission electron microscopy, XPS, and UV–Vis spectroscopy techniques. Direct synthesis of NPs in polymer has several advantages; even though it avoids time-consuming NPs mixing with polymer matrix, uniform silver distribution in polymethylmethacrylate (PMMA) films is achieved without necessity of additional stabilization. The influence of the silver concentration, reaction temperature and time on reaction conversion rate, and the size and size-distribution of the AgNPs was investigated. Polymer films doped with AgNPs were tested for their antibacterial activity on Gram-negative bacteria. Antimicrobial properties of AgNPs/PMMA films were found to be depended on NPs concentration, their size and distribution. Proposed one-step synthesis of functional polymer containing AgNPs is environmentally friendly, experimentally simple and extremely quick. It opens up new possibilities in development of antimicrobial coatings with medical and sanitation applications

A green two-step process for adipic acid production from cyclohexene. A study on parameters affecting selectivity

Energy Technology Data Exchange (ETDEWEB)

Cavani, F.; Macchia, F.; Pino, R.; Raabova, K.; Rozhko, E. [Bologna Univ. (Italy). Dipt. di Chimica Industriale e dei Materiali; Alini, S.; Accorinti, P.; Babini, G. [Radici Chimica SpA, Novara (Italy)

2011-07-01

In this paper, we report about the effect of reaction parameters on catalytic behavior in a twostep process aimed at the synthesis of adipic acid from cyclohexene. In the first step, cyclohexene reacts with an aqueous solution of hydrogen peroxide, under conditions leading to the formation of trans-1,2-cyclohexandiol as the prevailing product; the reaction is catalysed by tungstic acid, in the presence of phosphoric acid and of a PT agent. In the second step, 1,2-cyclohexandiol is oxidized with air, in the presence of an heterogeneous catalyst made of alumina-supported Ru(OH){sub 3}. This process is aimed at using the minimal amount of the costly hydrogen peroxide, since only one mole is theoretically needed per mole of cyclohexene. The first step afforded very high yield to the glycol, using only a slight excess of hydrogen peroxide. However, the second step turned out to be the more critical one, since the selectivity to adipic acid was very low because of the concomitant occurrence of several undesired side reactions. The latter were in part due to the reaction conditions used, which were necessary for the activation of cyclohexandiol. (orig.)

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

The Effect of First-Step Techniques from the Staggered Stance in American Football

DEFF Research Database (Denmark)

Knudsen, Nikolas Sten; Andersen, Thomas Bull

2017-01-01

.77±0.10 s) being faster than FFS (1.81±0.12 s) and BFS (2.01±0.13 s), and FFS being faster than BFS, although no differences were found in reaction time. In terms of mean force and power, NORM (331.1±39.2N, 542.2±72.3W) and FFS (320.8±43.2N, 550.9±81.4W) were significantly larger than BFS (256.9±36.2N, 443...... in each technique (normal (NORM), backwards false step (BFS) and forwards false step (FFS)) in random order. Sprint starts were performed on force plates to investigate ground reaction forces, reaction time and total sprint time. Analysis showed significant differences in sprint times, with NORM (1...

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.

Exchange reaction between hydrogen and deuterium. I. Importance of surface reactions in the steady-state mechanism

Energy Technology Data Exchange (ETDEWEB)

Marteau, C; Gaillard-Cusin, F; James, H [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

1978-05-01

Investigation of heterogeneous initiation process of gas phase linear chain reactions is carried out through the study of H/sub 2/-D/sub 2/ exchange reaction. Experimental data under study concern mainly the stationary rate of HD formation and the prestationary proceeding. Steady-state method accounts for the first one of these data; it allows to clearly compare the wall process part to the part played by the homogeneous chain reaction towards HD formation. Activation energy of exchange elementary step between chemisorbed hydrogen (on silica) and gaseous deuterium has been evaluated: Esub(e1)=52+-1 Kcal/mole.

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.

Step-to-step reproducibility and asymmetry to study gait auto-optimization in healthy and cerebral palsied subjects.

Science.gov (United States)

Descatoire, A; Femery, V; Potdevin, F; Moretto, P

2009-05-01

The purpose of our study was to compare plantar pressure asymmetry and step-to-step reproducibility in both able-bodied persons and two groups of hemiplegics. The relevance of the research was to determine the efficiency of asymmetry and reproducibility as indexes for diagnosis and rehabilitation processes. This study comprised 31 healthy young subjects and 20 young subjects suffering from cerebral palsy hemiplegia assigned to two groups of 10 subjects according to the severity of their musculoskeletal disorders. The peaks of plantar pressure and the time to peak pressure were recorded with an in-shoe measurement system. The intra-individual coefficient of variability was calculated to indicate the consistency of plantar pressure during walking and to define gait stability. The effect size was computed to quantify the asymmetry and measurements were conducted at eight footprint locations. Results indicated few differences in step-to-step reproducibility between the healthy group and the less spastic group while the most affected group showed a more asymmetrical and unstable gait. From the concept of self-optimisation and depending on the neuromotor disorders the organism could make priorities based on pain, mobility, stability or energy expenditure to develop the best gait auto-optimisation.

Anodic Cyclization Reactions and the Mechanistic Strategies That Enable Optimization.

Science.gov (United States)

Feng, Ruozhu; Smith, Jake A; Moeller, Kevin D

2017-09-19

Oxidation reactions are powerful tools for synthesis because they allow us to reverse the polarity of electron-rich functional groups, generate highly reactive intermediates, and increase the functionality of molecules. For this reason, oxidation reactions have been and continue to be the subject of intense study. Central to these efforts is the development of mechanism-based strategies that allow us to think about the reactive intermediates that are frequently central to the success of the reactions and the mechanistic pathways that those intermediates trigger. For example, consider oxidative cyclization reactions that are triggered by the removal of an electron from an electron-rich olefin and lead to cyclic products that are functionalized for further elaboration. For these reactions to be successful, the radical cation intermediate must first be generated using conditions that limit its polymerization and then channeled down a productive desired pathway. Following the cyclization, a second oxidation step is necessary for product formation, after which the resulting cation must be quenched in a controlled fashion to avoid undesired elimination reactions. Problems can arise at any one or all of these steps, a fact that frequently complicates reaction optimization and can discourage the development of new transformations. Fortunately, anodic electrochemistry offers an outstanding opportunity to systematically probe the mechanism of oxidative cyclization reactions. The use of electrochemical methods allows for the generation of radical cations under neutral conditions in an environment that helps prevent polymerization of the intermediate. Once the intermediates have been generated, a series of "telltale indicators" can be used to diagnose which step in an oxidative cyclization is problematic for less successful transformation. A set of potential solutions to address each type of problem encountered has been developed. For example, problems with the initial

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.

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)...

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

Mechanistic insights into the dehalogenation reaction of fluoroacetate/fluoroacetic acid

International Nuclear Information System (INIS)

Miranda-Rojas, Sebastián; Toro-Labbé, Alejandro

2015-01-01

Fluoroacetate is a toxic compound whose environmental accumulation may represent an important contamination problem, its elimination is therefore a challenging issue. Fluoroacetate dehalogenase catalyzes its degradation through a two step process initiated by an S N 2 reaction in which the aspartate residue performs a nucleophilic attack on the carbon bonded to the fluorine; the second step is hydrolysis that releases the product as glycolate. In this paper, we present a study based on density functional theory calculations of the S N 2 initiation reaction modeled through the interaction between the substrate and the propionate anion as the nucleophile. Results are analyzed within the framework of the reaction force and using the reaction electronic flux to identify and characterize the electronic activity that drives the reaction. Our results reveal that the selective protonation of the substrate catalyzes the reaction by decreasing the resistance of the structural and electronic reorganization needed to reach the transition state. Finally, the reaction energy is modulated by the degree of stabilization of the fluoride anion formed after the S N 2 reaction. In this way, a site-induced partial protonation acts as a chemical switch in a key process that determines the output of the reaction

Mechanistic insights into the dehalogenation reaction of fluoroacetate/fluoroacetic acid

Energy Technology Data Exchange (ETDEWEB)

Miranda-Rojas, Sebastián, E-mail: sebastian.miranda@unab.cl [Chemical Processes and Catalysis (CPC), Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Avenida República 275, Santiago (Chile); Toro-Labbé, Alejandro [Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago (Chile)

2015-05-21

Fluoroacetate is a toxic compound whose environmental accumulation may represent an important contamination problem, its elimination is therefore a challenging issue. Fluoroacetate dehalogenase catalyzes its degradation through a two step process initiated by an S{sub N}2 reaction in which the aspartate residue performs a nucleophilic attack on the carbon bonded to the fluorine; the second step is hydrolysis that releases the product as glycolate. In this paper, we present a study based on density functional theory calculations of the S{sub N}2 initiation reaction modeled through the interaction between the substrate and the propionate anion as the nucleophile. Results are analyzed within the framework of the reaction force and using the reaction electronic flux to identify and characterize the electronic activity that drives the reaction. Our results reveal that the selective protonation of the substrate catalyzes the reaction by decreasing the resistance of the structural and electronic reorganization needed to reach the transition state. Finally, the reaction energy is modulated by the degree of stabilization of the fluoride anion formed after the S{sub N}2 reaction. In this way, a site-induced partial protonation acts as a chemical switch in a key process that determines the output of the reaction.

Ultrasonic transesterification of Jatrophacurcas L. oil to biodiesel by a two-step process

International Nuclear Information System (INIS)

Deng Xin; Fang Zhen; Liu Yunhu

2010-01-01

Transesterification of high free fatty acid content Jatropha oil with methanol to biodiesel catalyzed directly by NaOH and high-concentrated H 2 SO 4 or by two-step process were studied in an ultrasonic reactor at 60 deg. C. If NaOH was used as catalyst, biodiesel yield was only 47.2% with saponification problem. With H 2 SO 4 as catalyst, biodiesel yield was increased to 92.8%. However, longer reaction time (4 h) was needed and the biodiesel was not stable. A two-step, acid-esterification and base-transesterification process was further used for biodiesel production. It was found that after the first-step pretreatment with H 2 SO 4 for 1 h, the acid value of Jatropha oil was reduced from 10.45 to 1.2 mg KOH/g, and subsequently, NaOH was used for the second-step transesterification. Stable and clear yellowish biodiesel was obtained with 96.4% yield after reaction for 0.5 h. The total production time was only 1.5 h that is just half of the previous reported. The two-step process with ultrasonic radiation is effective and time-saving for biodiesel production from Jatropha oil.

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.

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.

Modulation of EMG-EMG Coherence in a Choice Stepping Task

Directory of Open Access Journals (Sweden)

Ippei Nojima

2018-02-01

Full Text Available The voluntary step execution task is a popular measure for identifying fall risks among elderly individuals in the community setting because most falls have been reported to occur during movement. However, the neurophysiological functions during this movement are not entirely understood. Here, we used electromyography (EMG to explore the relationship between EMG-EMG coherence, which reflects common oscillatory drive to motoneurons, and motor performance associated with stepping tasks: simple reaction time (SRT and choice reaction time (CRT tasks. Ten healthy elderly adults participated in the study. Participants took a single step forward in response to a visual imperative stimulus. EMG-EMG coherence was analyzed for 1000 ms before the presentation of the stimulus (stationary standing position from proximal and distal tibialis anterior (TA and soleus (SOL muscles. The main result showed that all paired EMG-EMG coherences in the alpha and beta frequency bands were greater in the SRT than the CRT task. This finding suggests that the common oscillatory drive to the motoneurons during the SRT task occurred prior to taking a step, whereas the lower value of corticospinal activity during the CRT task prior to taking a step may indicate an involvement of inhibitory activity, which is consistent with observations from our previous study (Watanabe et al., 2016. Furthermore, the beta band coherence in intramuscular TA tended to positively correlate with the number of performance errors that are associated with fall risks in the CRT task, suggesting that a reduction in the inhibitory activity may result in a decrease of stepping performance. These findings could advance the understanding of the neurophysiological features of postural adjustments in elderly individuals.

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.

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.

Differentiation between solid-ankle cushioned heel and energy storage and return prosthetic foot based on step-to-step transition cost.

Science.gov (United States)

Wezenberg, Daphne; Cutti, Andrea G; Bruno, Antonino; Houdijk, Han

2014-01-01

Decreased push-off power by the prosthetic foot and inadequate roll-over shape of the foot have been shown to increase the energy dissipated during the step-to-step transition in human walking. The aim of this study was to determine whether energy storage and return (ESAR) feet are able to reduce the mechanical energy dissipated during the step-to-step transition. Fifteen males with a unilateral lower-limb amputation walked with their prescribed ESAR foot (Vari-Flex, Ossur; Reykjavik, Iceland) and with a solid-ankle cushioned heel foot (SACH) (1D10, Ottobock; Duderstadt, Germany), while ground reaction forces and kinematics were recorded. The positive mechanical work on the center of mass performed by the trailing prosthetic limb was larger (33%, p = 0.01) and the negative work performed by the leading intact limb was lower (13%, p = 0.04) when walking with the ESAR foot compared with the SACH foot. The reduced step-to-step transition cost coincided with a higher mechanical push-off power generated by the ESAR foot and an extended forward progression of the center of pressure under the prosthetic ESAR foot. Results can explain the proposed improvement in walking economy with this kind of energy storing and return prosthetic foot.

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.

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...

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....

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...

Effect of potential steps on porous silicon formation

International Nuclear Information System (INIS)

Cheng Xuan; Feng Zude; Luo Guangfeng

2003-01-01

Porous silicon microstructures were fabricated by applying potential steps through which both anodic and cathodic potentials were periodically applied to silicon wafers. The electrochemical behaviors of porous silicon layers were examined by performing polarization measurements, followed by analyzing the open-circuit potential (E ocp ) and the reaction rate in terms of corrosion current density (j corr ). The surface morphologies and surface products of porous silicon were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). It was found that the values of E ocp and j corr varied more significantly and irregularly during different polarization stages when the potentials were continuously applied to the wafer surface, while virtually unchanged after 2 min of periodic potential application. In addition, slower reaction rates were observed with applying potential steps, as indicated by smaller values of j corr . The enhancement on refreshment of silicon surfaces by periodic potential polarization significantly accelerated the growth of porous silicon. The microstructures became more uniformed and better defined due to the improved passivating nature of wafer surfaces

An autonomous organic reaction search engine for chemical reactivity

Science.gov (United States)

Dragone, Vincenza; Sans, Victor; Henson, Alon B.; Granda, Jaroslaw M.; Cronin, Leroy

2017-06-01

The exploration of chemical space for new reactivity, reactions and molecules is limited by the need for separate work-up-separation steps searching for molecules rather than reactivity. Herein we present a system that can autonomously evaluate chemical reactivity within a network of 64 possible reaction combinations and aims for new reactivity, rather than a predefined set of targets. The robotic system combines chemical handling, in-line spectroscopy and real-time feedback and analysis with an algorithm that is able to distinguish and select the most reactive pathways, generating a reaction selection index (RSI) without need for separate work-up or purification steps. This allows the automatic navigation of a chemical network, leading to previously unreported molecules while needing only to do a fraction of the total possible reactions without any prior knowledge of the chemistry. We show the RSI correlates with reactivity and is able to search chemical space using the most reactive pathways.

A study on the hierarchy model of nuclear reactions

International Nuclear Information System (INIS)

Kitazoe, Yasuhiro; Sekiya, Tamotsu

1975-01-01

The application of the hierarchy model of nuclear reaction is discussed, and the hierarchy model means that the compound nucleus state is formed after several steps, at least, one step of reaction. This model was applied to the analysis of the observed cross sections of 235 U and some other elements. Neglecting exchange scattering effect, the equations for the total neutron cross section of 235 U were obtained. One of these equations describes explicitly the hierarchy of the transition from intermediate reaction state Xm into the compound nucleus state Xs, and another one describes the cross section averaged over an energy interval larger than the average level spacing of compound nucleus eigenvalues. The hierarchy of reaction mechanism was investigated in more detail, and the hierarchy model was applied to the case of unresolved energy region. It was not tried to evaluate the strength function in the mass region (A>140), since the effect of nuclear deformation was neglected in the task. (Iwase, T.)

[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

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.

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.

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.

Study of parameters affecting the conversion in a plug flow reactor for reactions of the type 2A→B

Science.gov (United States)

Beltran-Prieto, Juan Carlos; Long, Nguyen Huynh Bach Son

2018-04-01

Modeling of chemical reactors is an important tool to quantify reagent conversion, product yield and selectivity towards a specific compound and to describe the behavior of the system. Proposal of differential equations describing the mass and energy balance are among the most important steps required during the modeling process as they play a special role in the design and operation of the reactor. Parameters governing transfer of heat and mass have a strong relevance in the rate of the reaction. Understanding this information is important for the selection of reactor and operating regime. In this paper we studied the irreversible gas-phase reaction 2A→B. We model the conversion that can be achieved as function of the reactor volume and feeding temperature. Additionally, we discuss the effect of activation energy and the heat of reaction on the conversion achieved in the tubular reactor. Furthermore, we considered that dimerization occurs instantaneously in the catalytic surface to develop equations for the determination of rate of reaction per unit area of three different catalytic surface shapes. This data can be combined with information about the global rate of conversion in the reactor to improve regent conversion and yield of product.

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.

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.

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

Reaction probability derived from an interpolation formula for diffusion processes with an absorptive boundary condition

International Nuclear Information System (INIS)

Misawa, T.; Itakura, H.

1995-01-01

The present article focuses on a dynamical simulation of molecular motion in liquids. In the simulation involving diffusion-controlled reaction with discrete time steps, lack of information regarding the trajectory within the time step may result in a failure to count the number of reactions of the particles within the step. In order to rectify this, an interpolated diffusion process is used. The process is derived from a stochastic interpolation formula recently developed by the first author [J. Math. Phys. 34, 775 (1993)]. In this method, the probability that reaction has occurred during the time step given the initial and final positions of the particles is calculated. Some numerical examples confirm that the theoretical result corresponds to an improvement over the Clifford-Green work [Mol. Phys. 57, 123 (1986)] on the same matter

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.

Thermal decomposition pathways of hydroxylamine: theoretical investigation on the initial steps.

Science.gov (United States)

Wang, Qingsheng; Wei, Chunyang; Pérez, Lisa M; Rogers, William J; Hall, Michael B; Mannan, M Sam

2010-09-02

Hydroxylamine (NH(2)OH) is an unstable compound at room temperature, and it has been involved in two tragic industrial incidents. Although experimental studies have been carried out to study the thermal stability of hydroxylamine, the detailed decomposition mechanism is still in debate. In this work, several density functional and ab initio methods were used in conjunction with several basis sets to investigate the initial thermal decomposition steps of hydroxylamine, including both unimolecular and bimolecular reaction pathways. The theoretical investigation shows that simple bond dissociations and unimolecular reactions are unlikely to occur. The energetically favorable initial step of decomposition pathways was determined as a bimolecular isomerization of hydroxylamine into ammonia oxide with an activation barrier of approximately 25 kcal/mol at the MPW1K level of theory. Because hydroxylamine is available only in aqueous solutions, solvent effects on the initial decomposition pathways were also studied using water cluster methods and the polarizable continuum model (PCM). In water, the activation barrier of the bimolecular isomerization reaction decreases to approximately 16 kcal/mol. The results indicate that the bimolecular isomerization pathway of hydroxylamine is more favorable in aqueous solutions. However, the bimolecular nature of this reaction means that more dilute aqueous solution will be more stable.

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

Efficient Isomerization of Glucose to Fructose over Zeolites in Consecutive Reactions in Alcohol and Aqueous Media

DEFF Research Database (Denmark)

Shunmugavel, Saravanamurugan; Paniagua, Marta; Melero, Juan A

2013-01-01

glucose isomerization to fructose and subsequent reaction with methanol to form methyl fructoside (step 1), followed by hydrolysis to re-form fructose after water addition (step 2). NMR analysis with (13)C-labeled sugars confirmed this reaction pathway. Conversion of glucose for 1 h at 120 °C with H......-USY (Si/Al = 6) gave a remarkable 55% yield of fructose after the second reaction step. A main advantage of applying alcohol media and a catalyst that combines Brønsted and Lewis acid sites is that glucose is isomerized to fructose at low temperatures, while direct conversion to industrially important...

Neutrino reactions in hot and dense matter

Energy Technology Data Exchange (ETDEWEB)

Lohs, Andreas

2015-04-13

In this thesis, neutrino reactions in hot and dense matter are studied. In particular, this work is concerned with neutrino-matter interactions that are relevant for neutrino transport in core-collapse supernovae (CCSNe). The majority of the energy from a CCSN is released in the form of neutrinos. Accurate understanding and computation of these interactions is most relevant to achieve sufficiently reliable predictions for the evolution of CCSNe and other related question such as the production of heavy elements or neutrino oscillations. For this purpose this work follows the combined approach of searching for new important neutrino reactions and improving the computation of those reactions that are already implemented. First we estimate the relevance of charged-current weak interactions that include muon-neutrinos or muons, as well as the role of neutron decay for neutrino transport in CCSNe. All of these reactions were previously neglected in CCSN-simulations. We derive and compute the matrix element and subsequent semi-analytic expressions for transport properties like the inverse mean free path of the new reactions. It is found that these reactions are important for muon neutrinos and low energy electron antineutrinos at very high densities in the protoneutron star surface. Consequently their implementation might lead to several changes in the prediction of CCSNe signatures such as the nucleosynthesis yields. Second we improve the precision in the computation of well known neutrino-nucleon reactions like neutrino absorption on neutrons. We derive semi-analytic expressions for transport properties that use less restrictive approximations while keeping the computational demand constant. Therefore we consider the full relativistic kinematics of all participating particles i.e. allowing for relativistic nucleons and finite lepton masses. Also the weak magnetism terms of the matrix elements are explicitly included to all orders. From our results we suggest that the

Neutrino reactions in hot and dense matter

International Nuclear Information System (INIS)

Lohs, Andreas

2015-01-01

In this thesis, neutrino reactions in hot and dense matter are studied. In particular, this work is concerned with neutrino-matter interactions that are relevant for neutrino transport in core-collapse supernovae (CCSNe). The majority of the energy from a CCSN is released in the form of neutrinos. Accurate understanding and computation of these interactions is most relevant to achieve sufficiently reliable predictions for the evolution of CCSNe and other related question such as the production of heavy elements or neutrino oscillations. For this purpose this work follows the combined approach of searching for new important neutrino reactions and improving the computation of those reactions that are already implemented. First we estimate the relevance of charged-current weak interactions that include muon-neutrinos or muons, as well as the role of neutron decay for neutrino transport in CCSNe. All of these reactions were previously neglected in CCSN-simulations. We derive and compute the matrix element and subsequent semi-analytic expressions for transport properties like the inverse mean free path of the new reactions. It is found that these reactions are important for muon neutrinos and low energy electron antineutrinos at very high densities in the protoneutron star surface. Consequently their implementation might lead to several changes in the prediction of CCSNe signatures such as the nucleosynthesis yields. Second we improve the precision in the computation of well known neutrino-nucleon reactions like neutrino absorption on neutrons. We derive semi-analytic expressions for transport properties that use less restrictive approximations while keeping the computational demand constant. Therefore we consider the full relativistic kinematics of all participating particles i.e. allowing for relativistic nucleons and finite lepton masses. Also the weak magnetism terms of the matrix elements are explicitly included to all orders. From our results we suggest that the

Separation of uranium and rare earth elements from Rirang ore leach solution by two-step precipitation

International Nuclear Information System (INIS)

Sradjono; Erni Rifandriyah, A.; Zahardi

1995-01-01

Separation of uranium and rare-earth elements from Rirang ore leach solution was carried out through a two-step precipitation. Several condition affecting the separation processes were examined including solution pH, reagent concentration, and reaction prepitation time. Optimum conditions for the first and second precipitation steps include adjustment of precipitation pH to 1.3 and 2.3, respectively by the addition of 7.3% of NH 4 OH solution and allowing 60 minutes precipitation/reaction time. Based on the conditions, about 6% of Th, 3% of U, 0.9% of PO 4 3- , and none of RE were recovered in the first precipitation step meanwhile, about 99% of RE, 55% of U, 76% of PO 4 3- , and of the Th were recovered in the second step. (author). 3 refs. 4 tabs. 4 figs

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

STEPS: efficient simulation of stochastic reaction–diffusion models in realistic morphologies

Directory of Open Access Journals (Sweden)

Hepburn Iain

2012-05-01

Full Text Available Abstract Background Models of cellular molecular systems are built from components such as biochemical reactions (including interactions between ligands and membrane-bound proteins, conformational changes and active and passive transport. A discrete, stochastic description of the kinetics is often essential to capture the behavior of the system accurately. Where spatial effects play a prominent role the complex morphology of cells may have to be represented, along with aspects such as chemical localization and diffusion. This high level of detail makes efficiency a particularly important consideration for software that is designed to simulate such systems. Results We describe STEPS, a stochastic reaction–diffusion simulator developed with an emphasis on simulating biochemical signaling pathways accurately and efficiently. STEPS supports all the above-mentioned features, and well-validated support for SBML allows many existing biochemical models to be imported reliably. Complex boundaries can be represented accurately in externally generated 3D tetrahedral meshes imported by STEPS. The powerful Python interface facilitates model construction and simulation control. STEPS implements the composition and rejection method, a variation of the Gillespie SSA, supporting diffusion between tetrahedral elements within an efficient search and update engine. Additional support for well-mixed conditions and for deterministic model solution is implemented. Solver accuracy is confirmed with an original and extensive validation set consisting of isolated reaction, diffusion and reaction–diffusion systems. Accuracy imposes upper and lower limits on tetrahedron sizes, which are described in detail. By comparing to Smoldyn, we show how the voxel-based approach in STEPS is often faster than particle-based methods, with increasing advantage in larger systems, and by comparing to MesoRD we show the efficiency of the STEPS implementation. Conclusion STEPS simulates

Proton transfers in the Strecker reaction revealed by DFT calculations

Directory of Open Access Journals (Sweden)

Shinichi Yamabe

2014-08-01

Full Text Available The Strecker reaction of acetaldehyde, NH3, and HCN to afford alanine was studied by DFT calculations for the first time, which involves two reaction stages. In the first reaction stage, the aminonitrile was formed. The rate-determining step is the deprotonation of the NH3+ group in MeCH(OH-NH3+ to form 1-aminoethanol, which occurs with an activation energy barrier (ΔE≠ of 9.6 kcal/mol. The stereochemistry (R or S of the aminonitrile product is determined at the NH3 addition step to the carbonyl carbon of the aldehyde. While the addition of CN− to the carbon atom of the protonated imine 7 appears to scramble the stereochemistry, the water cluster above the imine plane reinforces the CN− to attack the imine group below the plane. The enforcement hinders the scrambling. In the second stage, the aminonitrile transforms to alanine, where an amide Me-CH(NH2-C(=O-NH2 is the key intermediate. The rate-determining step is the hydrolysis of the cyano group of N(amino-protonated aminonitrile which occurs with an ΔE≠ value of 34.7 kcal/mol. In the Strecker reaction, the proton transfer along the hydrogen bonds plays a crucial role.

Ultrasonic transesterification of Jatrophacurcas L. oil to biodiesel by a two-step process

Energy Technology Data Exchange (ETDEWEB)

Deng, Xin; Fang, Zhen; Liu, Yun-hu [Biomass Group, Xishuangbanna Tropical Botanical Garden, Chinese Academy of Sciences, 88 Xuefulu, Kunming, Yunnan Province 650223 (China)

2010-12-15

Transesterification of high free fatty acid content Jatropha oil with methanol to biodiesel catalyzed directly by NaOH and high-concentrated H{sub 2}SO{sub 4} or by two-step process were studied in an ultrasonic reactor at 60 C. If NaOH was used as catalyst, biodiesel yield was only 47.2% with saponification problem. With H{sub 2}SO{sub 4} as catalyst, biodiesel yield was increased to 92.8%. However, longer reaction time (4 h) was needed and the biodiesel was not stable. A two-step, acid-esterification and base-transesterification process was further used for biodiesel production. It was found that after the first-step pretreatment with H{sub 2}SO{sub 4} for 1 h, the acid value of Jatropha oil was reduced from 10.45 to 1.2 mg KOH/g, and subsequently, NaOH was used for the second-step transesterification. Stable and clear yellowish biodiesel was obtained with 96.4% yield after reaction for 0.5 h. The total production time was only 1.5 h that is just half of the previous reported. The two-step process with ultrasonic radiation is effective and time-saving for biodiesel production from Jatropha oil. (author)

Ultrasonic transesterification of Jatrophacurcas L. oil to biodiesel by a two-step process

Energy Technology Data Exchange (ETDEWEB)

Deng Xin [Biomass Group, Xishuangbanna Tropical Botanical Garden, Chinese Academy of Sciences, 88 Xuefulu, Kunming, Yunnan Province 650223 (China); Fang Zhen, E-mail: zhenfang@xtbg.ac.c [Biomass Group, Xishuangbanna Tropical Botanical Garden, Chinese Academy of Sciences, 88 Xuefulu, Kunming, Yunnan Province 650223 (China); Liu Yunhu [Biomass Group, Xishuangbanna Tropical Botanical Garden, Chinese Academy of Sciences, 88 Xuefulu, Kunming, Yunnan Province 650223 (China)

2010-12-15

Transesterification of high free fatty acid content Jatropha oil with methanol to biodiesel catalyzed directly by NaOH and high-concentrated H{sub 2}SO{sub 4} or by two-step process were studied in an ultrasonic reactor at 60 deg. C. If NaOH was used as catalyst, biodiesel yield was only 47.2% with saponification problem. With H{sub 2}SO{sub 4} as catalyst, biodiesel yield was increased to 92.8%. However, longer reaction time (4 h) was needed and the biodiesel was not stable. A two-step, acid-esterification and base-transesterification process was further used for biodiesel production. It was found that after the first-step pretreatment with H{sub 2}SO{sub 4} for 1 h, the acid value of Jatropha oil was reduced from 10.45 to 1.2 mg KOH/g, and subsequently, NaOH was used for the second-step transesterification. Stable and clear yellowish biodiesel was obtained with 96.4% yield after reaction for 0.5 h. The total production time was only 1.5 h that is just half of the previous reported. The two-step process with ultrasonic radiation is effective and time-saving for biodiesel production from Jatropha oil.

Maximizing Efficiency in Two-step Solar-thermochemical Fuel Production

Energy Technology Data Exchange (ETDEWEB)

Ermanoski, I. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

2015-05-01

Widespread solar fuel production depends on its economic viability, largely driven by the solar-to-fuel conversion efficiency. In this paper, the material and energy requirements in two-step solar-thermochemical cycles are considered.The need for advanced redox active materials is demonstrated, by considering the oxide mass flow requirements at a large scale. Two approaches are also identified for maximizing the efficiency: optimizing reaction temperatures, and minimizing the pressure in the thermal reduction step by staged thermal reduction. The results show that each approach individually, and especially the two in conjunction, result in significant efficiency gains.

Reaction mechanism and spectroscopy of transfer reactions induced by heavy ions

International Nuclear Information System (INIS)

Lemaire, M.-C.

1977-01-01

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

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

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

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

The path to improved reaction rates for astrophysics

International Nuclear Information System (INIS)

Rauscher, T.

2011-01-01

This review focuses on nuclear reactions in astrophysics and, more specifically, on reactions with light ions (nucleons and α particles) proceeding via the strong interaction. It is intended to present the basic definitions essential for studies in nuclear astrophysics, to point out the differences between nuclear reactions taking place in stars and in a terrestrial laboratory, and to illustrate some of the challenges to be faced in theoretical and experimental studies of those reactions. The discussion revolves around the relevant quantities for astrophysics, which are the astrophysical reaction rates. The sensitivity of the reaction rates to the uncertainties in the prediction of various nuclear properties is explored and some guidelines for experimentalists are also provided. (author)

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

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.

Fully-Polymeric pH Sensor Realized by Means of a Single-Step Soft Embossing Technique

Science.gov (United States)

Fanzio, Paola; Chang, Chi-Tung; Skolimowski, Maciej; Tanzi, Simone; Sasso, Luigi

2017-01-01

We present here an electrochemical sensor microsystem for the monitoring of pH. The all-polymeric device is comprised of a cyclic olefin copolymer substrate, a 200 nm-thin patterned layer of conductive polymer (PEDOT), and a 70 nm electropolymerized layer of a pH sensitive conductive polymer (polyaniline). The patterning of the fluidic (microfluidic channels) and conductive (wiring and electrodes) functional elements was achieved with a single soft PDMS mold via a single embossing step process. A post-processing treatment with ethylene glycol assured the functional enhancement of the electrodes, as demonstrated via an electrical and electrochemical characterization. A surface modification of the electrodes was carried out, based on voltammetric electropolymerization, to obtain a thin layer of polyaniline. The mechanism for pH sensing is based on the redox reactions of the polyaniline layer caused by protonation. The sensing performance of the microsystem was finally validated by monitoring its potentiometric response upon exposure to a relevant range of pH. PMID:28531106

Fully-Polymeric pH Sensor Realized by Means of a Single-Step Soft Embossing Technique

Directory of Open Access Journals (Sweden)

Paola Fanzio

2017-05-01

Full Text Available We present here an electrochemical sensor microsystem for the monitoring of pH. The all-polymeric device is comprised of a cyclic olefin copolymer substrate, a 200 nm-thin patterned layer of conductive polymer (PEDOT, and a 70 nm electropolymerized layer of a pH sensitive conductive polymer (polyaniline. The patterning of the fluidic (microfluidic channels and conductive (wiring and electrodes functional elements was achieved with a single soft PDMS mold via a single embossing step process. A post-processing treatment with ethylene glycol assured the functional enhancement of the electrodes, as demonstrated via an electrical and electrochemical characterization. A surface modification of the electrodes was carried out, based on voltammetric electropolymerization, to obtain a thin layer of polyaniline. The mechanism for pH sensing is based on the redox reactions of the polyaniline layer caused by protonation. The sensing performance of the microsystem was finally validated by monitoring its potentiometric response upon exposure to a relevant range of pH.

Fully-Polymeric pH Sensor Realized by Means of a Single-Step Soft Embossing Technique.

Science.gov (United States)

Fanzio, Paola; Chang, Chi-Tung; Skolimowski, Maciej; Tanzi, Simone; Sasso, Luigi

2017-05-20

We present here an electrochemical sensor microsystem for the monitoring of pH. The all-polymeric device is comprised of a cyclic olefin copolymer substrate, a 200 nm-thin patterned layer of conductive polymer (PEDOT), and a 70 nm electropolymerized layer of a pH sensitive conductive polymer (polyaniline). The patterning of the fluidic (microfluidic channels) and conductive (wiring and electrodes) functional elements was achieved with a single soft PDMS mold via a single embossing step process. A post-processing treatment with ethylene glycol assured the functional enhancement of the electrodes, as demonstrated via an electrical and electrochemical characterization. A surface modification of the electrodes was carried out, based on voltammetric electropolymerization, to obtain a thin layer of polyaniline. The mechanism for pH sensing is based on the redox reactions of the polyaniline layer caused by protonation. The sensing performance of the microsystem was finally validated by monitoring its potentiometric response upon exposure to a relevant range of pH.

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)

Pre-equilibrium emission of nucleons from reactions induced by medium-energy heavy ions

International Nuclear Information System (INIS)

Korolija, M.; Holuh, E.; Cindro, N.; Hilscher, D.

1984-01-01

Recent data on fast-nucleon emission in heavy-ion-induced reactions are analysed successfully in terms of pre-equilibrium models; it is shown that the relevant parameters of those models preserve the physical meaning they have in light-ion-induced reactions. The initial exciton number obtained from a Griffin-plot analysis and the initial number of degrees of freedom, which is the relevant parameter of the modified HMB model, appear to be approximately equal for a given reaction at a given energy. It is inferred that, for heavy-ion reactions, the determination of such a parameter is substantially dominated by the centre-of-mass energy per nucleon above the Coulomb barrier, in contrast with the results of nucleon-induced reactions

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.

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....

A method for measuring light ion reaction cross-sections

International Nuclear Information System (INIS)

Carlson, R.F.; Ingemarsson, A.; Lantz, M.; Arendse, G.J.; Auce, A.; Cox, A.J.; Foertsch, S.V.; Jacobs, N.M.; Johansson, R.; Nyberg, J.; Peavy, J.; Renberg, P.-U.; Sundberg, O.; Stander, J.A.; Steyn, G.F.; Tibell, G.; Zorro, R.

2005-01-01

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 angle 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

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

Age-related changes in compensatory stepping in response to unpredictable perturbations.

Science.gov (United States)

McIlroy, W E; Maki, B E

1996-11-01

Recent studies highlight the importance of compensatory stepping to preserve stability, and the spatial and temporal demands placed on the control of this reaction. Age-related changes in the control of stepping could greatly influence the risk of falling. The present study compares, in healthy elderly and young adults, the characteristics of compensatory stepping responses to unpredictable postural perturbations. A moving platform was used to unpredictably perturb the upright stance of 14 naive, active and mobile subjects (5 aged 22 to 28 and 9 aged 65 to 81). The first 10 randomized trials (5 forward and 5 backward) were evaluated to allow a focus on reactions to relatively novel perturbations. The behavior of the subjects was not constrained. Forceplate and kinematic measures were used to evaluate the responses evoked by the brief (600 msec) platform translation. Subjects stepped in 98% of the trials. Although the elderly were less likely to execute a lateral anticipatory postural adjustment prior to foot-lift, the onset of swing-leg unloading tended to begin at the same time in the two age groups. There was remarkable similarity between the young and elderly in many other characteristics of the first step of the response. In spite of this similarity, the elderly subjects were twice as likely to take additional steps to regain stability (63% of trials for elderly). Moreover, in elderly subjects, the additional steps were often directed so as to preserve lateral stability, whereas the young rarely showed this tendency. Given the functional significance of base-of-support changes as a strategy for preserving stability and the age-related differences presently revealed, assessment of the capacity to preserve stability against unpredictable perturbation, and specific measures such as the occurrence or placement of multiple steps, may prove to be a significant predictor of falling risk and an important outcome in evaluating or developing intervention strategies to

Recent applications of intramolecular Diels-Alder reactions to natural product synthesis

DEFF Research Database (Denmark)

Juhl, M.; Tanner, David Ackland

2009-01-01

This tutorial review presents some recent examples of intramolecular Diels-Alder (IMDA) reactions as key complexity-generating steps in the total synthesis of structurally intricate natural products. The opportunities afforded by transannular (TADA) versions of the IMDA reaction in complex molecu...... comprehensive, reviews....

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,

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.

Alpha-induced reaction cross section measurements on 151Eu for the astrophysical γ-process

International Nuclear Information System (INIS)

Gyuerky, Gy.; Elekes, Z.; Farkas, J.; Fueloep, Zs.; Halasz, Z.; Kiss, G.G.; Somorjai, E.; Szuecs, T.; Gueraya, R.T.; Oezkana, N.

2010-01-01

Compete text of publication follows. The astrophysical γ-process is the main production mechanism of the p-isotopes, the heavy, proton-rich nuclei not produced by neutron capture reactions in the astrophysical sand r-processes. The γ-process is a poorly known process of nucleosynthesis, the models are not able to reproduce well the p-isotope abundances observed in nature. Experimental data on nuclear reactions involved in γ-process reaction networks are clearly needed to provide input for a more reliable γ-process network calculation. As a continuation of our systematic study of reactions relevant for the γ-process, the cross sections of the 151 Eu(α, γ) 155 Tb and 151 Eu(α,n) 154 Tb reactions have been measured. These reactions have been chosen because α-induced cross section data in the region of heavy p-isotopes are almost completely missing although the calculations show a strong influence of these cross section on the resulting abundances. Since the reaction products of both reactions are radioactive, the cross sections have been measured using the activation technique. The targets have been prepared by evaporating Eu 2 O 3 enriched to 99.2% in 151 Eu onto thin Al foils. The target thicknesses have been measured by weighing and Rutherford Backscattering Spectroscopy. The targets have been irradiated by typically 1-2 μA intensity α-beams from the cyclotron of ATOMKI. The investigated energy range between 12 and 17 MeV was covered with 0.5 MeV steps. This energy range is somewhat higher than the astrophysically relevant one, but the cross section at astrophysical energies is so low that the measurements are not possible there. The γ- activity of the reaction products has been measured by a shielded HPGe detector. The absolute efficiency of the detector was measured with several calibration sources. Since 154 Tb has two long lived isomeric states, partial cross sections of the 151 Eu(α,n) 154 Tb reaction leading to the ground and isomeric states

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.

Developing Boundary/PMI Solutions for Next-Step Fusion Devices

Science.gov (United States)

Guo, H. Y.; Leonard, A. W.; Thomas, D. M.; Allen, S. L.; Hill, D. N.; Unterberg, Z.

2014-10-01

The path towards next-step fusion development requires increased emphasis on the boundary/plasma-material interface. The new DIII-D Boundary/Plasma-Material Interactions (PMI) Center has been established to address these critical issues on a timescale relevant to the design of FNSF, adopting the following transformational approaches: (1) Develop and test advanced divertor configurations on DIII-D compatible with core plasma high performance operational scenarios in FNSF; (2) Validate candidate reactor PFC materials at reactor-relevant temperatures in DIII-D high-performance plasmas, in collaboration with the broad material research/development community; (3) Integrate validated boundary-materials interface with high performance plasmas to provide viable boundary/PMI solutions for next-step fusion devices. This program leverages unique DIII-D capabilities, promotes synergistic programs within the broad PMI community, including linear material research facilities. It will also enable us to build a compelling bridge for the US research on long-pulse facilities. Work supported by the US DOE under DE-FC02-04ER54698 and DE-AC52-07NA27344, DE-AC05-00OR2725.

Xylose Isomerization with Zeolites in a Two-Step Alcohol–Water Process

DEFF Research Database (Denmark)

Paniagua, Marta; Shunmugavel, Saravanamurugan; Melián Rodriguez, Mayra

2015-01-01

Isomerization of xylose to xylulose was efficiently catalyzed by large-pore zeolites in a two-step methanol–water process that enhanced the product yield significantly. The reaction pathway involves xylose isomerization to xylulose, which, in part, subsequently reacts with methanol to form methyl...

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).

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.

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.

A method for integrating and ranking the evidence for biochemical pathways by mining reactions from text

Science.gov (United States)

Miwa, Makoto; Ohta, Tomoko; Rak, Rafal; Rowley, Andrew; Kell, Douglas B.; Pyysalo, Sampo; Ananiadou, Sophia

2013-01-01

Motivation: To create, verify and maintain pathway models, curators must discover and assess knowledge distributed over the vast body of biological literature. Methods supporting these tasks must understand both the pathway model representations and the natural language in the literature. These methods should identify and order documents by relevance to any given pathway reaction. No existing system has addressed all aspects of this challenge. Method: We present novel methods for associating pathway model reactions with relevant publications. Our approach extracts the reactions directly from the models and then turns them into queries for three text mining-based MEDLINE literature search systems. These queries are executed, and the resulting documents are combined and ranked according to their relevance to the reactions of interest. We manually annotate document-reaction pairs with the relevance of the document to the reaction and use this annotation to study several ranking methods, using various heuristic and machine-learning approaches. Results: Our evaluation shows that the annotated document-reaction pairs can be used to create a rule-based document ranking system, and that machine learning can be used to rank documents by their relevance to pathway reactions. We find that a Support Vector Machine-based system outperforms several baselines and matches the performance of the rule-based system. The success of the query extraction and ranking methods are used to update our existing pathway search system, PathText. Availability: An online demonstration of PathText 2 and the annotated corpus are available for research purposes at http://www.nactem.ac.uk/pathtext2/. Contact: makoto.miwa@manchester.ac.uk Supplementary information: Supplementary data are available at Bioinformatics online. PMID:23813008

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 ...

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.)

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.)

Recent advances in the chemistry of Rh carbenoids: multicomponent reactions of diazocarbonyl compounds

International Nuclear Information System (INIS)

Medvedev, J J; Nikolaev, V A

2015-01-01

Multicomponent reactions of diazo compounds catalyzed by Rh II complexes become a powerful tool for organic synthesis. They enable three- or four-step processes to be carried out as one-pot procedures (actually as one step) with high stereoselectivity to give complex organic molecules, including biologically active compounds. This review addresses recent results in the chemistry of Rh-catalyzed multicomponent reactions of diazocarbonyl compounds with the intermediate formation of N-, O- and C=O–ylides. The diastereo- and enantioselectivity of these reactions and the possibility of using various co-catalysts to increase the efficiency of the processes under consideration are discussed. The bibliography includes 120 references

On Feature Relevance in Image-Based Prediction Models: An Empirical Study

DEFF Research Database (Denmark)

Konukoglu, E.; Ganz, Melanie; Van Leemput, Koen

2013-01-01

Determining disease-related variations of the anatomy and function is an important step in better understanding diseases and developing early diagnostic systems. In particular, image-based multivariate prediction models and the “relevant features” they produce are attracting attention from the co...

Transesterification of Jatropha curcas oil glycerides: Theoretical and experimental studies of biodiesel reaction

Energy Technology Data Exchange (ETDEWEB)

Neyda C. Om Tapanes; Donato A. Gomes Aranda; Jose W. de Mesquita Carneiro; Octavio A. Ceva Antunes [Universidade Federal do Rio de Janeiro, Rio de Janeiro (Brazil). Laboratorio GREENTEC

2008-08-15

Vegetal oil, also known as triglycerides, is a mixture of fatty acid triesters of glycerol. In the triglycerides alkyl chains of Jatropha curcas oil, predominate the palmitic, oleic and linoleic fatty acids. The process usually used to convert these triglycerides to biodiesel is called transesterification. The overall process is a sequence of three equivalent, consecutive and reversible reactions, in which di- and monoglycerides are formed as intermediates. Semi-empirical AM1 molecular orbital calculations were used to investigate the reaction pathways of base-catalyzed transesterification of glycerides of palmitic, oleic and linoleic acid. The most probable pathway and the rate determining-step of the reactions were estimated from the molecular orbital calculations. Our results suggest the formation of only one tetrahedral intermediate, which in a subsequent step rearranges to form the products. The rate determining-step is the break of this tetrahedral intermediate. 27 refs., 6 figs., 4 tabs.

Exposure-Relevant Ozone Chemistry in Occupied Spaces

Energy Technology Data Exchange (ETDEWEB)

Coleman, Beverly Kaye [Univ. of California, Berkeley, CA (United States)

2009-04-01

Ozone, an ambient pollutant, is transformed into other airborne pollutants in the indoor environment. In this dissertation, the type and amount of byproducts that result from ozone reactions with common indoor surfaces, surface residues, and vapors were determined, pollutant concentrations were related to occupant exposure, and frameworks were developed to predict byproduct concentrations under various indoor conditions. In Chapter 2, an analysis is presented of secondary organic aerosol formation from the reaction of ozone with gas-phase, terpene-containing consumer products in small chamber experiments under conditions relevant for residential and commercial buildings. The full particle size distribution was continuously monitored, and ultrafine and fine particle concentrations were in the range of 10 to>300 mu g m^-3. Particle nucleation and growth dynamics were characterized.Chapter 3 presents an investigation of ozone reactions with aircraft cabin surfaces including carpet, seat fabric, plastics, and laundered and worn clothing fabric. Small chamber experiments were used to determine ozone deposition velocities, ozone reaction probabilities, byproduct emission rates, and byproduct yields for each surface category. The most commonly detected byproducts included C1?C10 saturated aldehydes and skin oil oxidation products. For all materials, emission rates were higher with ozone than without. Experimental results were used to predict byproduct exposure in the cabin and compare to other environments. Byproduct levels are predicted to be similar to ozone levels in the cabin, which have been found to be tens to low hundreds of ppb in the absence of an ozone converter. In Chapter 4, a model is presented that predicts ozone uptake by and byproduct emission from residual chemicals on surfaces. The effects of input parameters (residue surface concentration, ozone concentration, reactivity of the residue and the surface, near-surface airflow conditions, and

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.

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...

Short-term step-to-step correlation in plantar pressure distributions during treadmill walking, and implications for footprint trail analysis.

Science.gov (United States)

Pataky, Todd C; Savage, Russell; Bates, Karl T; Sellers, William I; Crompton, Robin H

2013-09-01

The gait cycle is continuous, but for practical reasons one is often forced to analyze one or only a few adjacent cycles, for example in non-treadmill laboratory investigations and in fossilized footprint analysis. The nature of variability in long-term gait cycle dynamics has been well-investigated, but short-term variability, and specifically correlation, which are highly relevant to short gait bouts, have not. We presently tested for step-to-step autocorrelation in a total of 5243 plantar pressure (PP) distributions from ten subjects who walked at 1.1m/s on an instrumented treadmill. Following spatial foot alignment, data were analyzed both from three points of interest (POI): heel, central metatarsals, and hallux, and for the foot surface as a whole, in a mass-univariate manner. POI results revealed low average step-to-step autocorrelation coefficients (r=0.327±0.094; mean±st. dev.). Formal statistical testing of the whole-foot r distributions reached significance over an average of only 0.42±0.52% of the foot's surface, even for a highly conservative uncorrected threshold of p<0.05. The common assumption, that short gait bouts consist of independent cycles, is therefore not refuted by the present PP results. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

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.

To address surface reaction network complexity using scaling relations machine learning and DFT calculations

International Nuclear Information System (INIS)

Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas; Nørskov, Jens K.

2017-01-01

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying these methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Lastly, propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.

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)

Synthesis of porous gold nanoshells by controlled transmetallation reaction

Energy Technology Data Exchange (ETDEWEB)

Pattabi, Manjunatha, E-mail: manjupattabi@yahoo.com; M, Krishnaprabha [Department of Materials Science, Mangalore University, Mangalagangothri-574199 (India)

2015-06-24

Aqueous synthesis of porous gold nanoshells in one step is carried out through controlled transmetallation (TM) reaction using a naturally available egg shell membrane (ESM) as a barrier between the sacrificial silver particles (AgNPs) and the gold precursor solution (HAuCl{sub 4}). The formation of porous gold nanoshells via TM reaction is inferred from UV-Vis spectroscopy and the scanning electron microscopic (SEM) studies.

Mechanism of tellurium isomers excitation in (γ, n) reactions

International Nuclear Information System (INIS)

Mazur, V.M.; Symochko, D.M.; Bigan, Z.M.; Poltorzhytska, T.V.; Derechkey, P.S.

2012-01-01

Isomeric yield ratios for the 119 Te, 121 Te, 123 Te, 127 Te, 129 Te nuclei were obtained in (γ, n) reactions with bremsstrahlung end point energies ranging 10 - 22 MeV with δE = 0.5 MeV step. Experimental isomeric ratios were used to calculate the cross-sections of (γ, n) m reactions, that were further compared with TALYS-1.4 calculations

Modulation of individual steps in group I intron catalysis by a peripheral metal ion.

Science.gov (United States)

Forconi, Marcello; Piccirilli, Joseph A; Herschlag, Daniel

2007-10-01

Enzymes are complex macromolecules that catalyze chemical reactions at their active sites. Important information about catalytic interactions is commonly gathered by perturbation or mutation of active site residues that directly contact substrates. However, active sites are engaged in intricate networks of interactions within the overall structure of the macromolecule, and there is a growing body of evidence about the importance of peripheral interactions in the precise structural organization of the active site. Here, we use functional studies, in conjunction with published structural information, to determine the effect of perturbation of a peripheral metal ion binding site on catalysis in a well-characterized catalytic RNA, the Tetrahymena thermophila group I ribozyme. We perturbed the metal ion binding site by site-specifically introducing a phosphorothioate substitution in the ribozyme's backbone, replacing the native ligands (the pro-R (P) oxygen atoms at positions 307 and 308) with sulfur atoms. Our data reveal that these perturbations affect several reaction steps, including the chemical step, despite the absence of direct contacts of this metal ion with the atoms involved in the chemical transformation. As structural probing with hydroxyl radicals did not reveal significant change in the three-dimensional structure upon phosphorothioate substitution, the effects are likely transmitted through local, rather subtle conformational rearrangements. Addition of Cd(2+), a thiophilic metal ion, rescues some reaction steps but has deleterious effects on other steps. These results suggest that native interactions in the active site may have been aligned by the naturally occurring peripheral residues and interactions to optimize the overall catalytic cycle.

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...

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

Exploring the Reaction Pathways of Bioglycerol Hydrodeoxygenation to Propene over Molybdena-Based Catalysts.

Science.gov (United States)

Zacharopoulou, Vasiliki; Vasiliadou, Efterpi S; Lemonidou, Angeliki A

2018-01-10

The one-step reaction of glycerol with hydrogen to form propene selectively is a particularly challenging catalytic pathway that has not yet been explored thoroughly. Molybdena-based catalysts are active and selective to C-O bond scission; propene is the only product in the gas phase under the standard reaction conditions, and further hydrogenation to propane is impeded. Within this context, this work focuses on the exploration of the reaction pathways and the investigation of various parameters that affect the catalytic performance, such as the role of hydrogen on the product distribution and the effect of the catalyst pretreatment step. Under a hydrogen atmosphere, propene is produced primarily via 2-propenol, whereas under an inert atmosphere propanal and glycerol dissociation products are formed mainly. The reaction most likely proceeds through a reverse Mars-van Krevelen mechanism as partially reduced Mo species drive the reaction to the formation of the desired product. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

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.

Understanding the two neutron transfer reaction mechanism in {sup 206}Pb({sup 18}O,{sup 16}O){sup 208}Pb

Energy Technology Data Exchange (ETDEWEB)

Parmar, A.; Sonika [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai - 400 085 (India); Roy, B.J., E-mail: bjroy@barc.gov.in [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai - 400 085 (India); Jha, V.; Pal, U.K. [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai - 400 085 (India); Sinha, T. [High Energy Nuclear and Particle Physics Division, Saha Institute of Nuclear Physics, Kolkata - 700 064 (India); Pandit, S.K.; Parkar, V.V.; Ramachandran, K.; Mahata, K.; Santra, S.; Mohanty, A.K. [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai - 400 085 (India)

2015-08-15

The absolute cross sections for elastic scattering and two-neutron transfer reaction for {sup 18}O + {sup 206}Pb system have been measured at an incident energy near the Coulomb barrier. Detailed coupled reaction channel calculations have been carried out for description of the measured angular distributions for the elastic scattering and transfer reactions simultaneously. The two-neutron transfer reaction {sup 206}Pb({sup 18}O, {sup 16}O){sup 208}Pb in the g.s. → g.s. transition is analyzed in (i) extreme cluster model assuming a di-neutron transfer, (ii) two-step successive transfer, and (iii) microscopic approach (independent coordinate scheme) of simultaneous transfer of two neutrons. The relative importance of one step simultaneous transfer versus two-step successive transfer has been studied. Present analysis suggests dominance of cluster transfer of a di-neutron. The contribution from the two-step sequential processes is less significant, however, the combined “two-step plus simultaneous (microscopic)” calculations give a reasonably good agreement with the measurement. The possibility of multi-step route via projectile and target excitations and contribution from such indirect transfer paths to the present two-neutron transfer cross section has been investigated.

A tandem cross-metathesis/semipinacol rearrangement reaction.

Science.gov (United States)

Plummer, Christopher W; Soheili, Arash; Leighton, James L

2012-05-18

An efficient and (E)-selective synthesis of a 6-alkylidenebicyclo[3.2.1]octan-8-one has been developed. The key step is a tandem cross-metathesis/semipinacol rearrangement reaction, wherein the Hoveyda-Grubbs II catalyst, or more likely a derivative thereof, serves as the Lewis acid for the rearrangement. Despite the fact that both the starting alkene and the cross-metathesis product are viable rearrangement substrates, only the latter rearranges, suggesting that the Lewis acidic species is generated only after the cross-metathesis reaction is complete.

A theoretical model investigation of peptide bond formation involving two water molecules in ribosome supports the two-step and eight membered ring mechanism

International Nuclear Information System (INIS)

Wang, Qiang; Gao, Jun; Zhang, Dongju; Liu, Chengbu

2015-01-01

Highlights: • We theoretical studied peptide bond formation reaction mechanism with two water molecules. • The first water molecule can decrease the reaction barriers by forming hydrogen bonds. • The water molecule mediated three-proton transfer mechanism is the favorable mechanism. • Our calculation supports the two-step and eight membered ring mechanism. - Abstract: The ribosome is the macromolecular machine that catalyzes protein synthesis. The kinetic isotope effect analysis reported by Strobel group supports the two-step mechanism. However, the destination of the proton originating from the nucleophilic amine is uncertain. A computational simulation of different mechanisms including water molecules is carried out using the same reaction model and theoretical level. Formation the tetrahedral intermediate with proton transfer from nucleophilic nitrogen, is the rate-limiting step when two water molecules participate in peptide bond formation. The first water molecule forming hydrogen bonds with O9′ and H15′ in the A site can decrease the reaction barriers. Combined with results of the solvent isotope effects analysis, we conclude that the three-proton transfer mechanism in which water molecule mediate the proton shuttle between amino and carbon oxygen in rate-limiting step is the favorable mechanism. Our results will shield light on a better understand the reaction mechanism of ribosome

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.

Dropping and semimicrotest glass reactions on beryllium, lenthanum, vanadyl and uranyl cations with synthetic organic dyes and their mutual determination in binary mixtures

International Nuclear Information System (INIS)

Shemyakin, F.M.; Novikova, A.A.; Reshetnyak, V.Yu.; Teplyakov, G.K.; Nekrasov, E.L.

1978-01-01

Coloured reactions for beryllium, lanthanum, vanadyl and uranyl cations with a number of organic dyes, have been studied. These reactions are used in dropping analysis on papers, impregnated with relevant dyes, and for semimicro-test glass reactions on the above cations. Sensitivity and maximum permissible dilution have been determined for each of the reactions. Mutual determinations of relevant couples of the above cations have been performed. It is shown, that such binary mixtures enable to freely open relevant cations

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

A taxonomy of integral reaction path analysis

Energy Technology Data Exchange (ETDEWEB)

Grcar, Joseph F.; Day, Marcus S.; Bell, John B.

2004-12-23

W. C. Gardiner observed that achieving understanding through combustion modeling is limited by the ability to recognize the implications of what has been computed and to draw conclusions about the elementary steps underlying the reaction mechanism. This difficulty can be overcome in part by making better use of reaction path analysis in the context of multidimensional flame simulations. Following a survey of current practice, an integral reaction flux is formulated in terms of conserved scalars that can be calculated in a fully automated way. Conditional analyses are then introduced, and a taxonomy for bidirectional path analysis is explored. Many examples illustrate the resulting path analysis and uncover some new results about nonpremixed methane-air laminar jets.

Major mechanistic differences between the reactions of hydroxylamine with phosphate di- and tri-esters.

Science.gov (United States)

Medeiros, Michelle; Wanderlind, Eduardo H; Mora, José R; Moreira, Raphaell; Kirby, Anthony J; Nome, Faruk

2013-10-07

Hydroxylamine reacts as an oxygen nucleophile, most likely via its ammonia oxide tautomer, towards both phosphate di- and triesters of 2-hydroxypyridine. But the reactions are very different. The product of the two-step reaction with the triester TPP is trapped by the NH2OH present in solution to generate diimide, identified from its expected disproportionation and trapping products. The reaction with H3N(+)-O(-) shows general base catalysis, which calculations show is involved in the breakdown of the phosphorane addition-intermediate of a two-step reaction. The reactivity of the diester anion DPP(-) is controlled by its more basic pyridyl N. Hydroxylamine reacts preferentially with the substrate zwitterion DPP(±) to displace first one then a second 2-pyridone, in concerted S(N)2(P) reactions, forming O-phosphorylated products which are readily hydrolysed to inorganic phosphate. The suggested mechanisms are tested and supported by extensive theoretical calculations.

Late adverse reactions to intravascular iodine based contrast media

DEFF Research Database (Denmark)

Bellin, Marie-France; Stacul, Fulvio; Webb, Judith A W

2011-01-01

DEFINITION: Late adverse reactions (LAR) to contrast media (CM) are defined as reactions occurring 1 h to 1 week after exposure. NEED FOR REVIEW: In view of more prospective studies of LAR and new data about their pathophysiology, the Contrast Medium Safety Committee (CMSC) of the European Society...... or delayed reading intradermal). The main risk factors for LAR are a previous reaction to contrast medium, a history of allergy, and interleukin-2 treatment. Most skin reactions are mild or moderate and self-limiting. MANAGEMENT: Management is symptomatic and similar to the management of other drug......-induced skin reactions. To reduce the risk of repeat reactions avoidance of the relevant CM and any cross-reacting agents identified by skin testing is recommended....

Ferrous ions reused as catalysts in Fenton-like reactions for remediation of agro-food industrial wastewater.

Science.gov (United States)

Leifeld, Vanessa; Dos Santos, Tâmisa Pires Machado; Zelinski, Danielle Wisniewski; Igarashi-Mafra, Luciana

2018-09-15

Cassava is the most important tuberous root in tropical and subtropical regions of the world, being the third largest source of carbohydrates. The root processing is related to the production of starch, an important industrial input, which releases a highly toxic liquid wastewater due to its complex composition, which inhibits high performances of conventional effluent treatments. This study aims to evaluate Fenton-like and photo-Fenton-like reactions for treatment of cassava wastewater, reusing ferrous ions from the preliminary coagulation stage. Pre-treated cassava wastewater was submitted to oxidation in three variations of hydrogen peroxide concentrations, with more relevant analytical responses verified in color, turbidity, COD (Chemical Oxygen Demand), and acute toxicity in Artemia salina, besides the action of radicals during Fenton-like reactions. At higher peroxide concentrations, a decrease of 68% in turbidity and 70% in COD on the photo-Fenton-like system was observed, even at slow reaction rates (fastest rate constant k = 2 × 10 -4 min -1 ). Inclusion of UV increases the viability of the Fenton-like reactions by supplementing the reaction medium with hydroxyl radicals, verified by the tert-butanol tests. The oxidation process leads to high EC 50 values in 24 h of incubation in Fenton-like reactions and 48 h in photo-Fenton-like reactions. Final COD and turbidity suggests that the reuse of iron, which remains in the preliminary treatment step shows a great potential as a catalyst for Fenton-like advanced oxidation processes. Tertiary treatment can be less expensive and harmful to the environment, reducing production of residual sludge and metal content in the final effluent, which reduces polluting potential of the effluent regarding solid waste. Copyright © 2018 Elsevier Ltd. All rights reserved.

Theoretical study of the oxidation mechanisms of naphthalene initiated by hydroxyl radicals: the O2 addition reaction pathways.

Science.gov (United States)

Shiroudi, A; Deleuze, M S; Canneaux, S

2015-05-28

Atmospheric oxidation of the naphthalene-OH adduct [C10H8OH]˙ (R1) by molecular oxygen in its triplet electronic ground state has been studied using density functional theory along with the B3LYP, ωB97XD, UM05-2x and UM06-2x exchange-correlation functionals. From a thermodynamic viewpoint, the most favourable process is O2 addition at the C2 position in syn mode, followed by O2 addition at the C2 position in anti mode, O2 addition at the C4 position in syn mode, and O2 addition at the C4 position in anti mode, as the second, third and fourth most favourable processes. The syn modes of addition at these positions are thermodynamically favoured over the anti ones by the formation of an intramolecular hydrogen bond between the hydroxyl and peroxy substituents. Analysis of the computed structures, bond orders and free energy profiles demonstrate that the reaction steps involved in the oxidation of the naphthalene-OH adduct by O2 satisfy Hammond's principle. Kinetic rate constants and branching ratios under atmospheric pressure and in the fall-off regime have been supplied, using transition state and RRKM theories. By comparison with experiment, these data confirm the relevance of a two-step reaction mechanism. Whatever the addition mode, O2 addition in C4 position is kinetically favoured over O2 addition in C2 position, in contrast with the expectations drawn from thermodynamics and reaction energies. Under a kinetic control of the reaction, and in line with the computed reaction energy barriers, the most efficient process is O2 addition at the C4 position in syn mode, followed by O2 addition at the C2 position in syn mode, O2 addition at the C4 position in anti mode, and O2 addition at the C2 position in anti mode as the second, third and fourth most rapid processes. The computed branching ratios also indicate that the regioselectivity of the reaction decreases with increasing temperatures and decreasing pressures.

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)

The quantum dynamics of electronically nonadiabatic chemical reactions

Science.gov (United States)

Truhlar, Donald G.

1993-01-01

Considerable progress was achieved on the quantum mechanical treatment of electronically nonadiabatic collisions involving energy transfer and chemical reaction in the collision of an electronically excited atom with a molecule. In the first step, a new diabatic representation for the coupled potential energy surfaces was created. A two-state diabatic representation was developed which was designed to realistically reproduce the two lowest adiabatic states of the valence bond model and also to have the following three desirable features: (1) it is more economical to evaluate; (2) it is more portable; and (3) all spline fits are replaced by analytic functions. The new representation consists of a set of two coupled diabatic potential energy surfaces plus a coupling surface. It is suitable for dynamics calculations on both the electronic quenching and reaction processes in collisions of Na(3p2p) with H2. The new two-state representation was obtained by a three-step process from a modified eight-state diatomics-in-molecules (DIM) representation of Blais. The second step required the development of new dynamical methods. A formalism was developed for treating reactions with very general basis functions including electronically excited states. Our formalism is based on the generalized Newton, scattered wave, and outgoing wave variational principles that were used previously for reactive collisions on a single potential energy surface, and it incorporates three new features: (1) the basis functions include electronic degrees of freedom, as required to treat reactions involving electronic excitation and two or more coupled potential energy surfaces; (2) the primitive electronic basis is assumed to be diabatic, and it is not assumed that it diagonalizes the electronic Hamiltonian even asymptotically; and (3) contracted basis functions for vibrational-rotational-orbital degrees of freedom are included in a very general way, similar to previous prescriptions for locally

Constraining astrophysical reaction rates: using the storage rings at FAIR/GSI

Science.gov (United States)

Langer, Christoph; Glorius, Jan; Slavkovská, Zuzana; Litvinov, Sergey; Litvinov, Yuri A.; Reifarth, René

2018-01-01

Ion optical calculations for a storage ring at the present GSI facility for direct proton-induced reactions relevant for different astrophysical processes are presented. As an example case, the 59Cu(p,γ) and 59Cu(p,α) reactions are shown. The branching of these two reactions is important in X-ray burst scenarios, since it determines the breakout out of the major 56Ni waiting point.

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

Carbonyl-Olefin Exchange Reaction: Present State and Outlook

Science.gov (United States)

Kalinova, Radostina; Jossifov, Christo

The carbonyl-olefin exchange reaction (COER) is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis (OM) - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the COER. The question arises: is it possible the COER to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction became an alternative of the existing carbonyl olefination reactions?

Organometallic copper I, II or III species in an intramolecular dechlorination reaction

KAUST Repository

Poater, Albert; Cavallo, Luigi

2013-01-01

these species are less stable than other isomers. Thus this study constitutes an additional piece towards the full understanding of a class of reaction of biological relevance. Further, the lack of high energy barriers and deep energy wells along the reaction

A theoretical study of the alkylation reaction of toluene with methanol catalyzed by acidic mordenite

NARCIS (Netherlands)

Vos, A.M.; Rozanska, X.; Schoonheydt, R.A.; Santen, van R.A.; Hutschka, F.; Hafner, J.

2001-01-01

A theoretical study of the alkylation reaction of toluene with methanol catalyzed by the acidic Mordenite (Si/Al = 23) is reported. Cluster DFT as well as periodical structure DFT calculations have been performed. Full reaction energy diagrams of the elementary reaction steps that lead to the

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

Supersonic molecular beam experiments on surface chemical reactions.

Science.gov (United States)

Okada, Michio

2014-10-01

The interaction of a molecule and a surface is important in various fields, and in particular in complex systems like biomaterials and their related chemistry. However, the detailed understanding of the elementary steps in the surface chemistry, for example, stereodynamics, is still insufficient even for simple model systems. In this Personal Account, I review our recent studies of chemical reactions on single-crystalline Cu and Si surfaces induced by hyperthermal oxygen molecular beams and by oriented molecular beams, respectively. Studies of oxide formation on Cu induced by hyperthermal molecular beams demonstrate a significant role of the translational energy of the incident molecules. The use of hyperthermal molecular beams enables us to open up new chemical reaction paths specific for the hyperthermal energy region, and to develop new methods for the fabrication of thin films. On the other hand, oriented molecular beams also demonstrate the possibility of understanding surface chemical reactions in detail by varying the orientation of the incident molecules. The steric effects found on Si surfaces hint at new ways of material fabrication on Si surfaces. Controlling the initial conditions of incoming molecules is a powerful tool for finely monitoring the elementary step of the surface chemical reactions and creating new materials on surfaces. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of reaction products formed in the gas phase reaction of E,E-2,4-hexadienal with atmospheric oxidants: Reaction mechanisms and atmospheric implications

Science.gov (United States)

Colmenar, I.; Martin, P.; Cabañas, B.; Salgado, S.; Martinez, E.

2018-03-01

An analysis of reaction products for the reaction of E,E-2,4-hexadienal with chlorine atoms (Cl) and OH and NO3 radicals has been carried out at the first time with the aim of obtaining a better understanding of the tropospheric reactivity of α,β-unsaturated carbonyl compounds. Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography-Mass Spectrometry with a Time of Flight detector (GC-TOFMS) were used to carry out the qualitative and/or quantitative analyses. Reaction products in gas and particulate phase were observed from the reactions of E,E-2,4- hexadienal with all oxidants. E/Z-Butenedial and maleic anhydride were the main products identified in gas phase. E-butenedial calculated molar yield ranging from 4 to 10%. A significant amount of multifunctional compounds (chloro and hydroxy carbonyls) was identified. These compounds could be formed in particulate phase explaining the ∼90% of unaccounted carbon in gas phase. The reaction with Cl atoms in the presence of NOx with a long reaction time gave Peroxy Acetyl Nitrate (PAN) as an additional product, which is known for being an important specie in the generation of the photochemical smog. Nitrated compounds were the major organic products from the reaction with the NO3 radical. Based on the identified products, the reaction mechanisms have been proposed. In these mechanisms a double bond addition of the atmospheric oxidant at C4/C5 of E,E-2,4-hexadienal is the first step for tropospheric degradation.

GA(2)LEN skin test study II: clinical relevance of inhalant allergen sensitizations in Europe

DEFF Research Database (Denmark)

Burbach, G J; Heinzerling, L M; Edenharter, G

2009-01-01

BACKGROUND: Skin prick testing is the standard for diagnosing IgE-mediated allergies. A positive skin prick reaction, however, does not always correlate with clinical symptoms. A large database from a Global Asthma and Allergy European Network (GA(2)LEN) study with data on clinical relevance was ...... the clinical relevance of positive skin prick tests and calls for further studies, which may, ultimately, help increase the positive predictive value of allergy testing.......BACKGROUND: Skin prick testing is the standard for diagnosing IgE-mediated allergies. A positive skin prick reaction, however, does not always correlate with clinical symptoms. A large database from a Global Asthma and Allergy European Network (GA(2)LEN) study with data on clinical relevance...... was used to determine the clinical relevance of sensitizations against the 18 most frequent inhalant allergens in Europe. The study population consisted of patients referred to one of the 17 allergy centres in 14 European countries (n = 3034, median age = 33 years). The aim of the study was to assess...

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...

Investigation of the (p,p'), (p,d) and (p,t) reactions on some light Sn isotopes

International Nuclear Information System (INIS)

Blankert, P.J.

1979-01-01

The results are presented of the 112 Sn(p,p') 112 Sn reaction. Apart from the usual distorted-wave analysis the excitation of some states is described in the coupled-channels formalism. The results of the 112 Sn(p,d) 111 Sn and the 112 Sn(p,t) 110 Sn reactions are also reported. From the (p,d) reaction quasi-particle energies and occupation numbers are determined. Two-step DWBA calculations are performed for some states that are assumed to result from the coupling of a quasiparticle to the 2 + 1 or 3 - 1 state of the even core. In the gross structure above 3 MeV of excitation, pickup strength from deeply-bound hole states is observed. The (p,t) reaction provided spin and parity of a number of levels in 110 Sn. A two-step DWBA analysis of the excitation of the ground state and first excited 2 + state shows the importance of second-order processes. The combined results of the (p,t) reactions on 112 Sn, 114 Sn and 116 Sn are given with some emphasis on the systematic features. The derivation is given of some expressions for spectroscopic amplitudes necessary in the two-step DWBA calculations for the (p,t) reactions. For all reactions a comparison is made with other existing data and with the results of model calculations. (Auth.)

Evaluation of tri-steps modified styrene-butadiene-styrene block copolymer membrane for wound dressing

International Nuclear Information System (INIS)

Yang, Jen Ming; Huang, Huei Tsz

2012-01-01

Tri-steps modified styrene-butadiene-styrene block copolymer (SBS) membrane was prepared with epoxidation, ring opening reaction with maleated ionomer and layer-by-layer assembled polyelectrolyte technique. The tri-steps modified SBS membrane was characterized by infrared spectroscopy and X-ray photoelectron spectroscope (XPS). The structures of the modified SBS membranes were identified with methylene blue and azocarmine G. The content of amino group on the surface of the modified membrane was calculated from uptake of an acid dye. The values of the contact angle, water absorption, water vapor transmission rate and the adsorption of fibronectin on the membranes were determined. To evaluate the biocompatibility of the tri-steps modified SBS membrane, the cytotoxicity, antibacterial and growth profile of the cell culture of 3T3 fibroblasts on the membrane were evaluated. The bactericidal activity was found on the modified SBS. From the cell culture of 3T3 fibroblasts on the membrane, it revealed that the cells not only remained viable but also proliferated on the surface of the tri-steps modified SBS membranes. As the membranes are sterile semipermeable with bactericidal activity and transparent allowing wound checks, they can be considered for shallow wound with low exudates. - Highlights: ► Styrene-butadiene-styrene block copolymer (SBS) was modified with tri-steps. ► The tri-steps are epoxidation, ring opening reaction and layer-by-layer assembly. ► Modified SBS membrane for wound dressing is evaluated. ► Membranes are sterile semipermeable with bactericidal activity and transparent. ► Membranes can be considered for shallow wound with low exudates.

Advice on the management of reactions to intravenous contrast media

International Nuclear Information System (INIS)

1996-01-01

The College has previously issued guidelines for the management of adverse reactions to intravenous ionic and non-ionic contrast media. The following updated guidelines are applicable to both children and adults. The reported adverse reaction rate to conventional ionic contrast media is about 5%, the vast majority of reactions being of a minor nature, and to the newer non-ionic contrast media, approximately 1%. The rare serious reaction, with an estimated incidence of 0.05% with ionic contrast media and substantially less with non-ionic media, must be treated quickly and appropriately. Identification and symptomatic characterisation of the reaction are the key first steps and should be followed by ad hoc management based on general principles. (author)

Preparation of biodiesel from waste cooking oil via two-step catalyzed process

International Nuclear Information System (INIS)

Wang Yong; Liu Pengzhan; Ou Shiyi; Zhang Zhisen

2007-01-01

Waste cooking oils (WCO), which contain large amounts of free fatty acids produced in restaurants, are collected by the environmental protection agency in the main cities of China and should be disposed in a suitable way. In this research, a two step catalyzed process was adopted to prepare biodiesel from waste cooking oil whose acid value was 75.92 ± 0.036 mgKOH/g. The free fatty acids of WCO were esterified with methanol catalyzed by ferric sulfate in the first step, and the triglycerides (TGs) in WCO were transesterified with methanol catalyzed by potassium hydroxide in the second step. The results showed that ferric sulfate had high activity to catalyze the esterification of free fatty acids (FFA) with methanol, The conversion rate of FFA reached 97.22% when 2 wt% of ferric sulfate was added to the reaction system containing methanol to TG in10:1 (mole ratio) composition and reacted at 95 deg. C for 4 h. The methanol was vacuum evaporated, and transesterification of the remained triglycerides was performed at 65 deg. C for 1 h in a reaction system containing 1 wt% of potassium hydroxide and 6:1 mole ratio of methanol to TG. The final product with 97.02% of biodiesel, obtained after the two step catalyzed process, was analyzed by gas chromatography. This new process has many advantages compared with the old processes, such as no acidic waste water, high efficiency, low equipment cost and easy recovery of the catalyst

Influence of nature, concentration and pH of buffer acid-base system on rate determining step of the electrochemiluminescence of Ru(bpy)32+ with tertiary aliphatic amines

International Nuclear Information System (INIS)

Pastore, Paolo; Badocco, Denis; Zanon, Francesco

2006-01-01

The electrogenerated chemiluminescence (ECL) of Ru(bpy) 3 2+ (bpy 2,2'-bipyridyl) with tertiary aliphatic amines as co-reactants, was theoretically and experimentally studied as a function of the pre-equilibria involved in the ammonium proton lost and in relation to the nature of the rate determining step. Transient potential steps were used with a 3-mm glassy carbon disk electrode or carbon fiber ultramicroelectrodes array to investigate emission behavior in a variety of aqueous solution types, containing phosphate, tartrate and phthalate acid-base systems at differing pH values. The emission of Ru(bpy) 3 2+ resulting from the reaction with n-tripropylamine (TPrA), tri-isobutylamine (TisoBuA), n-tributylamine (TBuA), methyl-di-n-propylamine (MeDPrA) and triethylamine (TEtA) in varying acid-base media was interpreted on the basis of the quoted pre-equilibria, ammonium pK a being known. The nature of the rate determining steps changes depending on pH. Above pH ∼ 5 the amine neutral radical formation is the rate determining step and, is independent of pH with rate constant close to 10 3 s -1 ; below pH ∼ 5 the rate determining step becomes the deprotonation of the ammonium ion, operated by different bases present in solution. Different amines in the same acid-base system showed analogous ECL behavior, conditioned by the chosen acid base system. A single amine in different acid-base systems showed different kinetic behaviors, due to the dissociation constants of the chosen buffers. The concentration of the acid-base system also played an important role and influenced emission intensity and shape. ECL emission were simulated by finite difference methods, implementing a previously proposed mechanism by including the relevant pre-equilibria. Simulation may also give estimates of the pK a values of the ammonium ions. An ion pair formation between R 3 N· + and the mostly charged species present in solution is hypothesized to explain the contradictory experimental

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,

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.

Application of Carbohydrate-Templated Asymmetric Diels-Alder Reaction to the Syntheses of ent-Penicillones A and B.

Science.gov (United States)

Weng, Chia-Hao; Hsu, Day-Shin; Liao, Chun-Chen

2016-11-18

Total syntheses of ent-penicillones A (ent-1) and B (ent-2) from 3,5-dimethylcatechol (3) were accomplished in 10 and 9 synthetic steps, respectively. A carbohydrate-templated asymmetric intramolecular Diels-Alder reaction of a masked o-benzoquinone (MOB) 9 and an aqueous acid-catalyzed intramolecular aldol reaction are the key synthetic steps. In addition, the absolute configurations of the bicyclo[2.2.2]oct-5-en-2-one core obtained from the per-O-benzylated α-d-glucopyranosyl as a carbohydrate template in the intramolecular Diels-Alder reaction of MOBs were revised.

Quantitative comparison of catalytic mechanisms and overall reactions in convergently evolved enzymes: implications for classification of enzyme function.

Science.gov (United States)

Almonacid, Daniel E; Yera, Emmanuel R; Mitchell, John B O; Babbitt, Patricia C

2010-03-12

Functionally analogous enzymes are those that catalyze similar reactions on similar substrates but do not share common ancestry, providing a window on the different structural strategies nature has used to evolve required catalysts. Identification and use of this information to improve reaction classification and computational annotation of enzymes newly discovered in the genome projects would benefit from systematic determination of reaction similarities. Here, we quantified similarity in bond changes for overall reactions and catalytic mechanisms for 95 pairs of functionally analogous enzymes (non-homologous enzymes with identical first three numbers of their EC codes) from the MACiE database. Similarity of overall reactions was computed by comparing the sets of bond changes in the transformations from substrates to products. For similarity of mechanisms, sets of bond changes occurring in each mechanistic step were compared; these similarities were then used to guide global and local alignments of mechanistic steps. Using this metric, only 44% of pairs of functionally analogous enzymes in the dataset had significantly similar overall reactions. For these enzymes, convergence to the same mechanism occurred in 33% of cases, with most pairs having at least one identical mechanistic step. Using our metric, overall reaction similarity serves as an upper bound for mechanistic similarity in functional analogs. For example, the four carbon-oxygen lyases acting on phosphates (EC 4.2.3) show neither significant overall reaction similarity nor significant mechanistic similarity. By contrast, the three carboxylic-ester hydrolases (EC 3.1.1) catalyze overall reactions with identical bond changes and have converged to almost identical mechanisms. The large proportion of enzyme pairs that do not show significant overall reaction similarity (56%) suggests that at least for the functionally analogous enzymes studied here, more stringent criteria could be used to refine

Quantitative comparison of catalytic mechanisms and overall reactions in convergently evolved enzymes: implications for classification of enzyme function.

Directory of Open Access Journals (Sweden)

Daniel E Almonacid

2010-03-01

Full Text Available Functionally analogous enzymes are those that catalyze similar reactions on similar substrates but do not share common ancestry, providing a window on the different structural strategies nature has used to evolve required catalysts. Identification and use of this information to improve reaction classification and computational annotation of enzymes newly discovered in the genome projects would benefit from systematic determination of reaction similarities. Here, we quantified similarity in bond changes for overall reactions and catalytic mechanisms for 95 pairs of functionally analogous enzymes (non-homologous enzymes with identical first three numbers of their EC codes from the MACiE database. Similarity of overall reactions was computed by comparing the sets of bond changes in the transformations from substrates to products. For similarity of mechanisms, sets of bond changes occurring in each mechanistic step were compared; these similarities were then used to guide global and local alignments of mechanistic steps. Using this metric, only 44% of pairs of functionally analogous enzymes in the dataset had significantly similar overall reactions. For these enzymes, convergence to the same mechanism occurred in 33% of cases, with most pairs having at least one identical mechanistic step. Using our metric, overall reaction similarity serves as an upper bound for mechanistic similarity in functional analogs. For example, the four carbon-oxygen lyases acting on phosphates (EC 4.2.3 show neither significant overall reaction similarity nor significant mechanistic similarity. By contrast, the three carboxylic-ester hydrolases (EC 3.1.1 catalyze overall reactions with identical bond changes and have converged to almost identical mechanisms. The large proportion of enzyme pairs that do not show significant overall reaction similarity (56% suggests that at least for the functionally analogous enzymes studied here, more stringent criteria could be used to

Determination of thermodynamic parameters for enolization reaction of malonic and metylmalonic acids by using quartz crystal microbalance

Directory of Open Access Journals (Sweden)

Minoru Yoshimoto

2016-06-01

Full Text Available We investigated the process of a bromination reaction of malonic acid and methylmalonic acid in the Belousov-Zhabotinsky reaction by using a quartz crystal microbalance (QCM. The process involves an enolization reaction as a rate-determining step. We found that, in the step, the variation of Br2 concentration induced an exactly quantitative shift of a resonant frequency of the QCM, based on the change of the surface mass on the QCM and the solution viscosity and density. This new finding enabled us to estimate the reaction rate constants and the thermodynamic parameters of the enolization reaction due to a QCM measurement. The values measured by the QCM were in good agreement with those measured by a UV-spectrophotometer. As a result, we succeeded to develop a new measurement method of a nonlinear chemical reaction.

Self-consistent theory of charged current neutrino-nucleus reactions

Energy Technology Data Exchange (ETDEWEB)

Paar, Nils; Marketin, Tomislav; Vretenar, Dario [Physics Department, Faculty of Science, University Zagreb (Croatia); Ring, Peter [Physik-Department, Technischen Universitaet Muenchen, D-85748 Muenchen (Germany)

2009-07-01

A novel theoretical framework has been introduced for description of neutrino induced reactions with nuclei. The properties of target nuclei are determined in a self-consistent way using relativistic mean-field framework based on effective Lagrangians with density dependent meson-nucleon vertex functions. The weak lepton-hadron interaction is expressed in the standard current-current form, the nuclear ground state is described in the relativistic Hartree-Bogolyubov model, and the relevant transitions to excited nuclear states are calculated in the proton-neutron relativistic quasiparticle random phase approximation. This framework has been employed in studies of charged-current neutrino reactions involving nuclei of relevance for neutrino detectors, r-process nuclei, and neutrino-nucleus cross sections averaged over measured neutrino fluxes and supernova neutrino distributions.

Reactions of modulated molecular beams with pyrolytic graphite IV. Water vapor

International Nuclear Information System (INIS)

Olander, D.R.; Acharya, T.R.; Ullman, A.Z.

1977-01-01

The reaction of water vapor with the prism plane face of anneal pyrolytic graphite was investigated by modulated molecular beam--mass spectrometry methods. The equivalent water vapor pressure of the beam was approx.2 x 10 -5 Torr and the graphite temperature was varied from 300 to 2500 0 K. The mechanism was deduced from three types of experiments: isotope exchange utilizing modulated H 2 O and steady D 2 O beams; measurements of the phase difference between H 2 O and neon reflected from the surface from a mixed primary beam of these species; and reaction of a modulated H 2 O beam to produce CO and H 2 . Based upon the isotope exchange experiments chemisorption of water on graphite was found to be dissociative and reversible. Incident water molecules chemisorbed with a sticking probability of 0.15 +- 0.02 to form the complexes C--OH and C--H. Recombination of the surface complexes reverses the adsorption step and is responsible for the isotope exchange properties of the graphite surface. This process is unactivated. Reaction to produce CO and H 2 also results from collisions of the primary surface complexes, but this step has an activation energy of 170 kJ/mole. This reaction yields bound complexes tentatively identified as C--O and H--C--H, which then decompose to produce the stable reaction products. All of the above steps exhibit characteristic times on the order of milliseconds, and are therefore detectable by the modulated beam method. All surface intermediates are strongly affected by solution and diffusion in the bulk of the solid

SCScore: Synthetic Complexity Learned from a Reaction Corpus.

Science.gov (United States)

Coley, Connor W; Rogers, Luke; Green, William H; Jensen, Klavs F

2018-02-26

Several definitions of molecular complexity exist to facilitate prioritization of lead compounds, to identify diversity-inducing and complexifying reactions, and to guide retrosynthetic searches. In this work, we focus on synthetic complexity and reformalize its definition to correlate with the expected number of reaction steps required to produce a target molecule, with implicit knowledge about what compounds are reasonable starting materials. We train a neural network model on 12 million reactions from the Reaxys database to impose a pairwise inequality constraint enforcing the premise of this definition: that on average, the products of published chemical reactions should be more synthetically complex than their corresponding reactants. The learned metric (SCScore) exhibits highly desirable nonlinear behavior, particularly in recognizing increases in synthetic complexity throughout a number of linear synthetic routes.

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)

Proton induced nuclide production cross section by HETC-3STEP/FRG-R

Energy Technology Data Exchange (ETDEWEB)

Shigyo, Nobuhiro; Ishibashi, Kenji [Kyushu Univ., Fukuoka (Japan); Yoshizawa, Nobuaki; Takada, Hiroshi

1998-03-01

High Energy Transport Code (HETC) based on the intranuclear-cascade-evaporation model is modified to calculate the fragmentation cross section. The exciton model is adopted for improvement of backward nucleon-emission cross section for low-energy nucleon-incident events. The level density parameter depending on the excitation energy is taken in the evaporation process. The fragmentation reaction is incorporated into HETC as a subroutine set by the use of the systematics of the reaction. The modified HETC (HETC-3STEP/FRG-R) reproduces experimental fragment yields to a reasonable degree. (author)

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.

Suppression of the stellar enhancement factor and the reaction 85Rb(p,n)85Sr

International Nuclear Information System (INIS)

Rauscher, T.; Kiss, G. G.; Gyuerky, Gy.; Simon, A.; Fueloep, Zs.; Somorjai, E.

2009-01-01

It is shown that a Coulomb suppression of the stellar enhancement factor occurs in many endothermic reactions at and far from stability. Contrary to common assumptions, reaction measurements for astrophysics with minimal impact of stellar enhancement should be preferably performed for those reactions instead of their reverses, despite of their negative Q value. As a demonstration, the cross section of the astrophysically relevant 85 Rb(p,n) 85 Sr reaction has been measured by activation between 2.16≤E c.m. ≤3.96 MeV and the astrophysical reaction rates at p process temperatures for (p,n) as well as (n,p) are directly inferred from the data. Additionally, our results confirm a previously derived modification of a global optical proton potential. The presented arguments are also relevant for other α- and proton-induced reactions in the p, rp, and νp processes.

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...

Step-edge calibration of torsional sensitivity for lateral force microscopy

International Nuclear Information System (INIS)

Sul, Onejae; Jang, Seongjin; Yang, Eui-Hyeok

2009-01-01

A novel calibration technique has been developed for lateral force microscopy (LFM). Typically, special preparation of the atomic force microscope (AFM) cantilever or a substrate is required for LFM calibration. The new calibration technique reported in this paper greatly reduces the required preparation processes by simply scanning over a rigid step and measuring the response of the AFM photodiode in the normal and lateral directions. When an AFM tip touches a step while scanning, the tip experiences a reaction force from the step edge, and the amount of torsion can be estimated based on the ratio of the normal and torsional spring constants of an AFM cantilever. Therefore, the torsion can be calibrated using the measured response of the photodiode from the lateral movement of the AFM tip. This new calibration technique has been tested and confirmed by measuring Young's modulus of a nickel (Ni) nanowire

Amplitude and phase of surface plasmon polaritons excited at a step edge

DEFF Research Database (Denmark)

Klick, Alwin; de la Cruz, Sergio; Lemke, Christoph

2016-01-01

A combined experimental and theoretical study on the laser-induced excitation of surface plasmon polaritons (SPP) at well-defined step edges of a gold–vacuum interface is presented. As a relevant parameter determining the coupling efficiency between laser field and SPP, we identify the ratio betw...

Arousal and exposure duration affect forward step initiation

Directory of Open Access Journals (Sweden)

Daniëlle eBouman

2015-11-01

Full Text Available Emotion influences parameters of goal-directed whole-body movements in several ways. For instance, previous research has shown that approaching (moving toward pleasant stimuli is easier compared to approaching unpleasant stimuli. However, some studies found that when emotional pictures are viewed for a longer time, approaching unpleasant stimuli may in fact be facilitated. The effect of viewing duration may modulate whole-body approach movement in previous research but this has not been investigated before. In the current study, participants initiated a step forward after viewing neutral, high-arousal pleasant and high-arousal unpleasant stimuli. The viewing duration of the stimuli was set to 7 different durations, varying from 100 to 4000ms. Valence and arousal scores were collected for all stimuli.The results indicate that both viewing duration and the arousal of the stimuli influence kinematic parameters in forward gait initiation. Specifically, longer viewing duration, compared to shorter viewing duration, (a diminished the step length and peak velocity in both neutral and emotional stimuli, (b increased reaction time in neutral stimuli and, (c decreased reaction time in pleasant and unpleasant stimuli. Strikingly, no differences were found between high-arousal pleasant and high-arousal unpleasant stimuli. In other words, the valence of the stimuli did not influence kinematic parameters of forward step initiation. In contrast, the arousal level (neutral: low; pleasant and unpleasant: high explained the variance found in the results. The kinematics of forward gait initiation seemed to be reflected in the subjective arousal scores, but not the valence scores. So it seems arousal affects forward gait initiation parameters more strongly than valence. In addition, longer viewing duration seemed to cause diminished alertness, affecting GI parameters. These results shed new light on the prevailing theoretical interpretations regarding approach

Chemical cleavage reactions of DNA on solid support: application in mutation detection

Directory of Open Access Journals (Sweden)

Cotton Richard GH

2003-05-01

Full Text Available Abstract Background The conventional solution-phase Chemical Cleavage of Mismatch (CCM method is time-consuming, as the protocol requires purification of DNA after each reaction step. This paper describes a new version of CCM to overcome this problem by immobilizing DNA on silica solid supports. Results DNA test samples were loaded on to silica beads and the DNA bound to the solid supports underwent chemical modification reactions with KMnO4 (potassium permanganate and hydroxylamine in 3M TEAC (tetraethylammonium chloride solution. The resulting modified DNA was then simultaneously cleaved by piperidine and removed from the solid supports to afford DNA fragments without the requirement of DNA purification between reaction steps. Conclusions The new solid-phase version of CCM is a fast, cost-effective and sensitive method for detection of mismatches and mutations.

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).

Synthesis of 2-vinylic indoles and derivatives via a Pd-catalyzed tandem coupling reaction.

Science.gov (United States)

Fayol, Aude; Fang, Yuan-Qing; Lautens, Mark

2006-09-14

A novel one-step synthesis of valuable 2-vinylic indoles and their tricycle derivatives is described. This reaction, which utilizes a gem-dibromovinyl unit as a readily available starting material, occurs via an efficient Pd-catalyzed tandem Buchwald-Hartwig/Heck reaction.

Automotive exhaust gas conversion: from elementary step kinetics to prediction of emission dynamics

NARCIS (Netherlands)

Hoebink, J.H.B.J.; Harmsen, J.M.A.; Balenovic, M.; Backx, A.C.P.M.; Schouten, J.C.

2001-01-01

Elementary step based kinetics show a high added value to describe the performance of catalytic exhaust gas converters under dynamic conditions, as demonstrated with a Euro test cycle. Combination of such kinetic models for individual global reactions covers the mutual interactions via common

Steps to strengthen ethics in organizations: research findings, ethics placebos, and what works.

Science.gov (United States)

Pope, Kenneth S

2015-01-01

Research shows that many organizations overlook needs and opportunities to strengthen ethics. Barriers can make it hard to see the need for stronger ethics and even harder to take effective action. These barriers include the organization's misleading use of language, misuse of an ethics code, culture of silence, strategies of justification, institutional betrayal, and ethical fallacies. Ethics placebos tend to take the place of steps to see, solve, and prevent problems. This article reviews relevant research and specific steps that create change.

Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study

Directory of Open Access Journals (Sweden)

Shinichi Yamabe

2014-01-01

Full Text Available Wolff–Kishner reduction reactions were investigated by DFT calculations for the first time. B3LYP/6-311+G(d,p SCRF=(PCM, solvent = 1,2-ethanediol optimizations were carried out. To investigate the role of the base catalyst, the base-free reaction was examined by the use of acetone, hydrazine (H2N–NH2 and (H2O8. A ready reaction channel of acetone → acetone hydrazine (Me2C=N–NH2 was obtained. The channel involves two likely proton-transfer routes. However, it was found that the base-free reaction was unlikely at the N2 extrusion step from the isopropyl diimine intermediate (Me2C(H–N=N–H. Two base-catalyzed reactions were investigated by models of the ketone, H2N–NH2 and OH−(H2O7. Here, ketones are acetone and acetophenone. While routes of the ketone → hydrazone → diimine are similar, those from the diimines are different. From the isopropyl diimine, the N2 extrusion and the C–H bond formation takes place concomitantly. The concomitance leads to the propane product concertedly. From the (1-phenylethyl substituted diimine, a carbanion intermediate is formed. The para carbon of the phenyl ring of the anion is subject to the protonation, which leads to a 3-ethylidene-1,4-cyclohexadiene intermediate. Its [1,5]-hydrogen migration gives the ethylbenzene product. For both ketone substrates, the diimines undergoing E2 reactions were found to be key intermediates.

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.

Sequential Au(I-catalyzed reaction of water with o-acetylenyl-substituted phenyldiazoacetates

Directory of Open Access Journals (Sweden)

Jianbo Wang

2011-05-01

Full Text Available The gold(I-catalyzed reaction of water with o-acetylenyl-substituted phenyldiazoacetates provides 1H-isochromene derivatives in good yields. The reaction follows a catalytic sequence of gold carbene formation/water O–H insertion/alcohol-alkyne cyclization. The gold(I complex is the only catalyst in each of these steps.

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.

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.

Pathways of the Maillard reaction under physiological conditions.

Science.gov (United States)

Henning, Christian; Glomb, Marcus A

2016-08-01

Initially investigated as a color formation process in thermally treated foods, nowadays, the relevance of the Maillard reaction in vivo is generally accepted. Many chronic and age-related diseases such as diabetes, uremia, atherosclerosis, cataractogenesis and Alzheimer's disease are associated with Maillard derived advanced glycation endproducts (AGEs) and α-dicarbonyl compounds as their most important precursors in terms of reactivity and abundance. However, the situation in vivo is very challenging, because Maillard chemistry is paralleled by enzymatic reactions which can lead to both, increases and decreases in certain AGEs. In addition, mechanistic findings established under the harsh conditions of food processing might not be valid under physiological conditions. The present review critically discusses the relevant α-dicarbonyl compounds as central intermediates of AGE formation in vivo with a special focus on fragmentation pathways leading to formation of amide-AGEs.

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…

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.

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.

Kinetic mechanism of human DNA ligase I reveals magnesium-dependent changes in the rate-limiting step that compromise ligation efficiency.

Science.gov (United States)

Taylor, Mark R; Conrad, John A; Wahl, Daniel; O'Brien, Patrick J

2011-07-01

DNA ligase I (LIG1) catalyzes the ligation of single-strand breaks to complete DNA replication and repair. The energy of ATP is used to form a new phosphodiester bond in DNA via a reaction mechanism that involves three distinct chemical steps: enzyme adenylylation, adenylyl transfer to DNA, and nick sealing. We used steady state and pre-steady state kinetics to characterize the minimal mechanism for DNA ligation catalyzed by human LIG1. The ATP dependence of the reaction indicates that LIG1 requires multiple Mg(2+) ions for catalysis and that an essential Mg(2+) ion binds more tightly to ATP than to the enzyme. Further dissection of the magnesium ion dependence of individual reaction steps revealed that the affinity for Mg(2+) changes along the reaction coordinate. At saturating concentrations of ATP and Mg(2+) ions, the three chemical steps occur at similar rates, and the efficiency of ligation is high. However, under conditions of limiting Mg(2+), the nick-sealing step becomes rate-limiting, and the adenylylated DNA intermediate is prematurely released into solution. Subsequent adenylylation of enzyme prevents rebinding to the adenylylated DNA intermediate comprising an Achilles' heel of LIG1. These ligase-generated 5'-adenylylated nicks constitute persistent breaks that are a threat to genomic stability if they are not repaired. The kinetic and thermodynamic framework that we have determined for LIG1 provides a starting point for understanding the mechanism and specificity of mammalian DNA ligases.

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

Evaluation of tri-steps modified styrene-butadiene-styrene block copolymer membrane for wound dressing

Energy Technology Data Exchange (ETDEWEB)

Yang, Jen Ming, E-mail: jmyang@mail.cgu.edu.tw; Huang, Huei Tsz

2012-08-01

Tri-steps modified styrene-butadiene-styrene block copolymer (SBS) membrane was prepared with epoxidation, ring opening reaction with maleated ionomer and layer-by-layer assembled polyelectrolyte technique. The tri-steps modified SBS membrane was characterized by infrared spectroscopy and X-ray photoelectron spectroscope (XPS). The structures of the modified SBS membranes were identified with methylene blue and azocarmine G. The content of amino group on the surface of the modified membrane was calculated from uptake of an acid dye. The values of the contact angle, water absorption, water vapor transmission rate and the adsorption of fibronectin on the membranes were determined. To evaluate the biocompatibility of the tri-steps modified SBS membrane, the cytotoxicity, antibacterial and growth profile of the cell culture of 3T3 fibroblasts on the membrane were evaluated. The bactericidal activity was found on the modified SBS. From the cell culture of 3T3 fibroblasts on the membrane, it revealed that the cells not only remained viable but also proliferated on the surface of the tri-steps modified SBS membranes. As the membranes are sterile semipermeable with bactericidal activity and transparent allowing wound checks, they can be considered for shallow wound with low exudates. - Highlights: Black-Right-Pointing-Pointer Styrene-butadiene-styrene block copolymer (SBS) was modified with tri-steps. Black-Right-Pointing-Pointer The tri-steps are epoxidation, ring opening reaction and layer-by-layer assembly. Black-Right-Pointing-Pointer Modified SBS membrane for wound dressing is evaluated. Black-Right-Pointing-Pointer Membranes are sterile semipermeable with bactericidal activity and transparent. Black-Right-Pointing-Pointer Membranes can be considered for shallow wound with low exudates.

Methylene blue as a lignin surrogate in manganese peroxidase reaction systems.

Science.gov (United States)

Goby, Jeffrey D; Penner, Michael H; Lajoie, Curtis A; Kelly, Christine J

2017-11-15

Manganese peroxidase (MnP) is associated with lignin degradation and is thus relevant to lignocellulosic-utilization technologies. Technological applications require reaction mixture optimization. A surrogate substrate can facilitate this if its susceptibility to degradation is easily monitored and mirrors that of lignin. The dye methylene blue (MB) was evaluated in these respects as a surrogate substrate by testing its reactivity in reaction mixtures containing relevant redox mediators (dicarboxylic acids, fatty acids). Relative rates of MB degradation were compared to available literature reports of lignin degradation under similar conditions, and suggest that MB can be a useful lignin surrogate in MnP systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Tai Chi practitioners have better postural control and selective attention in stepping down with and without a concurrent auditory response task.

Science.gov (United States)

Lu, Xi; Siu, Ka-Chun; Fu, Siu N; Hui-Chan, Christina W Y; Tsang, William W N

2013-08-01

To compare the performance of older experienced Tai Chi practitioners and healthy controls in dual-task versus single-task paradigms, namely stepping down with and without performing an auditory response task, a cross-sectional study was conducted in the Center for East-meets-West in Rehabilitation Sciences at The Hong Kong Polytechnic University, Hong Kong. Twenty-eight Tai Chi practitioners (73.6 ± 4.2 years) and 30 healthy control subjects (72.4 ± 6.1 years) were recruited. Participants were asked to step down from a 19-cm-high platform and maintain a single-leg stance for 10 s with and without a concurrent cognitive task. The cognitive task was an auditory Stroop test in which the participants were required to respond to different tones of voices regardless of their word meanings. Postural stability after stepping down under single- and dual-task paradigms, in terms of excursion of the subject's center of pressure (COP) and cognitive performance, was measured for comparison between the two groups. Our findings demonstrated significant between-group differences in more outcome measures during dual-task than single-task performance. Thus, the auditory Stroop test showed that Tai Chi practitioners achieved not only significantly less error rate in single-task, but also significantly faster reaction time in dual-task, when compared with healthy controls similar in age and other relevant demographics. Similarly, the stepping-down task showed that Tai Chi practitioners not only displayed significantly less COP sway area in single-task, but also significantly less COP sway path than healthy controls in dual-task. These results showed that Tai Chi practitioners achieved better postural stability after stepping down as well as better performance in auditory response task than healthy controls. The improved performance that was magnified by dual motor-cognitive task performance may point to the benefits of Tai Chi being a mind-and-body exercise.

Reactions of nitrate salts with ammonia in supercritical water

International Nuclear Information System (INIS)

Dell'Orco, P.C.; Gloyna, E.F.; Buelow, S.J.

1997-01-01

Reactions involving nitrate salts and ammonia were investigated in supercritical water at temperatures from 450 to 530 C and pressures near 300 bar. Reaction products included nitrite, nitrogen gas, and nitrous oxide. Observed reaction rates and product distributions provided evidence for a free-radical reaction mechanism with NO 2 , NO, and NH 2 · as the primary reactive species at supercritical conditions. In the proposed elementary mechanism, the rate-limiting reaction step was determined to be the hydrolysis of MNO 3 species, which resulted in the formation of nitric acid and subsequently NO 2 . A simple second-order reaction model was used to represent the data. In developing an empirical kinetic model, nitrate and nitrate were lumped as an NO x - reactant. Empirical kinetic parameters were developed for four MNO x /NH 3 reacting systems, assuming first orders in both NH 3 and NO x - . Observed MNO x /NH 3 reaction rates and mechanisms suggest immediately a practical significance of these reactions for nitrogen control strategies in supercritical water oxidation processes

Towards a lumped reaction model for future designer fuels

Energy Technology Data Exchange (ETDEWEB)

Vandersickel, A.; Wright, Y.M.; Boulouchos, K. [ETH Zurich, Aerothermochemistry and Combustion Systems Laboratory, Zurich (Switzerland). Inst. of Energy Technology

2009-07-01

The homogeneous charge compression ignition (HCCI) is one of the most promising engine processes to simultaneously reduce nitrogen oxide and soot emissions. However, its applicability is hindered by its relatively limited operating range. Designer fuels offer unique possibilities for tailoring evaporation and auto-ignition properties, offering a means to control and expand the HCCI operation range. The identification of HCCI relevant fuel properties as well as the definition of a new fuel index able to describe a fuels suitability for HCCI was required in order to develop such designer fuels. This paper discussed a numerical and experimental investigation of a large set of technical fuels covering a wide range of properties. The paper discussed mechanism development approaches, optimization of the lumped mechanism, and and results. Zheng's 7-step reaction mechanism was successfully coupled with a genetic optimization algorithm and fitted to n-heptane ignition delay data. It was concluded that the presented coupled approach could improve the predictive quality of the model and demonstrate that the Zheng model was sufficiently elaborate to emulate the influence of temperature, pressure, exhaust gas recirculation and lambda on ignition. 8 refs., 1 tab., 3 figs.

Towards a lumped reaction model for future designer fuels

International Nuclear Information System (INIS)

Vandersickel, A.; Wright, Y.M.; Boulouchos, K.

2009-01-01

The homogeneous charge compression ignition (HCCI) is one of the most promising engine processes to simultaneously reduce nitrogen oxide and soot emissions. However, its applicability is hindered by its relatively limited operating range. Designer fuels offer unique possibilities for tailoring evaporation and auto-ignition properties, offering a means to control and expand the HCCI operation range. The identification of HCCI relevant fuel properties as well as the definition of a new fuel index able to describe a fuels suitability for HCCI was required in order to develop such designer fuels. This paper discussed a numerical and experimental investigation of a large set of technical fuels covering a wide range of properties. The paper discussed mechanism development approaches, optimization of the lumped mechanism, and and results. Zheng's 7-step reaction mechanism was successfully coupled with a genetic optimization algorithm and fitted to n-heptane ignition delay data. It was concluded that the presented coupled approach could improve the predictive quality of the model and demonstrate that the Zheng model was sufficiently elaborate to emulate the influence of temperature, pressure, exhaust gas recirculation and lambda on ignition. 8 refs., 1 tab., 3 figs.

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.

One-nucleon pickup reactions and compound-nuclear decays

Science.gov (United States)

Escher, J. E.; Burke, J. T.; Casperson, R. J.; Hughes, R. O.; Scielzo, N. D.

2018-05-01

One-nucleon transfer reactions, long used as a tool to study the structure of nuclei, are potentially valuable for determining reaction cross sections indirectly. This is significant, as many reactions of interest to astrophysics and other applications involve short-lived isotopes and cannot be measured directly. We describe a procedure for obtaining constraints for calculations of neutron capture cross sections using observables from experiments with transfer reactions. As a first step toward demonstrating the method, we outline the theory developments used to properly describe the production of the compound nucleus 88Y* via the one-nucleon pickup reaction 89Y(p,d)88Y* and test the description with data from a recent experiment. We indicate how this development can be used to extract the unknown 87Y(n,γ) cross section from 89Y(p,dγ) data. The example illustrates a more generally applicable method for determining unknown cross sections via a combination of theory and transfer (or inelastic scattering) experiments.

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.

Plasma fluctuations and confinement of fusion reaction products

International Nuclear Information System (INIS)

Coppi, B.; Pegoraro, F.

1981-01-01

The interaction between the fluctuations that can be excited in a magnetically confined plasma and the high-energy-particle population produced by fusion reactions is analyzed in view of its relevance to the process of thermonuclear ignition. The spectrum of the perturbations that, in the absence of fusion reaction products, would be described by the incompressible ideal magnetohydrodynamic approximation is studied considering finite value of the plasma pressure relative ot the magnetic pressure. The combined effects of the magnetic field curvature and shear are taken into account and the relevant spectrum is shown to consist of a continuous portion, that could be identified as a mixture of shear-Alfven and interchange oscillations, and a discrete unstable part corresponding to the so-called ballooning modes. The rate of diffusion of the fusion reaction products induced by oscillations in the continuous part of the spectrum, as estimated from the appropriate quasi-linear theory, is found to be significantly smaller than could be expected if normal modes (i.e., nonconvective solutions) were excited. However, a relatively wide intermediate region is identified where opalescent fluctuations, capable of achieving significant amplitudes and corresponding to a quasi-discrete spectrum, can be excited

Computational Approach to Electron Charge Transfer Reactions

DEFF Research Database (Denmark)

Jónsson, Elvar Örn

-molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical environments - chemical in the sense that solvent, counter ions and substrate surfaces are taken...... in to account - which directly influence the reactants and resulting reaction through both physical and chemical interactions. All methods are though general and can be applied to different types of chemistry. First, the basis of the various theoretical tools is presented and applied to several test systems...... and asymmetric charge transfer reactions between several first-row transition metals in water. The results are compared to experiments and rationalised with classical analytic expressions. Shortcomings of the methods are accounted for with clear steps towards improved accuracy. Later the analysis is extended...

Chemical tailoring of teicoplanin with site-selective reactions.

Science.gov (United States)

Pathak, Tejas P; Miller, Scott J

2013-06-05

Semisynthesis of natural product derivatives combines the power of fermentation with orthogonal chemical reactions. Yet, chemical modification of complex structures represents an unmet challenge, as poor selectivity often undermines efficiency. The complex antibiotic teicoplanin eradicates bacterial infections. However, as resistance emerges, the demand for improved analogues grows. We have discovered chemical reactions that achieve site-selective alteration of teicoplanin. Utilizing peptide-based additives that alter reaction selectivities, certain bromo-teicoplanins are accessible. These new compounds are also scaffolds for selective cross-coupling reactions, enabling further molecular diversification. These studies enable two-step access to glycopeptide analogues not available through either biosynthesis or rapid total chemical synthesis alone. The new compounds exhibit a spectrum of activities, revealing that selective chemical alteration of teicoplanin may lead to analogues with attenuated or enhanced antibacterial properties, in particular against vancomycin- and teicoplanin-resistant strains.

Electro-induced reactions of biologically important molecules

International Nuclear Information System (INIS)

Kocisek, J.

2010-01-01

The thesis presents the results of research activities in the field of electron interactions with biologically relevant molecules which was carried out during my PhD studies at the Department of Experimental Physics, Comenius University in Bratislava. Electron induced interactions with biologically relevant molecules were experimentally studied using crossed electron-molecule beams experiment. The obtained results, were presented in four publications in international scientific journals. First study of deals with electron impact ionisation of furanose alcohols [see 1. in list of author publications on page 22]. It has been motivated by most important works in the field of electron induced damages of DNA bases [4]. Studied 3-hydroxytetrahydrofuran and tetrahydrofurfuryl alcohol, are important model molecules for more complex biological systems (e.g. deoxyribose).The influence of hydroxyl group on stabilisation of the positive ions of the molecules, together with the stability of furan ring in ionized form are main themes of the study. The studies of small amides and aminoacids are connected to scientific studies in the field of formation of the aminoacids and other biologically relevant molecules in space and works trying to explain electron induced processes in more complex molecules[12, 13, 24]. The most important results were obtained for aminoacid Serine [see 2. in list of author publications on page 22]. We have showed that additional OH group of Serine considerably lower the reaction enthalpy limit of reactions resulting to formation of neutral water molecules, in comparison to other amino acids. Also the study of (M-H)- reaction channel using the electron beam with FWHM under 100 meV is of high importance in the field. The last part of the thesis is focused on the electron interactions with organosilane compounds. Materials prepared from organosilane molecules in plasmas have wide range of applications in both biology and medicine. We have studied electron

Recoil properties of radionuclides formed in photospallation reactions on complex nuclei at intermediate energies

International Nuclear Information System (INIS)

Haba, Hiromitsu; Oura, Yasuji; Shibata, Seiichi; Furukawa, Michiaki; Fujiwara, Ichiro

2001-01-01

A short review is given on our studies of recoil properties of radionuclides formed in photospallation reactions induced by bremsstrahlung of end-point energies (E 0 ) from 600 to 1100 MeV, in which the thick-target thick-catcher method was employed. The measurements have been successful on 14, 24, 26, 31, 21 and 20 nuclides from nat V, nat Cu, 93 Nb, nat Ag, nat Ta, and 197 Au, respectively. Reflecting the resonance character in a photonuclear reaction, the mean ranges FW and BW in the forward and backward directions, respectively, are E 0 -independent at the studied energies and classified into two groups accounting for the (γ, xn) (x ≥ 1) and (γ, xnyp) (x, y ≥ 1) processes. The forward-to-backward ratios (F/B) are independent of the mass difference (ΔA) between a product (A p ) and a target (A t ) and also of A t . The kinematic properties of the product nuclei were analyzed by the two-step vector velocity model. The forward velocity ν after the first step of photon-reaction is quite different from that of proton-reaction at proton energies of E p ≤ 3 GeV, though the difference disappears at higher energies. On the other hand, the mean kinetic energy T of the residual nucleus in the second step is almost equal to that of proton-reaction irrespective of E p . A comparison with T values calculated by the PICA (Photon-Induced Intranuclear Cascade Analysis) code at E 0 =400 MeV was also performed. It was found that although the code well reproduces the experimental results of nat V and nat Cu, the same calculation for heavier targets gives T values lower than the experimental results, indicating some nuclear-structure effect, such as a medium effect notably at A t ≥ 100. An average kinetic energy carried off by the emitted particles ε s =T/(ΔA/A t ) of both photon- and proton-reactions seem to increase with an increase of A t up to around A t =100, and become almost constant at larger A t , implying some change in the nuclear structure effect in this

Two-step excitation structure changes of luminescence centers and strong tunable blue emission on surface of silica nanospheres

Energy Technology Data Exchange (ETDEWEB)

Yang, Lei, E-mail: nanoyang@qq.com; Jiang, Zhongcheng; Dong, Jiazhang; Zhang, Liuqian [Hunan University, College of Materials Science and Engineering (China); Pan, Anlian, E-mail: anlian.pan@gmail.com; Zhuang, Xiujuan [Hunan University, Key Laboratory for Micro-Nano Physics and Technology of Hunan Province (China)

2015-10-15

We report a scheme for investigating two-step stimulated structure change of luminescence centers. Amorphous silica nanospheres with uniform diameter of 9–15 nm have been synthesized by Stöber method. Strong hydroxyl-related infrared-absorption band is observed in infrared spectrum. The surface hydroxyl groups exert great influence on the luminescent behavior of silica. They provide stable and intermediate energy states to accommodate excitation electrons. The existence of these surface states reduces the energy barrier of photochemical reactions, creating conditions for two-step excitation process. By carefully examining excitation and emission process, the nearest excitation band is absent in both optical absorption spectrum and excitation spectrum. This later generated state confirms the generation of new luminescence centers as well as the existence of photochemical reactions. Stimulated by different energies, two-step excitation process impels different photochemical reactions, prompting generation of different lattice defects on surface area of silica. Thereby, tunable luminescence is achieved. After thermal treatment, strong gap excitation band appears with the disappearance of strong surface excitation band. Strong blue luminescence also disappears. The research is significance to precise introducing structural defects and controlling position of luminescence peaks.

Production of radioactive nuclides in inverse reaction kinematics

International Nuclear Information System (INIS)

Traykov, E.; Rogachevskiy, A.; Bosswell, M.; Dammalapati, U.; Dendooven, P.; Dermois, O.C.; Jungmann, K.; Onderwater, C.J.G.; Sohani, M.; Willmann, L.; Wilschut, H.W.; Young, A.R.

2007-01-01

Efficient production of short-lived radioactive isotopes in inverse reaction kinematics is an important technique for various applications. It is particularly relevant when the isotope of interest is only a few nucleons away from a stable isotope. In this article production via charge exchange and stripping reactions in combination with a magnetic separator is explored. The relation between the separator transmission efficiency, the production yield, and the choice of beam energy is discussed. The results of some exploratory experiments will be presented

Fuzzy Mutual Information Based min-Redundancy and Max-Relevance Heterogeneous Feature Selection

Directory of Open Access Journals (Sweden)

Daren Yu

2011-08-01

Full Text Available Feature selection is an important preprocessing step in pattern classification and machine learning, and mutual information is widely used to measure relevance between features and decision. However, it is difficult to directly calculate relevance between continuous or fuzzy features using mutual information. In this paper we introduce the fuzzy information entropy and fuzzy mutual information for computing relevance between numerical or fuzzy features and decision. The relationship between fuzzy information entropy and differential entropy is also discussed. Moreover, we combine fuzzy mutual information with qmin-Redundancy-Max-Relevanceq, qMax-Dependencyq and min-Redundancy-Max-Dependencyq algorithms. The performance and stability of the proposed algorithms are tested on benchmark data sets. Experimental results show the proposed algorithms are effective and stable.

Two step continuous method to synthesize colloidal spheroid gold nanorods.

Science.gov (United States)

Chandra, S; Doran, J; McCormack, S J

2015-12-01

This research investigated a two-step continuous process to synthesize colloidal suspension of spheroid gold nanorods. In the first step; gold precursor was reduced to seed-like particles in the presence of polyvinylpyrrolidone and ascorbic acid. In continuous second step; silver nitrate and alkaline sodium hydroxide produced various shape and size Au nanoparticles. The shape was manipulated through weight ratio of ascorbic acid to silver nitrate by varying silver nitrate concentration. The specific weight ratio of 1.35-1.75 grew spheroid gold nanorods of aspect ratio ∼1.85 to ∼2.2. Lower weight ratio of 0.5-1.1 formed spherical nanoparticle. The alkaline medium increased the yield of gold nanorods and reduced reaction time at room temperature. The synthesized gold nanorods retained their shape and size in ethanol. The surface plasmon resonance was red shifted by ∼5 nm due to higher refractive index of ethanol than water. Copyright © 2015 Elsevier Inc. All rights reserved.

Electron transfer reactions in structural units of copper proteins

International Nuclear Information System (INIS)

Faraggi, M.

1975-01-01

In previous pulse radiolysis studies it was suggested that the reduction of the Cu(II) ions in copper proteins by the hydrated electron is a multi-step electron migration process. The technique has been extended to investigate the reduction of some structural units of these proteins. These studies include: the reaction of the hydrated electron with peptides, the reaction of the disulphide bridge with formate radical ion and radicals produced by the reduction of peptides, and the reaction of Cu(II)-peptide complex with esub(aq)sup(-) and CO 2 - . Using these results the reduction mechanism of copper and other proteins will be discussed. (author)

Quantum chemical modeling of enzymatic reactions: the case of 4-oxalocrotonate tautomerase.

Science.gov (United States)

Sevastik, Robin; Himo, Fahmi

2007-12-01

The reaction mechanism of 4-oxalocrotonate tautomerase (4-OT) is studied using the density functional theory method B3LYP. This enzyme catalyzes the isomerisation of unconjugated alpha-keto acids to their conjugated isomers. Two different quantum chemical models of the active site are devised and the potential energy curves for the reaction are computed. The calculations support the proposed reaction mechanism in which Pro-1 acts as a base to shuttle a proton from the C3 to the C5 position of the substrate. The first step (proton transfer from C3 to proline) is shown to be the rate-limiting step. The energy of the charge-separated intermediate (protonated proline-deprotonated substrate) is calculated to be quite low, in accordance with measured pKa values. The results of the two models are used to evaluate the methodology employed in modeling enzyme active sites using quantum chemical cluster models.

Reconstitution of Low Bandwidth Reaction History

International Nuclear Information System (INIS)

May, M.; Clancy, T.; Fittinghoff, D.; Gennaro, P.; Hagans, K.; Halvorson, G.; Lowry, M.; Perry, T.; Roberson, P.; Smith, D.; Teruya, A.; Blair, J.; Davis, B.; Hunt, E.; Emkeit, B.; Galbraith, J.; Kelly, B.; Montoya, R.; Nickel, G.; Ogle, J.; Wilson, K.; Wood, M.

2004-01-01

The goal of the Test Readiness Program is to transition to a 24 month test readiness posture and if approved move to an 18-month posture. One of the key components of the Test Readiness Program necessary to meet this goal is the reconstitution of the important diagnostics. Since the end of nuclear testing, the ability to field diagnostics on a nuclear test has deteriorated. Reconstitution of diagnostics before those who had experience in nuclear testing either retire or leave is essential to achieving a shorter test readiness posture. Also, the data recording systems have not been used since the end of testing. This report documents the reconstitution of one vital diagnostic: the low bandwidth reaction history diagnostic for FY04. Reaction history is one of the major diagnostics that has been used on all LLNL and LANL tests since the early days of nuclear testing. Reaction history refers to measuring the time history of the gamma and neutron output from a nuclear test. This gives direct information on the nuclear reactions taking place in the device. The reaction history measurements are one of the prime measurements the nuclear weapon scientists use to validate their models of device performance. All tests currently under consideration require the reaction history diagnostic. Thus moving to a shorter test readiness posture requires the reconstitution of the ability to make reaction history measurements. Reconstitution of reaction history was planned to be in two steps. Reaction history measurements that have been used in the past can be broadly placed into two categories. The most common type of reaction history and the one that has been performed on virtually all nuclear tests is termed low bandwidth reaction history. This measurement has a time response that is limited by the bandpass of kilometer length coaxial cables. When higher bandwidth has been required for specific measurements, fiber optic techniques have been used. This is referred to as high

Flexible single molecule simulation of reaction-diffusion processes

International Nuclear Information System (INIS)

Hellander, Stefan; Loetstedt, Per

2011-01-01

An algorithm is developed for simulation of the motion and reactions of single molecules at a microscopic level. The molecules diffuse in a solvent and react with each other or a polymer and molecules can dissociate. Such simulations are of interest e.g. in molecular biology. The algorithm is similar to the Green's function reaction dynamics (GFRD) algorithm by van Zon and ten Wolde where longer time steps can be taken by computing the probability density functions (PDFs) and then sample from the distribution functions. Our computation of the PDFs is much less complicated than GFRD and more flexible. The solution of the partial differential equation for the PDF is split into two steps to simplify the calculations. The sampling is without splitting error in two of the coordinate directions for a pair of molecules and a molecule-polymer interaction and is approximate in the third direction. The PDF is obtained either from an analytical solution or a numerical discretization. The errors due to the operator splitting, the partitioning of the system, and the numerical approximations are analyzed. The method is applied to three different systems involving up to four reactions. Comparisons with other mesoscopic and macroscopic models show excellent agreement.

Attention bias towards personally relevant stimuli: the individual emotional Stroop task.

Science.gov (United States)

Wingenfeld, Katja; Bullig, Renate; Mensebach, Christoph; Hartje, Wolfgang; Driessen, Martin; Beblo, Thomas

2006-12-01

The emotional Stroop task is a widely used method for investigating attentional bias towards stimuli due to mood or affect. In general, standardized stimuli are used, which might not be appropriate when investigating individual contextual frameworks. It was investigated whether words chosen to be related to individuals' personal life events would produce more pronounced Stroop interference (as an indicator of attentional bias) than stimuli without any personal relevance. Twenty-six nonclinical subjects, 20 female and 6 male, participated in the study. Mean age was 36.1 yr. (SD = 18.1). All were recruited by means of local advertising. Stimulus material consisted of four word types: personal words related to negative life events with and without current personal relevance, and negative and neutral words without any personal relevance. Words were presented in three blocks. Analysis of variance showed main effects for word type and blocks, with slower reactions in the personally relevant conditions than in the negative, or neutral conditions, and in response to the first blocks as opposed to the last. These findings indicate that regardless of the word valence, personally relevant stimuli evoke more pronounced Stroop interference than do stimuli without personal relevance.

DEMO relevance of the test blanket modules in ITER-Application to the European test blanket modules

International Nuclear Information System (INIS)

Magnani, E.; Gabriel, F.; Boccaccini, L.V.; Li-Puma, A.

2010-01-01

Test blanket module (TBM) testing programme in ITER as a support to DEMO design is a very important step on the road map to commercial fusion reactors although it is an ambitious task. Finding as much as possible DEMO relevant tests in view of the future DEMO blanket design is therefore a major goal since ITER and DEMO environment and loading conditions are different. To clarify and quantify the meaning of the DEMO relevance, criteria using a structural, functional and behavioural representation of the breeding blanket acting as a system are investigated. Then, a three-step strategy is proposed to carry out TBM DEMO relevant tests associated with a TBM design modification strategy. Key parameters should intensively be used as target for TBM characterization and numerical code validation. When assessing the relevance, on the other hand, not only the actual difference between DEMO and ITER values should be considered, but also whether the analyzed phenomena have a threshold and a range of applicability, as numerical simulations are usually permitted within these limits. The proposed methodology is at the end applied to the design of the HCLL TBM breeding unit configuration.

Eight-year randomized clinical evaluation of Class II nanohybrid resin composite restorations bonded with a one-step self-etch or a two-step etch-and-rinse adhesive

DEFF Research Database (Denmark)

van Dijken, Jan WV; Pallesen, Ulla

2015-01-01

(13.5 %) and nine in the two-step etch-and-rinse group (13.0 %). This resulted in nonsignificant different annual failure rates of 1.69 and 1.63 %, respectively. Fracture of restoration was the main reason for failure. Conclusion: Good clinical performance was shown during the 8-year evaluation....... Results: One hundred and fifty-eight restorations were evaluated after 8 years. Three participants with five restorations (three Xeno III, two Excite) were registered as dropouts. Twenty-one failed restorations (13.3 %) were observed during the follow-up. Twelve in the one-step self-etch adhesive group...... and no significant difference in overall clinical performance between the two adhesives. Fracture was the main reason for failure. Clinical relevance: The one-step self-etch adhesive showed a good long-term clinical effectiveness in combination with the nanohybrid resin composite in Class II restorations....

No-Core Shell Model and Reactions

International Nuclear Information System (INIS)

Navratil, P; Ormand, W E; Caurier, E; Bertulani, C

2005-01-01

There has been a significant progress in ab initio approaches to the structure of light nuclei. Starting from realistic two- and three-nucleon interactions the ab initio no-core shell model (NCSM) can predict low-lying levels in p-shell nuclei. It is a challenging task to extend ab initio methods to describe nuclear reactions. In this contribution, we present a brief overview of the NCSM with examples of recent applications as well as the first steps taken toward nuclear reaction applications. In particular, we discuss cross section calculations of p+ 6 Li and 6 He+p scattering as well as a calculation of the astrophysically important 7 Be(p, γ) 8 B S-factor